DE2609266A1 - PROCESS FOR COVERING OR ADHESIVE JOINING OF SURFACES, IN PARTICULAR FOR ADHESIVE JOINING OF SHOE SOLES TO SHOE UPPER PARTS - Google Patents

Description

Method of covering or adhesive bonding of Surfaces, especially for the adhesive ~ "* joining of shoe soles with Schuhobertexlen

The invention relates to a method for covering (coating) or adhesive bonding of surfaces; it concerns in particular a method for the adhesive connection of surfaces, such as shoe soles (treads), with shoe upperso

An important condition for the attachment of shoe soles (treads), such as outsoles, to shoe uppers is the fact that the adhesive is applied in the flowable state

§09830 / 0971

must be so that it can wet the surfaces to be connected and penetrate them to _a limited extent o It is also important that the adhesive then becomes tough and firm o The initial flowability has so far been achieved by using volatile organic solvent solutions of adhesives in which the Developed strength and toughness after application as the solvent evaporated. However, these solvent adhesives need a certain amount of time to dry the adhesive and are flammable and harmful to health because of the solvent vapors that develop in the process.

Hot-melt adhesives (in the Heat melting adhesives) are used, however, since a relatively high temperature is required to maintain the viscosity of the adhesive to a value that is sufficiently low for the surface to be wetted with the adhesive thereby problems both in relation to the degradation (decomposition) of the adhesive and in some cases in relation to it on the damage to the surfaces to be connected. In addition, the relatively short processing time undesirably high time requirements for the union of the surfaces with the still flowable adhesive in between.

It is therefore an object of the present invention to provide a method of coating or joining surfaces using a coating material which is initially flowable at relatively low temperatures so that it can more easily produce a wetting adhesive bond with a surface , and which can be converted into a tough, solid, but heat-softenable state through a relatively mild treatment, which can produce a virtually instant solid adhesive bond with a compatible adhesive or a resin surface _{or the like}

§09838 / 097 $

For this purpose, according to a feature of the door lying Invention of a polymeric urethane containing reactive -NGO groups and contains crystalline segments in the polymer molecule and a relatively low crystalline Has melting point, applied in the form of a layer on a surface at a relatively low temperature, in which it is still free-flowing, so that it can form a wetting adhesive bond with this surface «, Der Coating of the urethane material is made by reacting with a Chain extender containing a compound with active hydrogen atoms linked to the -NCO groups of the urethane react, converted into a tough, solid state. The coating mixed with the chain-extending agent can then be converted into the state softened by heat against a compatible surface, the one with the first-mentioned surface is to be connected, pressed to form an adhesive connection and this compound can then be cooled so that it is in a hard, solid state transforms. The method forming the subject of the invention is primarily suitable for the production of adhesive bonds, especially for gluing shoe soles (treads!) with shoe uppers, and is referred to below described in more detail on this preferred use. However, the method according to the invention is also suitable for coating (Coating) and adhesive bonding of other surfaces, such as those made of wood, resin or rubber materials, Metal and fabrics as well as in reinforcing and stiffening Foil materials, such as for stiffening the tips or Heels of shoes.

The invention is described below with reference to the enclosed Drawing explained in more detail show:

1 is a perspective view of an outsole fastening device with broken away parts that have a strip of adhesive applies to the attachment edge of an outsole;

Figure 2 is a schematic elevational view showing activation shows the adhesive on an outsole and the shoe upper by radiant heating, and

Figure 3 is a schematic elevational view showing the bonding Showed (bonding) an outsole to a shoe upper (shoe upper leather) in a sole fastening press

As shown in FIG. 1, the use of the adhesive in the method for gluing the outsole on can comprise the application of a strip 10 of the urethane adhesive in the flowable state to the fastening edge of an outsole 12, preferably by means of an outsole fastening device 14. The outsole fastening device 14 consists of a nozzle 16 for applying and distributing the adhesive, a drive wheel 18 for transporting the outsole 12 at the desired rate past the nozzle 16 and a guide device 20 around the edge of the outsole 12 in the desired position opposite the nozzle 16 to hold _e As shown in Fig. 1, a strip 10 is applied by means of the fastening device, which extends at least around the front portion of the outsole 12, but the strip 10 can also extend around the entire edge of the outsole, ge according to construction of the shoe to be manufactured _o The same or a different adhesive that is compatible with it can also be applied to the adhesive surface of the bottom of a shoe upper (shoe upper leather) Generation of moisture, and preferably the applied adhesive is subjected to limited heating in order to effect "chain elongation of the adhesive.,

