CA1059890A - Solvent free method of laminating using isocyanate adhesive - Google Patents
Solvent free method of laminating using isocyanate adhesiveInfo
- Publication number
- CA1059890A CA1059890A CA238,897A CA238897A CA1059890A CA 1059890 A CA1059890 A CA 1059890A CA 238897 A CA238897 A CA 238897A CA 1059890 A CA1059890 A CA 1059890A
- Authority
- CA
- Canada
- Prior art keywords
- reaction product
- application
- weight
- foil
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/14—Velocity, e.g. feed speeds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/04—Treatment by energy or chemical effects using liquids, gas or steam
- B32B2310/0445—Treatment by energy or chemical effects using liquids, gas or steam using gas or flames
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2375/00—Polyureas; Polyurethanes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31562—Next to polyamide [nylon, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
- Y10T428/3158—Halide monomer type [polyvinyl chloride, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
- Y10T428/31587—Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31605—Next to free metal
Abstract
SOLVENT FREE METHOD OF LAMINATING
USING ISOTHIOCYANATE ADHESIVE
Abstract of the Disclosure A method for joining foils which includes the steps of mechanically coating at a high speed at least one of the foil sides to be joined with a reaction product of a hydroxy-functional polyethers or polyesters with polyiso-cyanates, said reaction product containing free-NCO groups and being reactable with H-acid compounds, and subsequently laminating foils. The reaction product has an average molecular weight of from about 500-10,000 and a -NCO group content of from about 1-10% by weight, and is substan-tially solvent-free when applied and has a viscosity of at most 60 Pas under application conditions. The temperature of the reaction product application conditions is adjusted to at most 140°C but not less than a temperatare which is so far below the temperature of the ambient air that air humidity will be condensed in the reaction product to be applied in such an amount that its pot-life would drop the value required for the implementation of the method.
USING ISOTHIOCYANATE ADHESIVE
Abstract of the Disclosure A method for joining foils which includes the steps of mechanically coating at a high speed at least one of the foil sides to be joined with a reaction product of a hydroxy-functional polyethers or polyesters with polyiso-cyanates, said reaction product containing free-NCO groups and being reactable with H-acid compounds, and subsequently laminating foils. The reaction product has an average molecular weight of from about 500-10,000 and a -NCO group content of from about 1-10% by weight, and is substan-tially solvent-free when applied and has a viscosity of at most 60 Pas under application conditions. The temperature of the reaction product application conditions is adjusted to at most 140°C but not less than a temperatare which is so far below the temperature of the ambient air that air humidity will be condensed in the reaction product to be applied in such an amount that its pot-life would drop the value required for the implementation of the method.
Description
~L~591~9~ :
; BAC-KG~OU~IU OF THE [NVF.NlI()N
This inveTltion relat2s tc a method for joLning foils by means of mechanical coating at a speed O F preferably more than 50 m/min using an adhesi~e coating mass and subsequent lamination of ~he foils.
It is known that ~'oils, consisting o the ~S~ost varied materials, such as cellulose derivatives, polyolefins, poly-esters, polyamides, metals such as tin or aluminwm, which may also be subject to surface treatment by flaming or dark discharge or which, to improve the physical properties, can be coated with synthetic substances, for ex~nple, polyviny~idenechlo- ~
rîde, can be joined together by means of glue systems in order - -to combine the properties of the various foils into one complex.
It can be the objective of such an effort to achieve special decorative effects or to bring about technical ef~ects, such as . ~ , .
- protectlon for an imprint, production of highly heat resistant ` ~;
.:
complexes, stopping vapor diffusion, heat-sealability;, relia~Ie ~ . . . .
avoidance o porousity, and resistance against agressive . - . .
su~stances. ~;
Particularly appreciated among the adhesive systems employed for such coatings are cross~linked bonding agent systems `
involving a reaction of isocyanate groups ~ith hydroxy-functional - . compounds.
-~ According to t~e state of' the art, this adhesive system as a rule consists o~ the following: -, . .
.. ~ .
; BAC-KG~OU~IU OF THE [NVF.NlI()N
This inveTltion relat2s tc a method for joLning foils by means of mechanical coating at a speed O F preferably more than 50 m/min using an adhesi~e coating mass and subsequent lamination of ~he foils.
It is known that ~'oils, consisting o the ~S~ost varied materials, such as cellulose derivatives, polyolefins, poly-esters, polyamides, metals such as tin or aluminwm, which may also be subject to surface treatment by flaming or dark discharge or which, to improve the physical properties, can be coated with synthetic substances, for ex~nple, polyviny~idenechlo- ~
rîde, can be joined together by means of glue systems in order - -to combine the properties of the various foils into one complex.
It can be the objective of such an effort to achieve special decorative effects or to bring about technical ef~ects, such as . ~ , .
- protectlon for an imprint, production of highly heat resistant ` ~;
.:
complexes, stopping vapor diffusion, heat-sealability;, relia~Ie ~ . . . .
avoidance o porousity, and resistance against agressive . - . .
su~stances. ~;
Particularly appreciated among the adhesive systems employed for such coatings are cross~linked bonding agent systems `
involving a reaction of isocyanate groups ~ith hydroxy-functional - . compounds.
-~ According to t~e state of' the art, this adhesive system as a rule consists o~ the following: -, . .
.. ~ .
-2-~' V'.~s~S.~,~-~r~'i'~,.'~.".,~.S.trq rfr~ S~7i~ ~Js~ J!lr;~ s~ 7~1~
" ' : ' . ., ~s9~o (a) Solutions o hydroxyl-group-containillg polyes~ers, polyether or simultaneously ester-and ether-group containing hydroxy-functional condensation products ~1hich, shortly before being used or coating, are mixed with a solution of pol.yfunctional isocyanates and which then form cross-linkages while forming urethane-or polyurea compounds.
(b) Solutions of free-isocyanate-group-carrying pre-adduct from hydroxy-functional polyesters, polyethers, or mixed polyether-esters, which, ~ollowing the addition of polyol~
or simply due to the action of water from the envlronment (air humidity or adsorbed moisture from boundary surfaces~ cross-linh while forming higher-molecular polymers via urethane-and/or pol~1re~ --~ compounds -:
It is characteristic of such coating adhesive systems, ~.
which are used on a large scale today, that they are applied upon the foils to be joined from a relatively low-visosity, low-solid .; : solution, containing large quantities of solvent. The application ; is mostly via roller application mechanisms and in very small layer thickness at ambient temperature. It is also a character- :
istic that, prior to joining the coated foils in the laminating plant into layered systems having good initial and aging ad- ~
hesion values, the solvents, which account or 60-90% by .
weight of the wet application and which are mostly quite valuable, ~ :
.~.
volatile, combustible and partly physiologically obje~tionable~ ~
~ .
~' are completely removed to the greatest possible extent in e~fective
" ' : ' . ., ~s9~o (a) Solutions o hydroxyl-group-containillg polyes~ers, polyether or simultaneously ester-and ether-group containing hydroxy-functional condensation products ~1hich, shortly before being used or coating, are mixed with a solution of pol.yfunctional isocyanates and which then form cross-linkages while forming urethane-or polyurea compounds.
(b) Solutions of free-isocyanate-group-carrying pre-adduct from hydroxy-functional polyesters, polyethers, or mixed polyether-esters, which, ~ollowing the addition of polyol~
or simply due to the action of water from the envlronment (air humidity or adsorbed moisture from boundary surfaces~ cross-linh while forming higher-molecular polymers via urethane-and/or pol~1re~ --~ compounds -:
It is characteristic of such coating adhesive systems, ~.
which are used on a large scale today, that they are applied upon the foils to be joined from a relatively low-visosity, low-solid .; : solution, containing large quantities of solvent. The application ; is mostly via roller application mechanisms and in very small layer thickness at ambient temperature. It is also a character- :
istic that, prior to joining the coated foils in the laminating plant into layered systems having good initial and aging ad- ~
hesion values, the solvents, which account or 60-90% by .
weight of the wet application and which are mostly quite valuable, ~ :
.~.
volatile, combustible and partly physiologically obje~tionable~ ~
~ .
~' are completely removed to the greatest possible extent in e~fective
-3- :
:
10~9~9~ ~
drying stages and are disposed of without harrning the environment.
Here are some particular disadvantages deriving from the laminating adhesive systems (a) and (b) used in the production ;~ 5 of high grade foil coatings based on the state of the art~
~` 1. To generate sufficient initial adhesion, higher-molecular bonding agent systems are re~uired which can be applied only from solutions of relatively low concentration at room ~ -temperature and in a sufficiently thin, well-wetting ancl unifonn manner.
2. The solver~ts (ketones, esters, aromatic substances) are mostly very expensive and are of~en physiologically objectiona~le; ;~
considering the presently customary very high coating speeds, it is very difficult to remove them, that is to say, this can be done only with a tremendous energy expenditure, with plants ;~
-~ ~ having long evaporation assembly lines, large suctioning systems and room ventilation systems, exhaust air combustion (cataly~Lc or thenmal), large quantities of fresh air, and therefore high energy ;``~ ;
costs.
,, 3, The solvent-containing adhesive systems are undesira~le in terms of storage and transportation because o~ the level of hazard involved.
,: .
:
10~9~9~ ~
drying stages and are disposed of without harrning the environment.
Here are some particular disadvantages deriving from the laminating adhesive systems (a) and (b) used in the production ;~ 5 of high grade foil coatings based on the state of the art~
~` 1. To generate sufficient initial adhesion, higher-molecular bonding agent systems are re~uired which can be applied only from solutions of relatively low concentration at room ~ -temperature and in a sufficiently thin, well-wetting ancl unifonn manner.
2. The solver~ts (ketones, esters, aromatic substances) are mostly very expensive and are of~en physiologically objectiona~le; ;~
considering the presently customary very high coating speeds, it is very difficult to remove them, that is to say, this can be done only with a tremendous energy expenditure, with plants ;~
-~ ~ having long evaporation assembly lines, large suctioning systems and room ventilation systems, exhaust air combustion (cataly~Lc or thenmal), large quantities of fresh air, and therefore high energy ;``~ ;
costs.
,, 3, The solvent-containing adhesive systems are undesira~le in terms of storage and transportation because o~ the level of hazard involved.
,: .
4. The transportation and packaging volumes are dis-proportionately high compared to the thin layers of adhesive in the laminates to be produced.
.. . .
: -. ' . ~, . ' .
.. . .
: -. ' . ~, . ' .
5~ The residual solvents in the film, which are difficult `~ to remove, for example, in the case of packaging complexes, endanger the materlals to be packaged because they exert influence ln the form of taste and odor.
6. In the case of NC0-group-containing adhesive systems~
the solvents are particularly expensive because they must be completely free of water prior to use.
the solvents are particularly expensive because they must be completely free of water prior to use.
7. Two component systems are particularly hard to handle in the plant and entail the danger of mistakes during the combination of components in the plant.
8. The low-visosity isocyanate component solution entails dangers in handling, especially for inexperienced personnel~ such as this would be unavoidable during transportation.
The effort to avoid these dlsadvantages -~ by trying to develop cross-linking two-component larnination adhesive which would contain as little solvent as possible, and which involve ~;
reaction of isocyanate groups with alcholic hydroxyl groups and possibly water -- has so far failed because it was considered necessary, in order to achieve good adheslon (especially good initial adhesion)~ that the laminating adhesive bonding agents~
contained in the solution~ must possess a high "average ~olar ~eight" and high viscosity (i.e., firm consistency). These properties however rule out any application in a form devoid of solvents.
~5-,. . .
, It is further1nore Icnown tha~ one can apply thermoplastic synthetics in solvent-~ree ~orm, so-called hotmelts, that iY to say, waxes or copolymers from the melt~ upon the ~oils and that one can use them to laminate oils. Such composite structures in particular entail the disadvantage ~hat the coatings ;~ 5 must be applied in a comparatively great thickness, that the coatings are not transparent, and that the composite systems have ~; no heat resis~ance because of the thermoplastic nature of the coating. Moreover, these hotmelts are sensitive to aggressive -~
filler materials.
It is known that one can avoid the disadvantages o~ ther1no~
plastic hotmelts by means of solvent-free adhesiv ~ ~l9 consisting of several components (U.S. Patent No. 3~ 4 ~
The desired small application quantities o 0,5-5mu an~ achieved~ -through pre-dosing, by dosing elements known ~ se and by further stretching the medium to be applied by at least l:]0 by means of differing roller speeds in the application eleMents or through di~ferent speeds of the application roller and the~-~
~ substrate to be coated. A further compelling prerequi.slte in ~1~is ~ ~
', ~: ' , method is that the obviously very fast setting adhesive must always be transferred completely from one roller to the next one, ; respectively, from the application roller to the film to be coated, in order to avoid premature hardening on the rollers. -For this purpose, the adhesive is charged into the dosing device by means of a special feeder device and only in that quantity in which it is finally trans~erred to the film to be coated.
' "~,' : :' : , , 89~
SUMMARY OF THE INVENTION
_ _ _ ___ It is an object of the present invention, at least in its preferred forms, to provide a method for joining foils by means of coating with a laminating adhesive mixture and subsequent coating, where the use of solvents is at least extensively avoided, but where nevertheless a uniform application in extremely thin layers is possible at high-speed mechanical coating and where, i~mediately after coating, the foils are so firmly joined together, 10 that is to say, the shear strength is so great, that the laminated foil strips will not shift with respect to each ~ -other or become separated from each other or form bubbles -or folds during processing. Moreover, the foils must not "telescope" during rapid windup.
It is also an object of the invention, at least in its preferred forms, to provide an adhesive system which ~-is easy to handle and which does not require the mixing of several components and this system should be used to join foil complexes of the kind described, a system which, 20 through chemical cross-linking, creates heat-stable com-posite structures (for example, boil-proof, sterilizable, heat-sealable) compound structures, without revealing the ; ~ ;~
above-described disadvantages encountered in the usual coating adhesives. Furthermore, the adhesive should be capable of being processed according to the invention ~;
on customary coating or laminating machines without necessitating any expensive mixing-, feeder-, or dosing-subassemblies which are vulnerable in use. Apart from the possibility of varying the circumferential speeds of the individual rollers to a minor extent, no additional expen-sive regulator or drive mechanisms should be needed.
~135~39~ ~
According to the invention there is provided in a method for joining foils including the steps of mechan-ically coating at a high speed at least one of the foil sides to be joined with a reaction product of a hydroxy- .
functional polyethers or polyesters with polyisocyanates, said reaction product containing free-NCO groups and ~-:
being reactable with H-acid compounds, and s~bsequently laminating t'ne foils, the improvement which comprises said reaction product having an average molecular weight 10 of from about 500-10,000 and a -NCO group content of ; from about 1-10% by weight, said reaction product being ~ .
substantially solvent-free when applied and having a viscosity of at most 60 Pas under application conditions, and adjusting the temperature of the reaction product -application conditions to at most 140C but not less than a temperature which is so far below the temperature of the l ambient air that such an amount of air humidity will be ', condensed in the reaction product to be applied that its pot-life would drop the value required for the implemen-20 tation-of the method.
. . , One orm of the invention provides a method for ~, joining foils by the steps of: mechanical coating at a speed of preferably more than 50 m/min of one or both ;:: of the foil sides to be joined together with reaction --, products which are derived from hydroxyI-functional polyethers and/or polyesters and which contain free-NCO
groups, and possibly of polyamides~ amino-alcohols, or polyols with polyisocyanates, which reaction products can react with H-acid compounds, optionally in admixture with 30 auxiliary substances and/or additives used for technical ~ purposes in glueing; and subsequent laminating of the :~, ~ 8 -g~90 foils. The process is characterized by the fact that the mixing products possess an average molecular weight of between about 500-10,000 and a content of -NCO groups of from about 1-10% by weight, the fact that no solvents are added to the mass to be applied, the fact that the mass to be applied has a viscosity of at most 60 Pas under appli-cation conditions and that the temperature of the appli-, ~ , cation mass is at most 140C and also that its temperatureon the surface layer, which is cooled very considerably 10 because of the poor heat conductivity of the mass, is not so far below the temperature of the ambient air that suf-ficient quantities of air humidity will be condensed in the application mass located in the tank of the applica-tion machine so that the pot-life of the application mass in the tank will drop below the value required for imple-. .
mentation of the method.
The coating speed employed in the course of the methodaccording to the invention should be as fast as possible so that the method may be as economical as possible. For ~` 20 coating and laminating customary machines are used which have a heatable application mechanism. The coating speed is preferably more than 50 and particularly preferably in the range of about 100-300 m/min. Basically however one can also use faster speeds if the machines are designed accordingly. An extraordinarily thin coating application of, for example, about 0.1-10 g/m2, preferably about 0.5-5 g/m2, is sufficient.
The essential component of the application mass is a reaction product, containing free-NCO groups, said 30 reaction product being derived from hydroxyl-functional polyethers and/or polyesters and optionally from polyols ~9~
with polyisocyanates. Polyethers, which are used to make these reaction products, are preferably aliphatic, straight or branched-chain products which preferably possess a molecular weight of from about 300-4,000, ~ -particularly preferably from about 400-2,000. Such pro~
ducts are sold by various firms under trade names (for example, the Desmophene-U types [Trade Mark] of Bayer AG, Leverkusen, Pluracol-types [Trade Mark] of the Wyandotte Company, Niax-types [Trade Mark] of Union Carbide, U.S.A., 10 polyglycols of Farbwerke Hoechst, Germany).
Suitable linear or branched polyesters are, for ~ -example, made of aliphatic and/or aromatic polycarboxylic acids and polyols, whereby the molecular weight preferably is within the same ranges as those that were mentioned for the polyethers. These products likewise are offered by many companies in the trade (for example, Desmophen-types o~ Bayer AG, Leverkusen). One can also use those products which have both polyester and polyether bonds in the same molecule. Frequently the above-mentioned products are not 20 uniform compounds but rather mixtures of substances. This is well understood by those skilled in the art.
In addition to the polyethers and/or polyesters there ; can be used for the production of reaction products other such compounds which contain at least two groups which can react with -NCO- groups, whereby their share, related ; to the total weight of the reaction products, as a rule should not be more than about 30~ by weight, preferably no more than about 20~ by weight. Such suitable com-pounds include, among others, amines, aminoalcohols, 30 and especially polyols, for example, aliphatic compounds having 1 to 8 carbon atoms which preferably contain 2 to :, .
`''' ~L~5'9~
4 hydroxyl groups i~ the molecule, such as glycol, neo-pentyl-glycol, and glycerin.
The polyisocyanates which are used to make the above mentioned reaction products are aliphatic and/or aromatic and/or cycloaliphatic compounds with preferably 2 or 3 -NCO- groups in the molecule. These products are com-mercially available, for example, under the trade name of Desmodur [Trade Mark] by Bayer AG, Leverkusen. The molecular weight of the polyisocyanates which are used for 10 making the reaction products is pre~erably in the range of from about 100-1,500 and especially preferably between about 150-500.
-~ As said above, the reaction products have an average :. ~
molecular weight of from about 500-10,000 and a content of -NCO- groups of from about 1-10% by weight. The molecular weight is preferably in the range of about 1,000-6,000, particularly preferably in the range of about 1,000-4,500.
.~, ..................................................................... . .
The content of -NCO- groups is preferably in the range of about 2-8% by weight, particularly preferably in the range 20 of abou~ 3-6% by weight. By percent by weight, in the sense of this definition, is meant the share of the weight -.:
~- of the -NCO- groups out of the total amount of reaction products.
The application mass should have a maximum viscosity , :;, .
of 60 Pas under application conditions. The viscosity .
is preferably under about 20 Pas, particularly preferably under about 10 Pas. By viscosity under application con-ditions is meant that viscosity which the application mass exhibits in the tank of the application machine.
The processing temperature is selected so that the viscosity of the mass, when the application mechanism is correspondingly ., ' .
.' ' ' ' " ~
.' , . . ' " .
', t G
~' ~L~5~39~
~.
'i .
adjusted, permits ~he desired application volume, while avoiding that the foil, which is to be coated, is damaged by the temperature applied or is unfavorably influenced in terms of its quality and gauge. The temperature of the coating mass therefore should not be above 140C, preferably not above 120C, par~icularly pre-ferably not above 100C. By temperature, in this sense, is meant once again the temperature of the application mass in the tank of the application machine.
"~ Another essential requirement in the method according to the invention is that the temperature of the coating mass must ~~ 10 not be so far below the temperature of the ambient air that enough air humidity will be condensed into the coating mass ~ -:
located in the tank of the applieatiorl machine so that the ?
pot-life of the coating mass in the tank will drop below the ~`
value required for implementation of the method. When the temperature of the coating mass is too low, the moisture from the ambien~ air can be condensed on the surface of the coating mass because of the temperature drop and~ since the coating mass -as a rule is agitated in the tank of the application machine, more and more moisture is introduced into the coating mass.
The moisture brings about an incipient cross-linking of the reaction products contained in the coating mass~ as a result of ~;
which the pot-life of the coating mass is considera61y shortenedO
... .
The consequence is that the cross-linking becomes 50 strong as : .
~ time passes that the coating method can no longer be carried out.
" , ~ 25 :~,- ,, . ` '.
'~'''' ~ . :
: ,. ' ~. ` . . :
89~
If, on the other hand~ according to the method in th1s invention, the temperature of the coating mass is kept high - enough, then condensation of air h~midity is avoided and it is extraordinarily surprising thatg when this requirement is met~ the pot-life of the coating mass is not influenced and remains constantly high. By means of simple experiments, the artisan can determine the suitable average temperature by considering the particular existing air humidity and the ~;
tempera~ure of the surrourlding air~ that is to say~ the - ;
environmental temperature. As a rule~ it is enough when the temperature of the coating mass does not fail below the temperature of the ambient air or, at best, if it is a few degrees Centigrade below in order to prevent the pot-life from being disadvantageously influenced in the sense described above.
As explained above, no added solvents should be contained ~n the application mass according to th~ invention. The ., :
above-described disad~antages of ~sing solvents are thus ~
. , .
completely avoided because, when the above-defined parameters are maintained~ quite surprisingly a perfect application and a high initial shear strength are achieved~
By way of auxiliary substances and/or additi~es which are helpful in terms of glueing technique~ the application mi~ture according to the invention may contain, for example, reaction accelerators such as tertiary amines, metal-organic compounds, ' .
'~
~ 598~
such as dibu~yl-tin-dilaurate, lubricants, dyes, pigments, or filler materials, thermoplastic resins or plasticiæers.
he reaction products used according to the invention should have a reactivity of about 5 hours maximum. The reactivity preferably is l hour, maximum, and particularly preferably about 30 minutes. Fundamentally, the reactivity can and should be even higher than indicated above so that the reaction will take place as fast as possible after application upon the foil and this is why reactivity lO values about 15 minutes or even 10 minutes maximum are particularly practical. The reactivity is determined as follows:
S00 g of the glue used are placed in a tin with a diameter of lO0 mm which is sealed against the entry of - air and moisture and they are stirred at about 60C at a ` speed of about 300 rpm. The stirrer has four blades with an outside arc of 45 mm diameter. The end of the stirrer ; lS l cm away from the bottom of the tin. Then we add, to the glue in the tin, l Mol water per equivalent of the ; ;
free -NCO- groups contained therein, and we measure the time until the start of gelatinization, which can be recognized by the fact that the mass rises along the - ~-stirring shaft. The reactivity of the resin increases in proportion to the decrease in time until the start of this effect. (The entry of moisture is prevented by covering with aluminum foil through which the stirring shaft runs.) But if, in the same manner, this proce-dure is carried out without the addition of water, there will, after 13 hours of stirring, be only a ~ 30 -~
:' ' ' :' : "' '' ~ .
. .
.
.. . .