Bach's chain extension of the glue includes the completion of the sole fastening method (Fig. 2)

bring the outsole 12 and an upper 22, whereby on the bonding surface 24 on the lower part of the Shoe upper part of the adhesive is located on a frame 26 which is at a distance from a radiant heating unit 28 is arranged to heat the adhesive to a temperature above its crystalline melting point and it in a bring viscoelastic state. After heating the adhesive on the underside of the shoe upper leather 22 and on of the outsole 12, the outsole 12 is placed on the underside of the upper 22 and the composite of the outsole 12 and the shoe upper 22 is in a sole bonding press 30 (see. Fig. 3) used and exposed to the sole bonding pressure.

The inventive method offers the advantage of the ordered sequence of the development of physical properties resulting from the temperature and Ohemikalienwirkungen on the adhesive associated with the crystalline properties of the segments of the resin and the relatively low molecular weight of the adhesive _o The adhesive may for applying be converted into a liquid form by heating it to melt or by adding a solvent O

When the adhesive is applied in molten form, only a temperature above the crystalline melting point of the resin segments need be applied to give it the flowability required for crosslinking adhesive bond to a surface to be bonded to, the term used herein "Crystalline melting point" stands for the temperature at which the crystalline segments of the polymer melt, and it is determined as the temperature of the main endothermic maximum in a differential thermal analysis _o If the polymer is brought to a temperature above this temperature during activation, the crystalline segments melt and cause

that the polymer coating or film becomes soft, "Fach dem When applied, the adhesive is brought to a temperature below the crystalline melting point and crystallizes out left to have sufficient resistance to flow (creep) and deformation in the case of the subsequent stage applied temperatures to develop.

The adhesive can also be brought into a liquid form by dissolving it in an inert volatile solvent for application at room temperature or at slightly elevated temperatures. Examples of solvents that can be used are volatile organic liquids which do not contain active hydrogen. Such solvents that can be used include xylene, toluene, dimethylformamide, acetone, methyl ethyl ketone, ethyl acetate, cellulose acetate, methylene chloride and mixtures thereof. Particularly advantageous solvents are mixtures of toluene with up to about 85 wt .-% _o (based on the weight of the solvent mixture), methylene chloride or methyl ethyl ketone Due to the Matur the urethanes used in the novel process have solutions with a relatively high solids content, for example of 60 percent by .-% and more, have viscosities that are sufficiently low for the application to achieve adhesive bond with surfaces. Lower percentages of solvents can also be used if it is desired to apply the urethane material at moderately elevated temperatures, below the temperatures required to melt the urethane in the absence of solvents. If the applied adhesive is in the form of a solution, the solvent is evaporated before the subsequent treatment.

The step that follows the production of a coating from the adhesive is the reaction of the active isocyanate groups of the adhesive in the heat or at moderately elevated temperatures with a chain extender that is at least two provides active hydrogen atoms, such as water vapor, or the like

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, Resistant to the adhesive to a tough, against flow (creep) chain extenders, but "position ¹ by heat softenable condition au. In patients treated with the chain extender state of the crystalline melting point is compared to that of the original urethane adhesive practically unchanged, so that when this is heated to a temperature above the crystalline melting point, the adhesive treated with the chain extender becomes viseoelastic, namely somewhat rubber-like, but deformable and flowable under pressure, and it is sticky and able to bond with a compatible surface, such as For example, made of wood, metal or a fabric that is coated with the same or a compatible adhesive or with a resin, such as a yinyl resin, to be bonded Chain extender be If the adhesive is traded at temperatures above its crystalline melting point, the bonds created by the contact of the adhesive surface with another surface have a very high initial bond strength, so that, for example, when gluing a shoe sole to a shoe upper, the inclination of the sole, see from the upper part due to the resilience of the sole to disconnect, turned off,

The adhesive which the successive advantageous physical states in the successive physical and chemical treatments developed, based on a polyurethane with reactive -NGO groups, expediently one Prepolymer with terminal -UGO, which is used in the implementation a polyol having a relatively low molecular weight and a crystalline melting point within the range from about 40 to about 90 G, preferably from about 40 to about 65 ° C, with excess diisocyanate is obtained «