~ 5~
viscosity increase of, for example, from about 0.77 Pas to 1,38 Pas. It has so far not been considered possible to take g]ues with such a high reactivity toward water - that is to say, toward air humidity -~ in a solvent-free state over a period of even only 1 hour, not to mention longer periods of time of about 5 hours or more, and expose them to air humidlty in a standard application machine and thus process them, without getting gelatinization. On the other hand, after application ; :.
upon the foil to be coated, the hardening process begins so fast that the method according to the invention can be carried out -; 10 in a trouble-free and simple manner.
By pot-life; within the meaning of the invention here, there ~s meant the time for which the application mass remains viscosity-stable in the tank of the application machine, under conditions prevailing there, to such an extent that perfect pro-. ;; .
cessing will be assured. For trouble-free processing on hitherto customary machines, which have an open, tempered storage container ~;~ for the application mass, a pot-life of at least 5 hours is required which facilitiates trouble-free processing during one 8-hour shift.
When the above-defined measures are complied with, safe ., ~ .
implementation of coating during an 8-hour day or during continual shift operation is facilitated, and the foils are so firmly joined immediately after coating that, even at high machine speeds, ;~
there will be no bubble or crease formation as a result of the ~ ':
- foils being shifted with respect to each other, or there will be ~ ~ .
;~ -15-. .
~' .~, .
~ 9 ~
no shifting of the foil during windup, which is called "telescoping".
One unanticipated advantage of the method according to the invention is that, in spite of solvent-free application, a perfect, unlform coating, even in quantities of about 0.5 g/m2 is possible. It is likewise surprising that even at such small ~; application volumes, completely bubble-free laminates are ~`~ obtained which are highly transparent in the ease of clear films5 -and this is true both in the ease of laminating with hot (50-100C) and eold(20C) laminating rollers. Thus the transparency disturbanees, which appear, for example, at high processing speeds also in the case of the known adhesive systems, vanish eompletely within a short time In comparison to known methods, it is therefore possible to aehieve identical transpareney with smaller applieation quantities, and better transpareney with the same applieation quantity. The possibility of attaining, through solvent-free applieation of the adhesive, sueh small applieation quantities and sueh high transpareney in transparent foil eomplexes is particularly surprising if we realize that the quantity applied must bridge all uneven spots in the foils to be joined (peak-to-valley height, undulations, ete.) so that one can ereate a eomposite strueture without interstiees.
~ .
A eomplete as possible filling of all uneven spots was aehieved, according to the state of the art, by applying a diluted solùtion in a relatively large quantity in order, after the ~5~890 ~, ; evaporation of all solvents, to leave the desired thin film behind. The smaller the desired adhesive application, the more diluted was the solution used in order to attain a still sufficiently high and unifo~n wet application.
The method according ~o the invention can be carried out S on the most varied types of machinery, for example, pressure~
laminating, and hotmelt machines,whereby the only prerequisite is a heatable application mechanism which is suitable for thin application at the required machine operating speed. The adhesive application can be accomplished with smooth or patterned rollers~ either coaxially or counter-currently, ar also with suita~le wipers. Differing circumferential speeds of the application rollers, and/or relative speeds of the rollers of the application mechanism with respect to each other~ and/or ~ between the application roller and the foil web to be coated, may ?
be advantageous ~or the purpose of achieving optîmum applications but are not absolutely required. This is known to the artisan as part of the state of the art. To get the best and most uniform application possible, the lamination may be accomplished ., . . ~ .~
immediately after the application mechanism. It is not necessary to connect evaporation zones, IR or hot-air drying or heating ducts or additional devices between the steps, even at high machine operating speeds (~or example, in excess of lO0 m/sec).
~ ~ 5~ ~9 ~
One parL--icular Eeature oE the method according to the invention is that, in spite of the viscosity which is low at the applica~ion temperature, a suf~icient bondirlg o~ the ~oils is achieved in~ediately after they leave the laminating mechanism. This is the only way in which shifting of the foils toward each other can be prevented and this is the only way ln which fold formation, bubble formation~ telescoping, etc., can be avoided, and in this way the composite foil can be wound up perfectly into a roll~
~or this property it is important that the adhesive give the foil complex, in the desired application quantity, a high shear strength (for example, more than 200 g/cm2). Shear strength is measured as follows:
; A glued sample piece is traction-stressed wIIereby the orce attacks, on one side, along the upper individual foil and, on the other side, along the lower indlvidual foil, so that we get horizontal shearing. The force measured is divided by the sur~ace and gives us the system-specific "shear strengt1n" in g/cm2, at identical application quantities.
The essence of the invention furthermore includes that the laminates, made according to the invention, become bound as fast as those which have been made according to tlle hitherto known methods. That is to say3 they achieve the desired strength in the composite structures and resistance against mechanical, chemical (Erom aggressive filler materials) and thermal (boiling ~S989~
sterilization, heat-sealing) stress through chemical cross-linkin~. In practi.ce this means that the desired high adhesion values must be achieved after a few hours up to a few days ~;
and that the ability to be boilcd and sterilized must be achieved after 6-12 days.
Although the above requirement is met, it was unexpec~edly discovered thatg when the parameters of the method arcording : to the invention are co~plied with, the coating mass remains stable, that is to say, an adequate pot-life was preserved.
Thus it was found, for example5 that, wikh a temperature treatment at 90C lasting several days, the coating mass did reveal a rise in viscosity which however was so small that the processability of the aged material was not disadvantageously . :~:
.influenced. Even samples whic.h had been expos~d to the effect of air humidity in the open tank of a coat:ing machine for more than .`~
8 hours at 90C with constant thorough mixing by the application rollers, could once again be processed in the machine after an in~ermediate storage of 8 days in a closed container without loss of any of their properties.
This fact is all the more surprising since we know from the handling o~ solvent-containing isocyanate products that the pot-life, according to past experience, grows longer as the solution is more diluted and that one would have to expect a particularly poor`stability for solvent-free products. A~cordingly it is required in U.S. Patent No. 3,840,419 that the adhesive~ :
`:
~598~
during the transition frvm one dosing roller to another one, and/or, from tle dosing roller to the film to be coated, in ~ach case must be transferred practical1y completely so that there cannot be any hardening on a roller. According to Bri.tish Patent Mo. 1,158,740, premature gelatiniza~ion, or hardening of the material must ~e prevented by mixing the rem- ;
nants of the adhesive by the defined shearing forces, îmmediately with fresh material. In the cas~ of solvent-containing adhesives according to the ~tate of the art, it is frequently recon~ended J
I for ex~ple, that adhesive mixtures~ which are not used up at I the end of a working day, ~e d~l~ted ve.ry heavily in order to thuæ prevent overnight gelation.
This surprising and favorable effect of the method accorf.ling ;~
to the invention can perhaps be explained by saying that, ~uri~g the application of solvent-containing adhesives, there is lS always an evaporation of the solvents, especially on the rol lers.
The cooling of the surfdce, brought about by evaporative cooling ;~
promotes the absorption of moisture from the air especially when the dew point has been reached. In a solvent-containing adhesive, which has remained for 3 hours in the machine while the application mechanism was kept running, it is already possible to establish a water content of 1-1.5% depending upon the prevailing air humidity, while a solvent-free product did not absorb any noticeable quantities of water. The performance o~
the solvent-free adhesive, which is more favorable because there is no evaporative cooling, is further supported by heating because ~0-~ L~59~
the temperature difference to the dew point of the air is t~en even greater.
With this good stability of the application mass in the coating machine it furthermore could not be expected that the reactivity and hardening speed of the adhesive, after application on the foil surface, would be so great that the above-described requiements existing in practice would be met. Instead, it would be especially the very long pot-life during heating under the influence of air 10 humidity which would have led to the expectation that there would be no useful hardenin~ at all or that the time intervals would be too long 50 that they could not be useable in practice. Moreover, it was to be expected that the viscosity, which was kept relatively low for solvent-free application, would considerably increase the time until the complete hardening of the foil complexes due to the requirement for a large number of cross-linking steps, compared to the highly viscous materials, in order to achieve the desired duroplastic state.
The reaction products, contained in the adhesive mixture, also contain free -NCO- groups which can react with H-acid compounds. The artisan is familiar with this reaction capability. As H-acid compounds we can use all ~ ~-compounds which are present on the surface of the foils ``
to be joined, partly due to adsorption, or which are ~;
contained in the surface. Water is particularly important ;
as H-acid compound in the implementation of the method :.. . .:
according to the invention; water is present in the form of air humidity and, practically also on all surfaces, .
~ 8~ ~
as a thin adsorbed layer in quantities sufficient for the cross-linking of the adhesives used according to the invention. For cross-linking and to achieve good adherence, unctional groups in the foil surface, such as hydroxyl-, hydroperoxide - 3 and carboxyl groups can also be involved.
The terms "solvent-free" and "solvent-free application" mean that no solvents or other low-mvlecular substances need be added to the application mass to lower the viscosity. These substances are volatile at processing temperature and ~hus have a "transport - function." Due to the molecular weight distribution o~ polymer substances and due to the absorption of gases, moisture9 and other substances from its environment, every substance used in practice contains a cured mass which is just a ~ittle bit below the theoretically anticipated 100%.
According to the method in this illvention, one can join `~
together any of the foils which were mentioned in the introduction to the specification and any which are also bonded together according to the state of the art with the use of laminating adhesives which are cr~ss-linked via isocyanate groups.
The invention is further explained on the basis of the ~
attached drawings. Identical parts have been provided with the ~ -same reference numbers in the figures.
BRIEF DESCRIPTION OF THE APPLIC~TION DRAWINGS
Figure 1 is a diagrammatic view of a laminating machine modified in accordance with the present invention. `~
Figure 2 is a simplified form of mach;ne for implementing -~2-the method according to ~he present invention, and Figure 3 is 2 coating and laminating unit preferably used for working with "hot-melt" coating and laminating masses.
DETAILED DESCRIPTION OF T~E PRE_ERRED EMBODIMEN_ Figure 1 is a diagram showing a customary laminating machine for solvent-containing adhesives which however can -;~
be used according to the method in this in~ention whereby the drying duct is not used. The roller, which unreels one of the -oils to be joined, is numbered l. In tank 4 is the laminating adhesive, that is to say~ the coating mass according to the invention. This mass is applied via the dipping roller 5 and the application roller 6, onto one side of the foil strip running off roller 1, whereby pressing roller 7 forces the foil against `
application roller 6. The air nozzles 9 which are present in the machine in drying duct 8 are not used according to the .
method in this invention; instead, they are used only for the subsequentLy described comparative example, using the method according to the state of the art. For this purpose, air is piped through the drying duct via air inlet 10 and air outlet 11. The second foil, which is to be joined together with the-first foil, is unwound from roller 2 and is guided via deflection rollers 3 to the pressing mechanism 7 where the two foils are ..
pressed against each other by means of rollers. The composite foil structure, the foils laminated together, is wound up on roller 12.
''' ' .
': ~ ' ' ' ' ~59189~ ` :
Figure 2 is a diagram showing a simply designed machine for implementing the method according to the invention, not containing ~he drying duct because the latter is not requ~red for the method according to the invention. Such machines are used in the so-called hot-melt method. The foils to be jolned together are once again unreeled from rollers ~ and 2.
One of the foils is once again coated, after it has been guided ~ia deflection rollers 3 between application roller 6 and press-on roller 7. Application roller 6 brings the application mass from the tank on one side of the foil strip. Between the press-on rollers 7 and 13, the two foils are joined together and are wound up on roller 12.
Fi.gure 3 shows a coating and laminating unit, as is used ~-~
preferably for working with "hot-melt" coating and laminating , masses. ~
. . ;
The application medium is in tank 10. The non-rotating steel roller ~9~which can be heated,presses against the rubber roller 5, whereby the level of the pressure determines the quantity of adhesive which gets through the gap when roller 5 rotates.
.
This adhesive which is on the surface of roller 5, is taken off by roller 6 (steel roller, likewise heatable) which runs at higher speed in contact with roller 5 and it is applied upon the ; foil strip which is pressed on by rubber roller ~. It is a good idea here to keep the circumferential speed of rollers 6 and 7 -~
identical.
` -2~-;
~ .. '. 7 , ' ~ ~
. ' 5~
From the unreeling roll 2, the incoming strip is ~ed via the deflec~ion roller 3 to the coating mechanism in such a . . ~ .
manner that the film, coated with adhesive,can be joined with the incoming strip between rollers 7 and 8 without any bubble formation. Then comes the windup in winding station 9. The ` 5 glue becomes thoroughly hard in the rolls wit=hin a few days.
Production of B_nding A~ents Suitable For Method According to -~
The Invention Bonding Agent A~
To 250 parts by weight of polypropylene-etherglycol, with ;
an average molecular weight of about 2,000, is added, in a ~
reaction vessel, 62.5 parts by weight diphenylmethanediisocyanate ;-(MDJ)? whîle stirring, and the mixture is heated to 90C until -`
a viscosity of 1.5 Pas is attained, measured at 80C in a platecone yiscosity meter. The -NC0 content of the reaction - ;
- ~ .. ~ . ,, ~15 product is 3.5% by weight. This value is achieved after a reaction time of about 6 hours The solid, measured as cured residue after 1 hour at 150C, is 99% by weight. The reaction `
,. , ~
speed, calculated as above, is about 8 minutes.
,,~ , Bonding Agent B~
From 1,500 g polyglycol with a molecular weight of 1500, `;
348 g toluylenediisocyanate (TDI), a bonding agent is made, in the manner described above~ the NC0-content of which is 4.28%
by weight. The viscosity measured at 100C is 0.41 Pas. The `~
,, ~ " .
reaction speed is about 6 minutes.
: ' ~25-' : .' 59~
"
Bonding Agell~ C:
350 g of a polyester from ad:ipic acid and ethyleneglycol ; with a hydroxyl content of about 1.8% by weight~ 84.~ g MDI and 4.7 g TDI are mixed as described above up to a viscosit~ of 4.5 Pas, measured at 100C. NC0-content 2.39V/~ by weight.
Reaction speed: about 6 minutes.
~; Bonding ~gent D:
: . , 2,000 g polypropyleneglycol with a molecular weight of about 2000, 425 g MDI and 76.3 of a reaction product o 3 Mol hexamethylenediisocyanate and 1 Mol water are mixed as described above up to a viscosity of 1.7 Pas, measured at 100C. NC0~
~`l content: 4.95% by weight. Reaction speed: about 10.2 minutes.
~xample l ~-The bonding agent described above is filled into the ; heated storage tank 4 of the laminating machine of conventional design, illustrated in Figure 1, and it is heated to 12.0~C. ht ., the same time the application roller 6 is preheated to 100 C.
- After the given temperatures are obtained, a 12.5~mu thick polyester foil is coated with the application mixture whereby - the application roller is driven in the same direction. The foil thus coated is then guided through the drying duct 8 although ,t the latter ls not heated and is not charged with fresh air ; ~ecause this is not required in the method according to the invention. After the drying duct -- between a stationary-attached roller and press roller 7 -- a polyethylene foil ` -26-,~ with a thickness of 50 mu,which on tl~e side to be glued had earlier been subjected to a Corona treatment, is app'lied. --The temperature of the press-on roller is 40C. Ater rolling- -~
up, further hardening takes place during storage. The value given suhsequently for the composite adhesion and the sol~en~
residue are measurPd after 5 days. ' Table 1 , application weight 1.2/m ` ; movement speed 100 m/min ~' ~` composite adherence 400 g/20 mm solvent residue 0 mg/m2 , The composite adherence is measured as follows: a 20 millimeter wide strip of the foil composite made is clamped into '~
a tearing machine at the peeling angle of 2 x 90, then the joined ;~' '~ ~oil strips are separated at a feeding speed of 50 mm/min and the i 15 force required for separation is measured; this force is measured ; in g/20 mm. '-, The solvent residue is-determined as follows: from the ^`, middle position of the wound-up coated composite foil a sample '- -~
~ piece is taken and heated in a gas-proof tank for 1 hour up to ";~,20 a maximun of 120C so that no cracking'products of the laminated ~;~
', oil will develop, We take a sample from the gas ch~n'~er of the ,~ container and we examine it gaschromatographically.
, ," Comparative Example 1 ',~
',~ On the same coating nachLne, used according to Example 1, `
The effort to avoid these dlsadvantages -~ by trying to develop cross-linking two-component larnination adhesive which would contain as little solvent as possible, and which involve ~;
reaction of isocyanate groups with alcholic hydroxyl groups and possibly water -- has so far failed because it was considered necessary, in order to achieve good adheslon (especially good initial adhesion)~ that the laminating adhesive bonding agents~
contained in the solution~ must possess a high "average ~olar ~eight" and high viscosity (i.e., firm consistency). These properties however rule out any application in a form devoid of solvents.
~5-,. . .
, It is further1nore Icnown tha~ one can apply thermoplastic synthetics in solvent-~ree ~orm, so-called hotmelts, that iY to say, waxes or copolymers from the melt~ upon the ~oils and that one can use them to laminate oils. Such composite structures in particular entail the disadvantage ~hat the coatings ;~ 5 must be applied in a comparatively great thickness, that the coatings are not transparent, and that the composite systems have ~; no heat resis~ance because of the thermoplastic nature of the coating. Moreover, these hotmelts are sensitive to aggressive -~
filler materials.
It is known that one can avoid the disadvantages o~ ther1no~
plastic hotmelts by means of solvent-free adhesiv ~ ~l9 consisting of several components (U.S. Patent No. 3~ 4 ~
The desired small application quantities o 0,5-5mu an~ achieved~ -through pre-dosing, by dosing elements known ~ se and by further stretching the medium to be applied by at least l:]0 by means of differing roller speeds in the application eleMents or through di~ferent speeds of the application roller and the~-~
~ substrate to be coated. A further compelling prerequi.slte in ~1~is ~ ~
', ~: ' , method is that the obviously very fast setting adhesive must always be transferred completely from one roller to the next one, ; respectively, from the application roller to the film to be coated, in order to avoid premature hardening on the rollers. -For this purpose, the adhesive is charged into the dosing device by means of a special feeder device and only in that quantity in which it is finally trans~erred to the film to be coated.
' "~,' : :' : , , 89~
SUMMARY OF THE INVENTION
_ _ _ ___ It is an object of the present invention, at least in its preferred forms, to provide a method for joining foils by means of coating with a laminating adhesive mixture and subsequent coating, where the use of solvents is at least extensively avoided, but where nevertheless a uniform application in extremely thin layers is possible at high-speed mechanical coating and where, i~mediately after coating, the foils are so firmly joined together, 10 that is to say, the shear strength is so great, that the laminated foil strips will not shift with respect to each ~ -other or become separated from each other or form bubbles -or folds during processing. Moreover, the foils must not "telescope" during rapid windup.
It is also an object of the invention, at least in its preferred forms, to provide an adhesive system which ~-is easy to handle and which does not require the mixing of several components and this system should be used to join foil complexes of the kind described, a system which, 20 through chemical cross-linking, creates heat-stable com-posite structures (for example, boil-proof, sterilizable, heat-sealable) compound structures, without revealing the ; ~ ;~
above-described disadvantages encountered in the usual coating adhesives. Furthermore, the adhesive should be capable of being processed according to the invention ~;
on customary coating or laminating machines without necessitating any expensive mixing-, feeder-, or dosing-subassemblies which are vulnerable in use. Apart from the possibility of varying the circumferential speeds of the individual rollers to a minor extent, no additional expen-sive regulator or drive mechanisms should be needed.
~135~39~ ~
According to the invention there is provided in a method for joining foils including the steps of mechan-ically coating at a high speed at least one of the foil sides to be joined with a reaction product of a hydroxy- .
functional polyethers or polyesters with polyisocyanates, said reaction product containing free-NCO groups and ~-:
being reactable with H-acid compounds, and s~bsequently laminating t'ne foils, the improvement which comprises said reaction product having an average molecular weight 10 of from about 500-10,000 and a -NCO group content of ; from about 1-10% by weight, said reaction product being ~ .
substantially solvent-free when applied and having a viscosity of at most 60 Pas under application conditions, and adjusting the temperature of the reaction product -application conditions to at most 140C but not less than a temperature which is so far below the temperature of the l ambient air that such an amount of air humidity will be ', condensed in the reaction product to be applied that its pot-life would drop the value required for the implemen-20 tation-of the method.
. . , One orm of the invention provides a method for ~, joining foils by the steps of: mechanical coating at a speed of preferably more than 50 m/min of one or both ;:: of the foil sides to be joined together with reaction --, products which are derived from hydroxyI-functional polyethers and/or polyesters and which contain free-NCO
groups, and possibly of polyamides~ amino-alcohols, or polyols with polyisocyanates, which reaction products can react with H-acid compounds, optionally in admixture with 30 auxiliary substances and/or additives used for technical ~ purposes in glueing; and subsequent laminating of the :~, ~ 8 -g~90 foils. The process is characterized by the fact that the mixing products possess an average molecular weight of between about 500-10,000 and a content of -NCO groups of from about 1-10% by weight, the fact that no solvents are added to the mass to be applied, the fact that the mass to be applied has a viscosity of at most 60 Pas under appli-cation conditions and that the temperature of the appli-, ~ , cation mass is at most 140C and also that its temperatureon the surface layer, which is cooled very considerably 10 because of the poor heat conductivity of the mass, is not so far below the temperature of the ambient air that suf-ficient quantities of air humidity will be condensed in the application mass located in the tank of the applica-tion machine so that the pot-life of the application mass in the tank will drop below the value required for imple-. .
mentation of the method.
The coating speed employed in the course of the methodaccording to the invention should be as fast as possible so that the method may be as economical as possible. For ~` 20 coating and laminating customary machines are used which have a heatable application mechanism. The coating speed is preferably more than 50 and particularly preferably in the range of about 100-300 m/min. Basically however one can also use faster speeds if the machines are designed accordingly. An extraordinarily thin coating application of, for example, about 0.1-10 g/m2, preferably about 0.5-5 g/m2, is sufficient.
The essential component of the application mass is a reaction product, containing free-NCO groups, said 30 reaction product being derived from hydroxyl-functional polyethers and/or polyesters and optionally from polyols ~9~
with polyisocyanates. Polyethers, which are used to make these reaction products, are preferably aliphatic, straight or branched-chain products which preferably possess a molecular weight of from about 300-4,000, ~ -particularly preferably from about 400-2,000. Such pro~
ducts are sold by various firms under trade names (for example, the Desmophene-U types [Trade Mark] of Bayer AG, Leverkusen, Pluracol-types [Trade Mark] of the Wyandotte Company, Niax-types [Trade Mark] of Union Carbide, U.S.A., 10 polyglycols of Farbwerke Hoechst, Germany).
Suitable linear or branched polyesters are, for ~ -example, made of aliphatic and/or aromatic polycarboxylic acids and polyols, whereby the molecular weight preferably is within the same ranges as those that were mentioned for the polyethers. These products likewise are offered by many companies in the trade (for example, Desmophen-types o~ Bayer AG, Leverkusen). One can also use those products which have both polyester and polyether bonds in the same molecule. Frequently the above-mentioned products are not 20 uniform compounds but rather mixtures of substances. This is well understood by those skilled in the art.
In addition to the polyethers and/or polyesters there ; can be used for the production of reaction products other such compounds which contain at least two groups which can react with -NCO- groups, whereby their share, related ; to the total weight of the reaction products, as a rule should not be more than about 30~ by weight, preferably no more than about 20~ by weight. Such suitable com-pounds include, among others, amines, aminoalcohols, 30 and especially polyols, for example, aliphatic compounds having 1 to 8 carbon atoms which preferably contain 2 to :, .
`''' ~L~5'9~
4 hydroxyl groups i~ the molecule, such as glycol, neo-pentyl-glycol, and glycerin.
The polyisocyanates which are used to make the above mentioned reaction products are aliphatic and/or aromatic and/or cycloaliphatic compounds with preferably 2 or 3 -NCO- groups in the molecule. These products are com-mercially available, for example, under the trade name of Desmodur [Trade Mark] by Bayer AG, Leverkusen. The molecular weight of the polyisocyanates which are used for 10 making the reaction products is pre~erably in the range of from about 100-1,500 and especially preferably between about 150-500.