Examples of suitable polyol materials include the hydroxyl terminated polycaprolactones and polyesters

of aliphatic dicarboxylic acids with 6 to 12 carbon atoms, such as sebacic acid, adipic acid, azelaic acid, suberic acid and dodecanedioic acid with, preferably even-numbered, glycols with chains with 2 to 6 carbon atoms, such as 1,4-butanediolo The acid component of the polyester polyol can be about 5 to about 25 % (on a molar basis) of a cycloaliphatic acid such as 1,4-cyclohexanedicarboxylic acid or 1,2-cyclohexanedicarboxylic acid to promote adhesion, especially to resin-rubber surfaces, and about 5 to about 25% (on a molar basis) of an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid to improve resistance to plasticizers. The glycol component can contain about 5 to about 15% (based on molar basis) diethylene glycol or a cycloaliphatic glycol, such as 1,4-cyclohexanedimethanol, in order to improve the adhesive and wetting properties and to produce better reactivity with water vapor. These polyols should have a molecular weight within the range of from about 1,000 to about 10,000, preferably from about 2,000 to about 4,000, _{or the like}

The polyurethane material which is applied to the surface to be bonded is prepared by reacting one or more of the polyols given above with a diisocyanate in such proportions that an NCO / OH ratio is achieved which is within the range from about 1.5 to about 3.0 iso Any of the available diisocyanates can be used, such as tolylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanato The polyurethane material is preferably prepared without the use of a catalyst and it is convenient to use a stabilizer such as an acid chloride such as benzoyl chloride, acetyl chloride or sebacoyl chloride , to be incorporated in an amount of about 0.05 to about 0.2% by weight, based on the polyurethane material ₀

It has been found that the using diphenylmethane

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Polyurethanes made from diisocyanate react with water much faster than polyurethane materials made using solylene diisocyanate, but the latter polyurethane materials are more stable on storage «. Because of the differences in reaction rate, it is preferred to add the tolylene diisocyanate first and allow it to react for a limited time so that the NCO group in the p-position can react with the POI7 / OI, after which the diphenylmethane diisocyanate is added can. Useful ratios between these diisocyanates can equal parts (on a molar basis) to 80 moles of diisocyanate to 20 mole T olylendiisocyanat be.

The rate of the chain extension reaction of the urethane layers can be increased by using catalysts »If a chain extension caused by moisture tertiary amines, such as N-methylmorpholine, triethylenediamine and other known catalysts such as dibutyltin dilaurate and stannous octoate are incorporated into the urethane material will. Generally, amounts of catalyst from about 0.05 to about 1 weight percent based on the weight of the urethane can be used will.

While urethane itself makes an excellent adhesive or coating, it may be useful to incorporate other materials such as plasticizers, fillers, and tackifiers. Plasticizers, especially normally solid plasticizers, serve to both reduce the viscosity of the urethane when it is melted state, as well as the properties of the finished film to modify _e softeners that are valuable in conjunction with the urethane include, dicyclohexyl phthalate, triphenyl phosphate, diphenyl phthalate and cycloaliphatic epoxides, or epoxy monomers bisphenol a

§09838 / 0918

Type. Tackifiers that are effective in enhancing the achievement of an adhesive bond include tackifiers of the hydrocarbon type, such as terpenes, e.g. α- and ß-pinene polymers, Low molecular weight styrenes such as poly-oc-methylstyrene and rosins “In the urethane masses Inert fillers such as clays, carbonates, titanium dioxide and others can also be incorporated.

It was found that the reaction of the diisocyanate with the polyol increases the crystalline melting point only a few degrees above the crystalline melting point of the polyol itself NCO / OH of 1.5: 1 is reacted, as the polyurethane has thereby obtained a crystalline melting point of only 54- ⁰ C.

The polyurethane material can be applied in the flowable state to a surface, for example to the sole bonding surface on the underside of a shoe upper or to the bonding surface of an outsole using a conventional application device or even by hand. It has been found that relatively low application temperatures, for example temperatures of 80 to 100 ° C, _o solvent polyurethane materials containing useful in solvent-free polyurethane materials having crystalline melting points of up to about 70 ⁰ C can be applied at room temperature or at slightly elevated temperatures _o

It is desirable that the thickness of the coatings of the urethane material be uniform so that the action of the chain extender is uniform over the entire extent of the thickness of the urethane coating or filler _o Preferably the coating has a thickness of about 0.025 to about 0.125 mm (1 to 5 mils) for achieving a highly satisfactory and equal

moderate chain extension over the entire thickness of the coating ₀ Relatively thin coatings, the thickness of which is only 0.025 mm, are effective on relatively regular surfaces, such as the bonding surface of an outsole, while coatings with a thickness of 0.075 mm on more irregular surfaces, such as o the sole bonding surface on the underside of a shoe upper can be applied. After the polyurethane has been applied, the material of the coating is preferably allowed to crystallize before it is subjected to chain extension. That is, the development of crystallinity serves to make the material resistant to deformation caused by the flow of the applied material under the higher temperatures to which the coating in the chain extension rod is exposed, _{or the like}

In order to bring the applied polyurethane into the state desired to achieve a bond, it is subjected to a chain extension treatment in which the surface of the coating is exposed to a compound with two active hydrogen atoms for reaction with the NCO groups of the polyurethane. A preferred chain extender is water, preferably in the form of steam or gaseous water, for example in a room with high humidity or in the vicinity of a water vapor source. Other chain extenders such as diamines or glycols can also be used. Preferably, temperatures slightly above room temperature are employed in the chain extension step and, with relative humidity of about 50 to about 95 ° / ° , temperatures of about 32 to about 88 ° C have been found to be effective in providing chain extension at an acceptable rate to ensure, for example within about 10 to about 30 minutes, without deformation of the urethane coating occurring ο The chain extension reaction should be carried out to such a degree that the film becomes elastoplastic on heat activation, but is not noticeably crosslinked, ie the film is still soluble or of active

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Polyurethane solvents such as dimethylformamide or tetrahydrofuran is attacked _o

After chain extension and after removal of the free water or other chain extenders from the surface of the urethane coating, the coating can be heated to bring it into an active adhesive state. Radiant heating is preferred, but other forms of heating, such as convection heating, can also be used. The heating should be carried out in such a way that at least the surface of the urethane coating is rapidly, preferably within about 15 to about 30 seconds , is brought to a temperature above the crystalline melting point, preferably to a temperature within the range of about 4-9 to about 82 ⁰ G, so that at least the surface is in a viscoelastic state that is compatible with a compatible surface, such as a Vinyl resin or adhesive layer on the object that is to be bonded to the coated surface can create an adhesive _{bond o} When using urethanes with crystalline melting points of up to about 70 ⁰ G, excellent bonds were achieved at bonding temperatures of only 5 ° G (9 ^{0 G)} I ¹ ) above the crystalline melting point _o

To complete the adhesive bond, the surfaces are brought together with the interposed heat-activated urethane and the resulting composite is subjected to pressure in order to ensure a good overall _{bond o} It has been found that a limited relative movement of the surfaces to be bonded against each other after the initial assembly and can be carried out before the pressure is applied because of the viscoelastic state of the adhesive, but that a bond with a high initial strength is achieved after the pressure is applied to the composite the adhesive will withstand the tension with success

can that when using a shoe with the means of the adhesive according to the invention to occur thereon attached «.

The coating or bonding process according to the invention has been described above with reference to the application of the Adhesive in the flowable molten state or in the form a solution described, but the process can also be carried out in such a way that one with the chain extender treated adhesive in the form of a film applied to a carrier or in the form of a self-supporting film and connects it in the heat-activated form with a compatible surface as a coating or between Compatible surfaces arranged as an adhesive bond between the surfaces

The invention is illustrated in more detail by the following examples, it should be noted, however, that the invention relates to the specific materials given in the following examples, Quantities and procedural details by no means is limited.

example 1

A prepolymer with a terminal NGO was prepared by reacting a butanediol adipate polyester with a terminal hydroxyl and a molecular weight of 2600 and a crystalline melting point of about 4-9 ° C. with Diphenylme chandiisocyanate in proportions such that an NCO / OH ratio of 1.5 was obtained ₀ the prepolymer thus obtained had a melting point of about 5 ^ ⁰ C and was flowable at a viscosity of about 8000 cP at 100 ⁰ C in the above and indicated in the examples below melting points it was crystalline melting points than Endothermee -Maxima were determined by thermal differential analysis _o