-~ As said above, the reaction products have an average :. ~
molecular weight of from about 500-10,000 and a content of -NCO- groups of from about 1-10% by weight. The molecular weight is preferably in the range of about 1,000-6,000, particularly preferably in the range of about 1,000-4,500.
.~, ..................................................................... . .
The content of -NCO- groups is preferably in the range of about 2-8% by weight, particularly preferably in the range 20 of abou~ 3-6% by weight. By percent by weight, in the sense of this definition, is meant the share of the weight -.:
~- of the -NCO- groups out of the total amount of reaction products.
The application mass should have a maximum viscosity , :;, .
of 60 Pas under application conditions. The viscosity .
is preferably under about 20 Pas, particularly preferably under about 10 Pas. By viscosity under application con-ditions is meant that viscosity which the application mass exhibits in the tank of the application machine.
The processing temperature is selected so that the viscosity of the mass, when the application mechanism is correspondingly ., ' .
.' ' ' ' " ~
.' , . . ' " .
', t G
~' ~L~5~39~
~.
'i .
adjusted, permits ~he desired application volume, while avoiding that the foil, which is to be coated, is damaged by the temperature applied or is unfavorably influenced in terms of its quality and gauge. The temperature of the coating mass therefore should not be above 140C, preferably not above 120C, par~icularly pre-ferably not above 100C. By temperature, in this sense, is meant once again the temperature of the application mass in the tank of the application machine.
"~ Another essential requirement in the method according to the invention is that the temperature of the coating mass must ~~ 10 not be so far below the temperature of the ambient air that enough air humidity will be condensed into the coating mass ~ -:
located in the tank of the applieatiorl machine so that the ?
pot-life of the coating mass in the tank will drop below the ~`
value required for implementation of the method. When the temperature of the coating mass is too low, the moisture from the ambien~ air can be condensed on the surface of the coating mass because of the temperature drop and~ since the coating mass -as a rule is agitated in the tank of the application machine, more and more moisture is introduced into the coating mass.
The moisture brings about an incipient cross-linking of the reaction products contained in the coating mass~ as a result of ~;
which the pot-life of the coating mass is considera61y shortenedO
... .
The consequence is that the cross-linking becomes 50 strong as : .
~ time passes that the coating method can no longer be carried out.
" , ~ 25 :~,- ,, . ` '.
'~'''' ~ . :
: ,. ' ~. ` . . :
89~
If, on the other hand~ according to the method in th1s invention, the temperature of the coating mass is kept high - enough, then condensation of air h~midity is avoided and it is extraordinarily surprising thatg when this requirement is met~ the pot-life of the coating mass is not influenced and remains constantly high. By means of simple experiments, the artisan can determine the suitable average temperature by considering the particular existing air humidity and the ~;
tempera~ure of the surrourlding air~ that is to say~ the - ;
environmental temperature. As a rule~ it is enough when the temperature of the coating mass does not fail below the temperature of the ambient air or, at best, if it is a few degrees Centigrade below in order to prevent the pot-life from being disadvantageously influenced in the sense described above.
As explained above, no added solvents should be contained ~n the application mass according to th~ invention. The ., :
above-described disad~antages of ~sing solvents are thus ~
. , .
completely avoided because, when the above-defined parameters are maintained~ quite surprisingly a perfect application and a high initial shear strength are achieved~
By way of auxiliary substances and/or additi~es which are helpful in terms of glueing technique~ the application mi~ture according to the invention may contain, for example, reaction accelerators such as tertiary amines, metal-organic compounds, ' .
'~
~ 598~
such as dibu~yl-tin-dilaurate, lubricants, dyes, pigments, or filler materials, thermoplastic resins or plasticiæers.
he reaction products used according to the invention should have a reactivity of about 5 hours maximum. The reactivity preferably is l hour, maximum, and particularly preferably about 30 minutes. Fundamentally, the reactivity can and should be even higher than indicated above so that the reaction will take place as fast as possible after application upon the foil and this is why reactivity lO values about 15 minutes or even 10 minutes maximum are particularly practical. The reactivity is determined as follows:
S00 g of the glue used are placed in a tin with a diameter of lO0 mm which is sealed against the entry of - air and moisture and they are stirred at about 60C at a ` speed of about 300 rpm. The stirrer has four blades with an outside arc of 45 mm diameter. The end of the stirrer ; lS l cm away from the bottom of the tin. Then we add, to the glue in the tin, l Mol water per equivalent of the ; ;
free -NCO- groups contained therein, and we measure the time until the start of gelatinization, which can be recognized by the fact that the mass rises along the - ~-stirring shaft. The reactivity of the resin increases in proportion to the decrease in time until the start of this effect. (The entry of moisture is prevented by covering with aluminum foil through which the stirring shaft runs.) But if, in the same manner, this proce-dure is carried out without the addition of water, there will, after 13 hours of stirring, be only a ~ 30 -~
:' ' ' :' : "' '' ~ .
. .
.
.. . .
~ 5~
viscosity increase of, for example, from about 0.77 Pas to 1,38 Pas. It has so far not been considered possible to take g]ues with such a high reactivity toward water - that is to say, toward air humidity -~ in a solvent-free state over a period of even only 1 hour, not to mention longer periods of time of about 5 hours or more, and expose them to air humidlty in a standard application machine and thus process them, without getting gelatinization. On the other hand, after application ; :.
upon the foil to be coated, the hardening process begins so fast that the method according to the invention can be carried out -; 10 in a trouble-free and simple manner.
By pot-life; within the meaning of the invention here, there ~s meant the time for which the application mass remains viscosity-stable in the tank of the application machine, under conditions prevailing there, to such an extent that perfect pro-. ;; .
cessing will be assured. For trouble-free processing on hitherto customary machines, which have an open, tempered storage container ~;~ for the application mass, a pot-life of at least 5 hours is required which facilitiates trouble-free processing during one 8-hour shift.
When the above-defined measures are complied with, safe ., ~ .
implementation of coating during an 8-hour day or during continual shift operation is facilitated, and the foils are so firmly joined immediately after coating that, even at high machine speeds, ;~
there will be no bubble or crease formation as a result of the ~ ':
- foils being shifted with respect to each other, or there will be ~ ~ .
;~ -15-. .
~' .~, .
~ 9 ~
no shifting of the foil during windup, which is called "telescoping".
One unanticipated advantage of the method according to the invention is that, in spite of solvent-free application, a perfect, unlform coating, even in quantities of about 0.5 g/m2 is possible. It is likewise surprising that even at such small ~; application volumes, completely bubble-free laminates are ~`~ obtained which are highly transparent in the ease of clear films5 -and this is true both in the ease of laminating with hot (50-100C) and eold(20C) laminating rollers. Thus the transparency disturbanees, which appear, for example, at high processing speeds also in the case of the known adhesive systems, vanish eompletely within a short time In comparison to known methods, it is therefore possible to aehieve identical transpareney with smaller applieation quantities, and better transpareney with the same applieation quantity. The possibility of attaining, through solvent-free applieation of the adhesive, sueh small applieation quantities and sueh high transpareney in transparent foil eomplexes is particularly surprising if we realize that the quantity applied must bridge all uneven spots in the foils to be joined (peak-to-valley height, undulations, ete.) so that one can ereate a eomposite strueture without interstiees.
~ .
A eomplete as possible filling of all uneven spots was aehieved, according to the state of the art, by applying a diluted solùtion in a relatively large quantity in order, after the ~5~890 ~, ; evaporation of all solvents, to leave the desired thin film behind. The smaller the desired adhesive application, the more diluted was the solution used in order to attain a still sufficiently high and unifo~n wet application.
The method according ~o the invention can be carried out S on the most varied types of machinery, for example, pressure~
laminating, and hotmelt machines,whereby the only prerequisite is a heatable application mechanism which is suitable for thin application at the required machine operating speed. The adhesive application can be accomplished with smooth or patterned rollers~ either coaxially or counter-currently, ar also with suita~le wipers. Differing circumferential speeds of the application rollers, and/or relative speeds of the rollers of the application mechanism with respect to each other~ and/or ~ between the application roller and the foil web to be coated, may ?
be advantageous ~or the purpose of achieving optîmum applications but are not absolutely required. This is known to the artisan as part of the state of the art. To get the best and most uniform application possible, the lamination may be accomplished ., . . ~ .~
immediately after the application mechanism. It is not necessary to connect evaporation zones, IR or hot-air drying or heating ducts or additional devices between the steps, even at high machine operating speeds (~or example, in excess of lO0 m/sec).
~ ~ 5~ ~9 ~
One parL--icular Eeature oE the method according to the invention is that, in spite of the viscosity which is low at the applica~ion temperature, a suf~icient bondirlg o~ the ~oils is achieved in~ediately after they leave the laminating mechanism. This is the only way in which shifting of the foils toward each other can be prevented and this is the only way ln which fold formation, bubble formation~ telescoping, etc., can be avoided, and in this way the composite foil can be wound up perfectly into a roll~
~or this property it is important that the adhesive give the foil complex, in the desired application quantity, a high shear strength (for example, more than 200 g/cm2). Shear strength is measured as follows:
; A glued sample piece is traction-stressed wIIereby the orce attacks, on one side, along the upper individual foil and, on the other side, along the lower indlvidual foil, so that we get horizontal shearing. The force measured is divided by the sur~ace and gives us the system-specific "shear strengt1n" in g/cm2, at identical application quantities.
The essence of the invention furthermore includes that the laminates, made according to the invention, become bound as fast as those which have been made according to tlle hitherto known methods. That is to say3 they achieve the desired strength in the composite structures and resistance against mechanical, chemical (Erom aggressive filler materials) and thermal (boiling ~S989~
sterilization, heat-sealing) stress through chemical cross-linkin~. In practi.ce this means that the desired high adhesion values must be achieved after a few hours up to a few days ~;
and that the ability to be boilcd and sterilized must be achieved after 6-12 days.
Although the above requirement is met, it was unexpec~edly discovered thatg when the parameters of the method arcording : to the invention are co~plied with, the coating mass remains stable, that is to say, an adequate pot-life was preserved.
Thus it was found, for example5 that, wikh a temperature treatment at 90C lasting several days, the coating mass did reveal a rise in viscosity which however was so small that the processability of the aged material was not disadvantageously . :~:
.influenced. Even samples whic.h had been expos~d to the effect of air humidity in the open tank of a coat:ing machine for more than .`~
8 hours at 90C with constant thorough mixing by the application rollers, could once again be processed in the machine after an in~ermediate storage of 8 days in a closed container without loss of any of their properties.
This fact is all the more surprising since we know from the handling o~ solvent-containing isocyanate products that the pot-life, according to past experience, grows longer as the solution is more diluted and that one would have to expect a particularly poor`stability for solvent-free products. A~cordingly it is required in U.S. Patent No. 3,840,419 that the adhesive~ :
`:
~598~
during the transition frvm one dosing roller to another one, and/or, from tle dosing roller to the film to be coated, in ~ach case must be transferred practical1y completely so that there cannot be any hardening on a roller. According to Bri.tish Patent Mo. 1,158,740, premature gelatiniza~ion, or hardening of the material must ~e prevented by mixing the rem- ;
nants of the adhesive by the defined shearing forces, îmmediately with fresh material. In the cas~ of solvent-containing adhesives according to the ~tate of the art, it is frequently recon~ended J
I for ex~ple, that adhesive mixtures~ which are not used up at I the end of a working day, ~e d~l~ted ve.ry heavily in order to thuæ prevent overnight gelation.
This surprising and favorable effect of the method accorf.ling ;~
to the invention can perhaps be explained by saying that, ~uri~g the application of solvent-containing adhesives, there is lS always an evaporation of the solvents, especially on the rol lers.
The cooling of the surfdce, brought about by evaporative cooling ;~
promotes the absorption of moisture from the air especially when the dew point has been reached. In a solvent-containing adhesive, which has remained for 3 hours in the machine while the application mechanism was kept running, it is already possible to establish a water content of 1-1.5% depending upon the prevailing air humidity, while a solvent-free product did not absorb any noticeable quantities of water. The performance o~
the solvent-free adhesive, which is more favorable because there is no evaporative cooling, is further supported by heating because ~0-~ L~59~
the temperature difference to the dew point of the air is t~en even greater.
With this good stability of the application mass in the coating machine it furthermore could not be expected that the reactivity and hardening speed of the adhesive, after application on the foil surface, would be so great that the above-described requiements existing in practice would be met. Instead, it would be especially the very long pot-life during heating under the influence of air 10 humidity which would have led to the expectation that there would be no useful hardenin~ at all or that the time intervals would be too long 50 that they could not be useable in practice. Moreover, it was to be expected that the viscosity, which was kept relatively low for solvent-free application, would considerably increase the time until the complete hardening of the foil complexes due to the requirement for a large number of cross-linking steps, compared to the highly viscous materials, in order to achieve the desired duroplastic state.
The reaction products, contained in the adhesive mixture, also contain free -NCO- groups which can react with H-acid compounds. The artisan is familiar with this reaction capability. As H-acid compounds we can use all ~ ~-compounds which are present on the surface of the foils ``
to be joined, partly due to adsorption, or which are ~;
contained in the surface. Water is particularly important ;
as H-acid compound in the implementation of the method :.. . .:
according to the invention; water is present in the form of air humidity and, practically also on all surfaces, .
~ 8~ ~
as a thin adsorbed layer in quantities sufficient for the cross-linking of the adhesives used according to the invention. For cross-linking and to achieve good adherence, unctional groups in the foil surface, such as hydroxyl-, hydroperoxide - 3 and carboxyl groups can also be involved.
The terms "solvent-free" and "solvent-free application" mean that no solvents or other low-mvlecular substances need be added to the application mass to lower the viscosity. These substances are volatile at processing temperature and ~hus have a "transport - function." Due to the molecular weight distribution o~ polymer substances and due to the absorption of gases, moisture9 and other substances from its environment, every substance used in practice contains a cured mass which is just a ~ittle bit below the theoretically anticipated 100%.
According to the method in this illvention, one can join `~
together any of the foils which were mentioned in the introduction to the specification and any which are also bonded together according to the state of the art with the use of laminating adhesives which are cr~ss-linked via isocyanate groups.
The invention is further explained on the basis of the ~
attached drawings. Identical parts have been provided with the ~ -same reference numbers in the figures.
BRIEF DESCRIPTION OF THE APPLIC~TION DRAWINGS
Figure 1 is a diagrammatic view of a laminating machine modified in accordance with the present invention. `~
Figure 2 is a simplified form of mach;ne for implementing -~2-the method according to ~he present invention, and Figure 3 is 2 coating and laminating unit preferably used for working with "hot-melt" coating and laminating masses.
DETAILED DESCRIPTION OF T~E PRE_ERRED EMBODIMEN_ Figure 1 is a diagram showing a customary laminating machine for solvent-containing adhesives which however can -;~
be used according to the method in this in~ention whereby the drying duct is not used. The roller, which unreels one of the -oils to be joined, is numbered l. In tank 4 is the laminating adhesive, that is to say~ the coating mass according to the invention. This mass is applied via the dipping roller 5 and the application roller 6, onto one side of the foil strip running off roller 1, whereby pressing roller 7 forces the foil against `
application roller 6. The air nozzles 9 which are present in the machine in drying duct 8 are not used according to the .
method in this invention; instead, they are used only for the subsequentLy described comparative example, using the method according to the state of the art. For this purpose, air is piped through the drying duct via air inlet 10 and air outlet 11. The second foil, which is to be joined together with the-first foil, is unwound from roller 2 and is guided via deflection rollers 3 to the pressing mechanism 7 where the two foils are ..
pressed against each other by means of rollers. The composite foil structure, the foils laminated together, is wound up on roller 12.
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Figure 2 is a diagram showing a simply designed machine for implementing the method according to the invention, not containing ~he drying duct because the latter is not requ~red for the method according to the invention. Such machines are used in the so-called hot-melt method. The foils to be jolned together are once again unreeled from rollers ~ and 2.
One of the foils is once again coated, after it has been guided ~ia deflection rollers 3 between application roller 6 and press-on roller 7. Application roller 6 brings the application mass from the tank on one side of the foil strip. Between the press-on rollers 7 and 13, the two foils are joined together and are wound up on roller 12.
Fi.gure 3 shows a coating and laminating unit, as is used ~-~
preferably for working with "hot-melt" coating and laminating , masses. ~
. . ;
The application medium is in tank 10. The non-rotating steel roller ~9~which can be heated,presses against the rubber roller 5, whereby the level of the pressure determines the quantity of adhesive which gets through the gap when roller 5 rotates.
.
This adhesive which is on the surface of roller 5, is taken off by roller 6 (steel roller, likewise heatable) which runs at higher speed in contact with roller 5 and it is applied upon the ; foil strip which is pressed on by rubber roller ~. It is a good idea here to keep the circumferential speed of rollers 6 and 7 -~
identical.
` -2~-;
~ .. '. 7 , ' ~ ~
. ' 5~
From the unreeling roll 2, the incoming strip is ~ed via the deflec~ion roller 3 to the coating mechanism in such a . . ~ .
manner that the film, coated with adhesive,can be joined with the incoming strip between rollers 7 and 8 without any bubble formation. Then comes the windup in winding station 9. The ` 5 glue becomes thoroughly hard in the rolls wit=hin a few days.
Production of B_nding A~ents Suitable For Method According to -~
The Invention Bonding Agent A~
To 250 parts by weight of polypropylene-etherglycol, with ;
an average molecular weight of about 2,000, is added, in a ~
reaction vessel, 62.5 parts by weight diphenylmethanediisocyanate ;-(MDJ)? whîle stirring, and the mixture is heated to 90C until -`
a viscosity of 1.5 Pas is attained, measured at 80C in a platecone yiscosity meter. The -NC0 content of the reaction - ;
- ~ .. ~ . ,, ~15 product is 3.5% by weight. This value is achieved after a reaction time of about 6 hours The solid, measured as cured residue after 1 hour at 150C, is 99% by weight. The reaction `
,. , ~
speed, calculated as above, is about 8 minutes.
,,~ , Bonding Agent B~
From 1,500 g polyglycol with a molecular weight of 1500, `;
348 g toluylenediisocyanate (TDI), a bonding agent is made, in the manner described above~ the NC0-content of which is 4.28%
by weight. The viscosity measured at 100C is 0.41 Pas. The `~
,, ~ " .
reaction speed is about 6 minutes.
: ' ~25-' : .' 59~
"
Bonding Agell~ C:
350 g of a polyester from ad:ipic acid and ethyleneglycol ; with a hydroxyl content of about 1.8% by weight~ 84.~ g MDI and 4.7 g TDI are mixed as described above up to a viscosit~ of 4.5 Pas, measured at 100C. NC0-content 2.39V/~ by weight.
Reaction speed: about 6 minutes.
~; Bonding ~gent D:
: . , 2,000 g polypropyleneglycol with a molecular weight of about 2000, 425 g MDI and 76.3 of a reaction product o 3 Mol hexamethylenediisocyanate and 1 Mol water are mixed as described above up to a viscosity of 1.7 Pas, measured at 100C. NC0~
~`l content: 4.95% by weight. Reaction speed: about 10.2 minutes.
~xample l ~-The bonding agent described above is filled into the ; heated storage tank 4 of the laminating machine of conventional design, illustrated in Figure 1, and it is heated to 12.0~C. ht ., the same time the application roller 6 is preheated to 100 C.
- After the given temperatures are obtained, a 12.5~mu thick polyester foil is coated with the application mixture whereby - the application roller is driven in the same direction. The foil thus coated is then guided through the drying duct 8 although ,t the latter ls not heated and is not charged with fresh air ; ~ecause this is not required in the method according to the invention. After the drying duct -- between a stationary-attached roller and press roller 7 -- a polyethylene foil ` -26-,~ with a thickness of 50 mu,which on tl~e side to be glued had earlier been subjected to a Corona treatment, is app'lied. --The temperature of the press-on roller is 40C. Ater rolling- -~
up, further hardening takes place during storage. The value given suhsequently for the composite adhesion and the sol~en~
residue are measurPd after 5 days. ' Table 1 , application weight 1.2/m ` ; movement speed 100 m/min ~' ~` composite adherence 400 g/20 mm solvent residue 0 mg/m2 , The composite adherence is measured as follows: a 20 millimeter wide strip of the foil composite made is clamped into '~
a tearing machine at the peeling angle of 2 x 90, then the joined ;~' '~ ~oil strips are separated at a feeding speed of 50 mm/min and the i 15 force required for separation is measured; this force is measured ; in g/20 mm. '-, The solvent residue is-determined as follows: from the ^`, middle position of the wound-up coated composite foil a sample '- -~
~ piece is taken and heated in a gas-proof tank for 1 hour up to ";~,20 a maximun of 120C so that no cracking'products of the laminated ~;~
', oil will develop, We take a sample from the gas ch~n'~er of the ,~ container and we examine it gaschromatographically.
, ," Comparative Example 1 ',~
',~ On the same coating nachLne, used according to Example 1, `
9~g~ :~
a composit~ ~oil structure is made of the same foils as those in Example l; this is done wi~h a customary solvent-containing coating adhesive which is made of an esterification product from phthalic acid, adipic acid, and ethyleneglycol, and, a second coMponent, triisocyanate (made from 1 mole ~
trimethylolpropane and 3 moles toluylenediisocyanate3, which --`
has solvent ethylacetate and a solids content of 35% by weight. The operating conditions are the same with the exception o~ the heating of the application roller and the . ~
tank and the insertion of the drying duct. Hot air with a ` temperature of 80C is blown on the coated foil in the drying ~ duct.
`;~ application weight (wet) 4.6 g/m2 .,-~ ~' application weight (dry) 1.6 g/m2 `
; 15 operating speed 100 m/min !`~
~ somposite adhesion 400 g/20 mm `~ solvent residue 40 ~g/m2 exhaust air volume 3,600 m3/hr energy consumption for heating the air, approximately 65 3 000 ~cal/hr The residual quantity o~ glue clouded after 1 day and gela- ~-tinized a~ter 2 days.
:, .
Example 2 On a machine without drying duct (see Figure 2) -- which essentlally ConSistB of a directly powered application mechanism ;~
; .~' ~ 059~3~
with three superposed rollers, two unreeling devices and one windup device -- a laminate from a 12.5-mu thick polyester ;.
~ foil and a 9 mu thick aluminum foil is made, in that the polyester . foil is coated with the solvent-~ree adhesive which had been ; -.:. 5 heated to 90C and is joined together with the aluminum foil . :
:.:
... between rollers 7 and 14. After 5 days of storage, the composite :
adherence and the solvent residl.te are measured. ' '~
. .
Table 3 . :' '.~ application weight 1.5 g/m2 operating speed 100 m/min composite adherence 420 g/20mm --s~-~ent-residue ---~-mg~m :'.:
.. ' .
~, ' The application mass ~ccording to the invention has a flash :~l .point of more than 150 C while the application mass, used according ' .to the comparative example 1, has a flash point below-4C.
When the ~pplication mass according to the state of the art s used, explosion-protected systems must be employed, something -~ .
, ~ . which is not required in the method according to the invention.
. .,.~ , . . .
~' Example 3 .... .
.,. ~, ~
,''~! 20 On a machine without drying duct (Figure 3) -- essentially ~:~" '~''consisting of a''directly p'owered combined'applicat'ion`and coating ~' . ~ .
':. mechanism with five rollers, two unreeling devices and one windup .., .: 'device -- a laminate is made from a 30-mu thîck polyamide foil :;
.. ~ .
.': and a 50-mu thick pretreated polyethylene oil, in that the ~.
, .i , 25 polyamide foil is coated wit'h solvent-free adhesive B which is : ' heated to 95C and is joined with the polyethylene foil between .';~ -29-. :
:', , s~
rollers 7 and 8. The composite adherence and the solvent residues are measured after 7 days of storage.