The prepolymer was melted and brought to a temperature of 100 ° C. and applied in the form of a 0.075 m thick coating to the previously roughened sole bonding surface of a shoe upper leather and to the bonding surface of an outsole made from a vulcanized synthetic butadiene / styrene copolymer rubber. The applied coatings were exposed to a high humidity atmosphere in a heating cabinet for 15 minutes at 70 ^° O to cause a reaction between the moisture and the NCO groups of the prepolymer to cause chain extension. After this treatment, the material was the coatings tough, it adhered firmly to the bond surface and could be calibrated at temperatures of about 65 G to a tacky state that adhered to similar adhesive surfaces. The coatings on the "bond surfaces" were subjected to infrared heat activation in a radiant heat activator for a period of 30 seconds, the thermal unit being set to a power of 60%. The sole was pressed against the bond surfaces of the underside of the shoe upper and the point bond was Excellent The entire assembly was pressed in a sole paste press to complete the bond, a strong initial bond was produced with no separation or "wrinkling" and the bond strength was satisfactory for the use of the shoe.

Example 2

2, yi · cm 17j78 cm large test strips made of the materials listed in Table I below were coated with the molten prepolymer of Example 1 at 80 to 90 ° G to achieve a layer thickness of 0.075 bobu Applying the coatings, the strips were placed in a high humidity atmosphere in a warming cabinet of 70 ⁰ G or in a room of about $ 6 C and a relative humidity of 68 % for the after-

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The periods given in the following table were placed in order to allow the NCO groups in the material of the coating to react with the water to effect chain extension. The strips were then activated by infrared heating in a conventional radiant heating activator (EHA) for 30 seconds , with the heat unit of the activator being set to a power of 60% ₀ As a result of the activation, the temperature of the coatings on the strips rose to about 68 to 75 ° C as. The activated strips were then, as indicated in Table I below, joined together in pairs and pressed together to complete the bonds, followed by cooling the combined together strips to room temperature and the bonds thereby obtained were subjected to a test _o the results of these tests are also shown in the following table.

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Table I.

Pre-test
poly no.
meris at
No.

Substrate Curing Activation Condition Point Initial Peel Strength Dead Load
conditions stipulations connection of the 16 at

time d.RHA-kle- days old 65.56 C
after d. Ligation bond
Curing dung

SBE sole

SBR soles

15 min. 70 ⁰ steam

15 min. 30 sec. Bad

at 60% ß ^e ~

ring

45

. 2 8th 9 Material material It Il Il It Il 28 RP - 1 3 »" 10 min. 70 ° C
Steam 20 hours Il very 7
Well out
draws , 70 kg 23 RP 5.08 cm
per hour 1 4th »" 15 min. 70 ° C
Steam II ti 9 M. , 07 kg 20th VP 1 5 ¹¹ vinyl 10 min. 70 ⁰ C
Gberteil water vapor
material It Il It 74 LP 0 cm
per hour 1 6th Leather / leather " 16 days Il very 8
Well very
high 35 - 1 7th SBR- SBR- 15 min. 70 ⁰ C
Sole- sole- water vapor
Material material Il Il It 36 1 "Vinyl"
Top part
material It Il Il 28 - 1 "Leather" 60 min. It , 61 kg 22nd RP 5.08 cm 1 "" 22 ⁰ C Std.35,6
(96 ⁰ P) 68% RH

Table I (continued)

Pre-test

poly no.

meri-

s at

No.

10

Substrate curing activation condi- tion point conditions time delay d.RHA- klenach d. Setting hardening

Initial peel strength dead load bond

16
Days old
binding

at
65.56 ⁰ C

SBR- Vinyl- 22 hours 35.6 ° C 30 seconds excellent- 7.25 kg soles- upper part- (96 ⁰ F) 68; ό HH 25 hours with 60% drawing material net

RF

co

CU

RF = rubber break
VF = vinyl break
LF = leather break

ad-

Example 3

An NCO-terminated prepolymer was prepared by reacting a hydroxyl-terminated butanediol adipate polyester with a molecular weight of 3000 and a melting point of about 50 G with a mixed diisocyanate in a molar ratio of 2 parts of diphenylmethane diisocyanate to 1 part of tolylene diisocyanate in such amounts that an NCOA OH- Ratio of 2.0 was achieved. The prepolymer obtained in this way had a melting point of etvra. 54- ⁰ C and was flowable at a viscosity of about 11,000 cP at 100 ° C.

There were 2.54 cm 17) 78 cm test strips made of an outsole sheet material, that as a surface-chlorinated "Kraton" is commercially available which is a styrene / butadiene block copolymer the surface of which has been chlorinated, made of a polyvinyl chloride outsole sheet material and a styrene / butadiene copolymer outsole material. Similar stripes were made from the bodice material as well (Upper leather material) cut, which is the polyvinyl chloride applied to a base, known as "Pattina", and contained leather

The strips of the outsole material were coated with the molten prepolymer at 80 to 90 ^° C. to achieve a coating thickness of 0.075 mm and after the coatings had been applied and cooled, the strips were placed in an atmosphere with a high humidity of 90 % EH about 1 / Placed in a heating cabinet at 70 ^° C. for 4 hours. The strips of the upper material (upper leather material) were each coated with a solvent-type polyurethane adhesive (Estane) on the backed polyvinyl chloride upper material and with a phenolic resin-polychloroprene-sole adhesive bonding agent of the solvent type on the upper leather material allowed to dry to remove solvent.

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The surfaces of the outsole material test strips and upper shoe material test strips coated with the adhesive were introduced into a radiant heat activator for 10 seconds, the radiant heat unit being set to a power of 55 % . The surface temperature of the adhesive on the surfaces of the strips was about 80 ⁰ G ₀

Strips of the adhesive coated, backed polyvinyl chloride upper material were made with strips of the block polymer outsole material coated with the adhesive and combined with the styrene / butadiene copolymer outsole material and strips off the leather coated with the adhesive were matched with the polyvinyl chloride outsole material combined and the composite assemblies pressed to complete the bonds. When tested after 7 days, the peel bond strengths were 14.06 kg per 2.54 cm (linear inch) between the polyvinyl chloride material and the block copolymer, 12.25 kg per 2.54 cm (linear inch) between the leather and the polyginyl chloride outsole material and 17.69 kg per 2.54 cm (linear inch) between the polyvinyl chloride material and the styrene A Butadiene copolymer outsole material.

Example 4

A prepolymer with NCO at the end was prepared by reacting diphenylmethane diisocyanate with a polycyclic prolactone with a molecular weight of about 2860 and a melting point of about 54 ° C., the prepolymer having a content of free NGO groups of 2.18% brought to a temperature of 100 ⁰ O and applied in the form of a 0.075 mm thick coating to a previously roughened surface of an outsole material consisting of a styrene / isoprene / styrene block copolymer. The applied coating was applied in a heating cabinet at 70 ° G for 30 minutes Long exposed to a humid atmosphere of 95 % RH in order to mix with the NCO groups

609838- / 0979

of the prepolymer to implement to achieve chain extension _o

A viscous adhesive was made by. Dissolving a thermoplastic linear polyester urethane elastomer in a solvent mixture of approximately equal parts of tetrahydrofuran and methyl ethyl ketone, the solids content of this solution being about 20 % of 1 mol of an OH-terminated polyester, an aliphatic glycol and a diphenyl diisocyanate was prepared in such proportions that practically no unreacted isocyanate or hydroxyl groups remained _o The solution obtained had a viscosity at room temperature of about 2000 to about 3000 cP, determined with the Brookfield viscometer.

The above solvent-type adhesive was brushed onto the previously roughened surface of a polyvinyl chloride shoe upper on a G-woven fabric backing 24 hours after the adhesive was applied to the backed polyvinyl chloride material, the coating was subjected to infrared heat activation in a radiant heat activator for 30 seconds, wherein the thermal unit was set to a power of 60 % ₀ The heat-activated polyvinyl chloride material applied to a base was pressed with its adhesive-coated surface against the correspondingly heat-activated adhesive coating on the block copolymer sole material. The spot-bonding was good _e The arrangement thus obtained was pressed together for completion of the binding, "the initial binding, determined by the peeling test, was 6.80 to 9.07 kg per 2.54 cm (linear inch) _e If the binding after 7 days When tested, the peel bond strength was 20.41 kg per 2.54 cm (linear inch) and the break occurred in the block copolymer ο