; Table 4 application wPight 1.3 g/m2 ~ -operating speed 80 m/min composite adherence ~900 g/20 mm (film torn~
solvent residue 0 mg/m2 ,~ Example 4 On a machine according to Figure 3, aluminum foil with a 1 .. .
thickness of 10~mu is coated with solvent-free adhesive A
and is applied to a paper of 80 g/m2. The temperature of the `~ material in the tank and an rollers 4 and 6 i5 about 100C~
`; Ta~le S
application speed 1.2 g/m2 --operating speed 300 m/min :.l .. .
; composite adherence not separable, paper split -; solvent residue O~mg/m2 .~
Example 5 ~; On a machine according to Figure 3 3 -12-mu aluminum foil is 20 coated with solvent-free adhesive B and is applied to a 50-mu thick Corona-pretreated polyethylene. Temperature in tank and on rollers: about 75C.
Table 6 application weight 2.0 g/m2 operating speed 100 m/min.
, .
.
~59890 ~`:
Table 6 (continued) - ;~
composite adherence ~430 g/2 cm, solvent residue 0 mg/m2 xample 6 On a laminating machine with an applicc~tion mechanism ~ ~-according to ~igure 2, an oriented, Corona-pretreated poly-~ ,.
~' propylene foil is coated with solvent-free adl~esive C and i is laminated between roller pair 7 and 13 with a 30-mu thick -Corona-pretreated polyethylene foil. Temperature in tank and .
of roller 6: about 120C.
.
Table 7 ; ::~
application weight 1.4 g/m2 .
operating speed 14 mlmin composite adherence ~350 g/2cm, film torn ~:
, f 15 solvent residue 0 mg/m2 i, i .
Experimental setup as in Example 6, but adhesive is used ~ ;
: this time and, in place of the oriented polypropylene foil, i ~ ;
a nonoriented polypropylene ~ilm is used. Temperature in the :~ 20 tank and of rolIer 6: about 95C. .
Table 8 ~ -~
application weight 1.4 g/m op~rating speed 14 m/min composite adherence 700 g/3cm, film torn solvent residue 0 mg/m2 .
.' ' , ' ,, ' " .
-. .
.
.
: ~ ,. . .
15~8~
Exam~ 8 Experimental setup as of Example 6, but instead of the oriented polypropylene film, a biaxially-stretched polypropylene film is used with a thickness of 30 mu which is coated on both 5 sides with PVDC, whereby adhesive is applied. Temperature in tank and of roller 6: about 80C.
Table 9 application weight 1.4 g/m2 operating speed 14 m/min -~ 10 composite adherence 400 g/2cm, ~ilm tor~
solvent residue 0 mg/m ~` Example 9 ~:
;
Experimental setup as of Example 6, but instead of the oriented polypropylene film, a cellulose glass web (34 g/m2 v surface weight) is used which is lacquered with nitrocellulose on one side and which is coated on the non-lacquered cellulose glass side with solvent-free adhesive C and this combination is then applied to a 50-mu thick polyethylene layer. Temperature in tank and on roller 6: about 120C.
Table 10 - application weight 1.5 g/m2 operatlng speed 14 m/min - :
composite adherence 500-700 g/2cm solvent residue about 1 mg/m2 (from cellulose : ~:
Z5 glass lacquering) -32- :
a composit~ ~oil structure is made of the same foils as those in Example l; this is done wi~h a customary solvent-containing coating adhesive which is made of an esterification product from phthalic acid, adipic acid, and ethyleneglycol, and, a second coMponent, triisocyanate (made from 1 mole ~
trimethylolpropane and 3 moles toluylenediisocyanate3, which --`
has solvent ethylacetate and a solids content of 35% by weight. The operating conditions are the same with the exception o~ the heating of the application roller and the . ~
tank and the insertion of the drying duct. Hot air with a ` temperature of 80C is blown on the coated foil in the drying ~ duct.
`;~ application weight (wet) 4.6 g/m2 .,-~ ~' application weight (dry) 1.6 g/m2 `
; 15 operating speed 100 m/min !`~
~ somposite adhesion 400 g/20 mm `~ solvent residue 40 ~g/m2 exhaust air volume 3,600 m3/hr energy consumption for heating the air, approximately 65 3 000 ~cal/hr The residual quantity o~ glue clouded after 1 day and gela- ~-tinized a~ter 2 days.
:, .
Example 2 On a machine without drying duct (see Figure 2) -- which essentlally ConSistB of a directly powered application mechanism ;~
; .~' ~ 059~3~
with three superposed rollers, two unreeling devices and one windup device -- a laminate from a 12.5-mu thick polyester ;.
~ foil and a 9 mu thick aluminum foil is made, in that the polyester . foil is coated with the solvent-~ree adhesive which had been ; -.:. 5 heated to 90C and is joined together with the aluminum foil . :
:.:
... between rollers 7 and 14. After 5 days of storage, the composite :
adherence and the solvent residl.te are measured. ' '~
. .
Table 3 . :' '.~ application weight 1.5 g/m2 operating speed 100 m/min composite adherence 420 g/20mm --s~-~ent-residue ---~-mg~m :'.:
.. ' .
~, ' The application mass ~ccording to the invention has a flash :~l .point of more than 150 C while the application mass, used according ' .to the comparative example 1, has a flash point below-4C.
When the ~pplication mass according to the state of the art s used, explosion-protected systems must be employed, something -~ .
, ~ . which is not required in the method according to the invention.
. .,.~ , . . .
~' Example 3 .... .
.,. ~, ~
,''~! 20 On a machine without drying duct (Figure 3) -- essentially ~:~" '~''consisting of a''directly p'owered combined'applicat'ion`and coating ~' . ~ .
':. mechanism with five rollers, two unreeling devices and one windup .., .: 'device -- a laminate is made from a 30-mu thîck polyamide foil :;
.. ~ .
.': and a 50-mu thick pretreated polyethylene oil, in that the ~.
, .i , 25 polyamide foil is coated wit'h solvent-free adhesive B which is : ' heated to 95C and is joined with the polyethylene foil between .';~ -29-. :
:', , s~
rollers 7 and 8. The composite adherence and the solvent residues are measured after 7 days of storage.
; Table 4 application wPight 1.3 g/m2 ~ -operating speed 80 m/min composite adherence ~900 g/20 mm (film torn~
solvent residue 0 mg/m2 ,~ Example 4 On a machine according to Figure 3, aluminum foil with a 1 .. .
thickness of 10~mu is coated with solvent-free adhesive A
and is applied to a paper of 80 g/m2. The temperature of the `~ material in the tank and an rollers 4 and 6 i5 about 100C~
`; Ta~le S
application speed 1.2 g/m2 --operating speed 300 m/min :.l .. .
; composite adherence not separable, paper split -; solvent residue O~mg/m2 .~
Example 5 ~; On a machine according to Figure 3 3 -12-mu aluminum foil is 20 coated with solvent-free adhesive B and is applied to a 50-mu thick Corona-pretreated polyethylene. Temperature in tank and on rollers: about 75C.
Table 6 application weight 2.0 g/m2 operating speed 100 m/min.
, .
.
~59890 ~`:
Table 6 (continued) - ;~
composite adherence ~430 g/2 cm, solvent residue 0 mg/m2 xample 6 On a laminating machine with an applicc~tion mechanism ~ ~-according to ~igure 2, an oriented, Corona-pretreated poly-~ ,.
~' propylene foil is coated with solvent-free adl~esive C and i is laminated between roller pair 7 and 13 with a 30-mu thick -Corona-pretreated polyethylene foil. Temperature in tank and .
of roller 6: about 120C.
.
Table 7 ; ::~
application weight 1.4 g/m2 .
operating speed 14 mlmin composite adherence ~350 g/2cm, film torn ~:
, f 15 solvent residue 0 mg/m2 i, i .
Experimental setup as in Example 6, but adhesive is used ~ ;
: this time and, in place of the oriented polypropylene foil, i ~ ;
a nonoriented polypropylene ~ilm is used. Temperature in the :~ 20 tank and of rolIer 6: about 95C. .
Table 8 ~ -~
application weight 1.4 g/m op~rating speed 14 m/min composite adherence 700 g/3cm, film torn solvent residue 0 mg/m2 .
.' ' , ' ,, ' " .
-. .
.
.
: ~ ,. . .
15~8~
Exam~ 8 Experimental setup as of Example 6, but instead of the oriented polypropylene film, a biaxially-stretched polypropylene film is used with a thickness of 30 mu which is coated on both 5 sides with PVDC, whereby adhesive is applied. Temperature in tank and of roller 6: about 80C.
Table 9 application weight 1.4 g/m2 operating speed 14 m/min -~ 10 composite adherence 400 g/2cm, ~ilm tor~
solvent residue 0 mg/m ~` Example 9 ~:
;
Experimental setup as of Example 6, but instead of the oriented polypropylene film, a cellulose glass web (34 g/m2 v surface weight) is used which is lacquered with nitrocellulose on one side and which is coated on the non-lacquered cellulose glass side with solvent-free adhesive C and this combination is then applied to a 50-mu thick polyethylene layer. Temperature in tank and on roller 6: about 120C.
Table 10 - application weight 1.5 g/m2 operatlng speed 14 m/min - :
composite adherence 500-700 g/2cm solvent residue about 1 mg/m2 (from cellulose : ~:
Z5 glass lacquering) -32- :
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS.
1. In a method for joining foils including the steps of mechanically coating at a high speed at least one of the foil sides to be joined with a reaction product of a hydroxy-functional polyethers or polyesters with poly-isocyanates, said reaction product containing free-NCO
groups and being reactable with H-acid compounds, and subsequently laminating the foils, the improvement which comprises said reaction product having an average molecular weight of from about 500-10,000 and a -NCO group content of from about 1-10% by weight, said reaction pro-duct being substantially solvent-free when applied and having a viscosity of at most 60 Pas under application conditions, and adjusting the temperature of the reaction product application conditions to at most 140°C but not less than a temperature which is so far below the temperatuare of the ambient air that such an amount of air humidity will be condensed in the reaction product to be applied that its pot-life would drop the value required for the implementation of the method.
groups and being reactable with H-acid compounds, and subsequently laminating the foils, the improvement which comprises said reaction product having an average molecular weight of from about 500-10,000 and a -NCO group content of from about 1-10% by weight, said reaction pro-duct being substantially solvent-free when applied and having a viscosity of at most 60 Pas under application conditions, and adjusting the temperature of the reaction product application conditions to at most 140°C but not less than a temperature which is so far below the temperatuare of the ambient air that such an amount of air humidity will be condensed in the reaction product to be applied that its pot-life would drop the value required for the implementation of the method.
2. The method according to claim 1, wherein said foil is coated with from about 0.1-10 g/m2 of said reaction product.
3. The method according to claim 1 wherein the polyester or polyether, used to make the reaction product, has a molecular weight of from about 300-4,000.
4. The method according to claim 1, wherein reaction products contain a co-polymerized polyol in a quantity of less than about 30% by weight.
5. The method according to claim 1, wherein the polyisocyanate has a molecular weight in the range of about 100-1,500.
6. The method of Claim 1, wherein said coating speed is greater than about 50 m/min.
7. The method of Claim 2, wherein the amount of said reaction product is between about 0.5 and 5 g/m2.
8. The method of Claim 3, wherein said molecular weight is between about 400 and 2,000.
9. The method of claim 4, wherein said polyol is present in an amount of less than about 20% by weight.
10. The method of Claim 5, wherein said polyisocyanate has a molecular weight of between about 150 and 500.
11. The method of Claim 1, wherein said reaction product contains co-polymerized therein at least one component selected from a polyamine, and amino alcohol and a polyol.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT880774A AT347698B (en) | 1974-11-04 | 1974-11-04 | METHOD OF JOINING FILMS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1059890A true CA1059890A (en) | 1979-08-07 |
Family
ID=3608692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA238,897A Expired CA1059890A (en) | 1974-11-04 | 1975-11-03 | Solvent free method of laminating using isocyanate adhesive |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US4092202A (en) |
| JP (1) | JPS5850165B2 (en) |
| AR (1) | AR206361A1 (en) |
| AT (1) | AT347698B (en) |
| BE (1) | BE835022A (en) |
| BR (1) | BR7507221A (en) |
| CA (1) | CA1059890A (en) |
| DE (1) | DE2549227C2 (en) |
| DK (1) | DK494475A (en) |
| ES (1) | ES442282A1 (en) |
| FI (1) | FI65570C (en) |
| FR (1) | FR2289589A1 (en) |
| GB (2) | GB1531413A (en) |
| IT (1) | IT1054359B (en) |
| MX (1) | MX142840A (en) |
| NL (1) | NL180767C (en) |
| SE (1) | SE419870B (en) |
Families Citing this family (42)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55102668A (en) * | 1979-01-31 | 1980-08-06 | Nitto Electric Ind Co Ltd | Method of adhering |
| US4242488A (en) * | 1979-05-09 | 1980-12-30 | National Starch And Chemical Corporation | Modified polyurethane adhesive compositions containing a carbamate ester additive useful in laminating substrates |
| EP0022502A1 (en) * | 1979-07-04 | 1981-01-21 | Herberts Gesellschaft mit beschränkter Haftung | Laminate, method of its manufacture and use of silanes therefor |
| US4342613A (en) * | 1979-09-21 | 1982-08-03 | Leary James N O | Method of bonding surfaces with a solid adhesive |
| DK144429C (en) * | 1979-12-12 | 1982-08-23 | Superfos Glasuld As | PROCEDURE FOR MANUFACTURING A BUILDING ELEMENT |
| JPS575777A (en) * | 1980-06-12 | 1982-01-12 | Nissan Motor Co Ltd | Method for bonding part to formed product |
| JPS57205469A (en) * | 1981-06-10 | 1982-12-16 | Toyo Ink Mfg Co Ltd | Solventless polyurethane adhesive for dry laminate |
| DE3130430A1 (en) | 1981-07-31 | 1983-02-17 | Bayer Ag, 5090 Leverkusen | METHOD FOR GLUING FILMS |
| DE3239065C2 (en) * | 1982-10-22 | 1984-08-30 | Peguform-Werke GmbH, 7805 Bötzingen | Process for the production of textile-laminated molded parts |
| DE3334692C3 (en) * | 1983-09-24 | 1993-12-02 | Uhde Gmbh | Device for the curing treatment of plastic-clad metal foils, in particular aluminum foils |
| US4530230A (en) * | 1983-11-14 | 1985-07-23 | Aluminum Company Of America | Foil rolling method and apparatus |
| DE3343779A1 (en) * | 1983-12-03 | 1985-06-13 | Basf Ag, 6700 Ludwigshafen | METHOD FOR IMPROVING THE LIABILITY OF ADHESIVE LAYERS APPLIED FROM AQUEOUS DISPERSION ON POLYOLEFINE SURFACES |
| US4654240A (en) * | 1984-09-28 | 1987-03-31 | Baxter Travenol Laboratories, Inc. | Laminate film for flexible containers |
| US4692361A (en) * | 1984-09-28 | 1987-09-08 | Baxter Travenol Laboratories, Inc. | Film laminate with gas barrier for sterile flexible containers |
| US4686125A (en) * | 1984-09-28 | 1987-08-11 | Baxter Travenol Laboratories, Inc. | Film laminate for sterile flexible containers |
| GB8503561D0 (en) * | 1985-02-12 | 1985-03-13 | Bostik Ltd | Adhesive compositions |
| JPH01223226A (en) * | 1988-03-01 | 1989-09-06 | Kubota Ltd | Hydraulic circuit for back hoe working vehicle |
| NO891754L (en) * | 1988-06-02 | 1989-12-04 | Minnesota Mining & Mfg | NON-TREATIVE MOISTURIZING-CURING MIXTURES. |
| EP0346512A1 (en) * | 1988-06-15 | 1989-12-20 | Nordson Corporation | Process and apparatus for laminating metal foils with films |
| US4976817A (en) * | 1988-12-09 | 1990-12-11 | Morton International, Inc. | Wet lamination process and apparatus |
| GB2234704B (en) * | 1989-07-28 | 1993-04-14 | Toyo Kohan Co Ltd | Method for producing steel sheet laminated with a polyester resin film |
| CA2000356C (en) * | 1989-11-09 | 1995-08-22 | Atsuo Tanaka | Copolyester resin film laminated metal sheet and method for production thereof |
| IT1238377B (en) * | 1990-02-19 | 1993-07-16 | Rossetti Renzo | PLASTICIZING MACHINE, FOR COUPLING SHEETS OF PAPER OR CARDBOARD WITH TRANSPARENT FILM, THROUGH SOLVENT-FREE ADHESIVES. |
| CA2039964A1 (en) * | 1990-04-27 | 1991-10-28 | Charles W. Stobbie, Iv | Mixture of isocyanate-terminated polyurethane prepolymers |
| US5418310A (en) * | 1990-04-27 | 1995-05-23 | Minnesota Mining And Manufacturing Company | Mixture of isocyanate-terminated polyurethane prepolymers having good adhesion |
| DE4124457C2 (en) * | 1991-07-24 | 2000-05-31 | Windmoeller & Hoelscher | Device for gluing plastic films |
| DE4215609A1 (en) * | 1992-05-12 | 1993-11-18 | Huels Chemische Werke Ag | Thermoplastic multilayer composites |
| DE4215608A1 (en) * | 1992-05-12 | 1993-11-18 | Huels Chemische Werke Ag | Multi-layer plastic pipe |
| DE4240658A1 (en) * | 1992-12-03 | 1994-06-09 | Huels Chemische Werke Ag | Multi-layer plastic tube |
| AU6552094A (en) * | 1993-04-07 | 1994-10-24 | Rexam Industries Corporation | Method of forming laminated fire resistant flexible sheet material and resulting product |
| DK171704B1 (en) * | 1995-07-19 | 1997-04-01 | Max Otto Henri Rasmussen | Process for preparing a laminate, laminate obtainable by the method, use of this laminate and packaging comprising laminate |
| JP2000514376A (en) | 1996-07-15 | 2000-10-31 | マックス、オットー、ヘンリー、ラスムサン | Laminate manufacturing method and laminate obtained thereby |
| US6291574B1 (en) | 1999-08-27 | 2001-09-18 | General Electric Company | Polyester molded articles |
| US20030014947A1 (en) * | 2001-07-19 | 2003-01-23 | Sarojini Deevi | Laminated metal foil packaging material and method of making |
| US6630527B2 (en) | 2001-10-19 | 2003-10-07 | General Electric Company | UV stabilized, impact modified polyester/polycarbonate blends, articles, and methods of manufacture thereof |
| DE10235583A1 (en) * | 2002-08-03 | 2004-02-19 | Alcan Deutschland Holdings Gmbh & Co. Kg | Sealing foil comprises an extruded barrier layer which is located between the primer layer and the extruded functional layer, and serves to prevent migration of constituents of these two layers |
| NO317776B1 (en) | 2003-04-14 | 2004-12-13 | Bodil Korshamn | children Pose |
| WO2008058703A1 (en) * | 2006-11-17 | 2008-05-22 | Bostik S.A. | Solvent-free laminating adhesive |
| PL238500B1 (en) * | 2017-12-08 | 2021-08-30 | Dramers Spolka Akcyjna | Method for coating of metal substrate with the coating material, device for coating of metal substrate with the coating material and a can made of metal |
| CN107955571A (en) * | 2017-12-11 | 2018-04-24 | 浙江工业大学 | A kind of silane modified polyether base rubber of low viscosity and preparation method thereof |
| BE1028470B1 (en) | 2020-07-10 | 2022-02-08 | De Roeve Koen | THERMOPLASTIC COMPOSITE ELEMENT WITH IMPROVED RESISTANCE TO DELAMINATION |
| CN112143458A (en) * | 2020-08-11 | 2020-12-29 | 湖南省春龙竹艺有限公司 | Aldehyde-free adhesive for bamboo summer sleeping mat and preparation method thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2430479A (en) * | 1941-07-23 | 1947-11-11 | Du Pont | Bonding of laminates by means of isocyanates |
| GB731071A (en) * | 1951-07-19 | 1955-06-01 | Du Pont | Preparation of elastomers from polyalkylene ether glycols and diisocyanates |
| US3061557A (en) * | 1957-12-12 | 1962-10-30 | Union Carbide Corp | Method of reacting an active hydrogen containing compound with an isocyanate or isothiocyanate in contact with a polystannate catalyst |
| US3261813A (en) * | 1963-02-13 | 1966-07-19 | Ramos Thomas | Room temperature curing system for urethane prepolymers utilizing bischloroaniline and dibutyltin dilaurate |
| US3198692A (en) * | 1963-02-26 | 1965-08-03 | Tee Pak Inc | Polyolefin laminate |
| US3471445A (en) * | 1966-06-27 | 1969-10-07 | Allied Chem | Curable urethane compositions |
| US3577295A (en) * | 1968-04-10 | 1971-05-04 | Goodyear Tire & Rubber | Method of bonding textile fabric belts |
| US3658939A (en) * | 1968-12-11 | 1972-04-25 | Usm Corp | Polyurethane and adhesive solution of a polyurethane |
| GB1331627A (en) * | 1970-12-21 | 1973-09-26 | Ucb Sa | Composite packing material |
-
1974
- 1974-11-04 AT AT880774A patent/AT347698B/en not_active IP Right Cessation
-
1975
- 1975-01-01 AR AR26096775A patent/AR206361A1/en active
- 1975-10-27 GB GB4406275A patent/GB1531413A/en not_active Expired
- 1975-10-27 GB GB2917977A patent/GB1531414A/en not_active Expired
- 1975-10-30 BE BE2054637A patent/BE835022A/en not_active IP Right Cessation
- 1975-11-03 BR BR7507221A patent/BR7507221A/en unknown
- 1975-11-03 FI FI753067A patent/FI65570C/en not_active IP Right Cessation
- 1975-11-03 FR FR7533592A patent/FR2289589A1/en active Granted
- 1975-11-03 DK DK494475A patent/DK494475A/en not_active Application Discontinuation
- 1975-11-03 US US05/628,384 patent/US4092202A/en not_active Expired - Lifetime
- 1975-11-03 ES ES442282A patent/ES442282A1/en not_active Expired
- 1975-11-03 IT IT2898675A patent/IT1054359B/en active
- 1975-11-03 DE DE2549227A patent/DE2549227C2/en not_active Expired
- 1975-11-03 CA CA238,897A patent/CA1059890A/en not_active Expired
- 1975-11-04 JP JP50132385A patent/JPS5850165B2/en not_active Expired
- 1975-11-04 NL NL7512917A patent/NL180767C/en not_active IP Right Cessation
- 1975-11-04 SE SE7512342A patent/SE419870B/en unknown
- 1975-11-04 MX MX16167275A patent/MX142840A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB1531413A (en) | 1978-11-08 |
| US4092202A (en) | 1978-05-30 |
| BE835022A (en) | 1976-04-30 |
| GB1531414A (en) | 1978-11-08 |
| FR2289589B1 (en) | 1980-03-21 |
| JPS5169579A (en) | 1976-06-16 |
| NL7512917A (en) | 1976-05-06 |
| SE7512342L (en) | 1976-05-05 |
| BR7507221A (en) | 1976-08-03 |
| JPS5850165B2 (en) | 1983-11-09 |
| FR2289589A1 (en) | 1976-05-28 |
| DE2549227A1 (en) | 1976-05-26 |
| DE2549227C2 (en) | 1984-08-02 |
| ATA880774A (en) | 1978-05-15 |
| AR206361A1 (en) | 1976-07-15 |
| NL180767C (en) | 1987-04-16 |
| IT1054359B (en) | 1981-11-10 |
| AT347698B (en) | 1979-01-10 |
| SE419870B (en) | 1981-08-31 |
| FI753067A (en) | 1976-05-05 |
| DK494475A (en) | 1976-05-05 |
| MX142840A (en) | 1981-01-05 |
| ES442282A1 (en) | 1977-04-01 |
| FI65570C (en) | 1984-06-11 |
| FI65570B (en) | 1984-02-29 |
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