Example 5

The procedure of Example 4- was repeated, this time instead of the block copolymer material a styrene A. Butadiene block copolymer / rubber outsole material was used, the arrangement had a good initial tack, a very good initial bond strength and a peel bond strength after 7 days of 17.69 kg per 2.54 cm (linear inch) o In this case the break occurred in the one Underlay applied polyvinyl chloride shoe upper material on "

Example 6

The prepolymers indicated below terminated NGO were prepared by reacting polyols with diphenylmethane diisocyanate in amounts specified in the further Table II below NG0 / 0H ratios _o The polyol of the prepolymer 2 concerned it is a polycaprolactone having a molecular weight of 2890 and a melting point of about 56 ⁰ and the prepolymer was prepared by reacting the polyol with diphenylmethane diisocyanate in proportions such that an NCO / OH ratio of 1.75 was achieved. The polyol of the prepolymer 3 there was a Butandiolsebacatpolyester terminated OH and a molecular weight of about 2000 and a melting point of about 64 ⁰ C and the prepolymer was prepared by reacting the polyol with diphenylmethane diisocyanate in proportions such that an NGO / OH ratio of 1.75 was achieved «,

2.5 cm by 17.78 cm in size test strips made of the materials given in Table II below were coated with the molten prepolymer at 80 to 90 ° G to achieve a coating thickness of 0.075 m. After 15 minutes, measured from the application of the Coating, the strips were placed in a 70 ⁰ G warming cabinet with a high humidity atmosphere for 15 minutes to allow the reaction of the

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To effect NCO groups in the material of the coating with the water and the chain extension to recoverable en _o The strips were then activator by infrared heating in a conventional radiant heat (EEA) is activated for a period of 30 seconds, with the thermal unit of the activator to a Power of 60 % has been set.

Upon activation, the temperature of the coatings on the strip rose to about 68 to about 75 ° C. The activated strips were then paired as indicated in the table below and to complete the bonds pressed, after which the assembled strips were cooled to room temperature and the bonds obtained were tested. the Results obtained in the tests are summarized in the table below.

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Table II

Pre-test poly- Mr. meri-. sat no.

Substrate curing activation condi- tion point initial pull-off dead load conditions stipulations connection of the 16 at

time d.EHA- kle- days old 65.56 o after d «setting binding
Curing dung

SBE- SBE- 15 min. 70 min. 30 sec. Off- 10.48 kg 38
Soles soles water vapor at 60%

Material Material 7O ⁰ O net

5 surface-vinyl _o 15 min. Chenchlorier- above 70 tes partially water-styrene, styrene-butadiene material atten at Blockmischpolymeris

O min o 30 sec " at 60%

3.18 kg 67

EF O cm cn

per hour CD

ro cn cn

2 2 dd π Il 5 Hours. Il Il 8.16 kg 45 EF 2 3 ti Vinyl-
Whether grant-
material It dd Il Il 27 CSP 2 4th Il ti dd 23 Hours. dd ti 4.08 kg 35 EF

KF O cm

per hour

3 6th ti Il Il 3 hours. It ti 9 , 07 kg 60 Theatrical Version 2.54 cm
per hour 3 7th SBE-
Sole
material SBE-
Sole
material It Il Il ιΓ 8th , 16 kg 24 EF 3 8th "II Vinyl-
Top part
material ti Il H Il 5 , 44 kg 22nd EF

Table II (continued)

Pre-test poly- no. Meris at no.

Substrate Curing Activation Condition Point Initial Peel Strength Dead Load conditions stipulations connection of the 16 at

time d.EHA- kle- days old 65.56 ⁰ C after d. Setting bond hardening

Vinyl vinyl sole uppers material

15 min. 70 ⁰ O

Steam off for min. 30 sec. 10.43kg 20
at drawing
% net

10

Styrene isopro

pyi-

Block copolymer 8.16 kg 50

KF 2.54- cm per
Hours.

SBE- SBR-

Sole-Sole-Mater eial material days

29

EF

EF = rubber break YF = vinyl break

OSP = binder strips from Pattina

KF = styrene / butadiene / styrene block copolymer fraction

PF = break in the vinyl top Ol CD (JO NJ CT) CO

-25- 26G9266

Example 7

An ETGO-terminated prepolymer was prepared by reacting a hydroxyl terminated butanediol adipate polyester with a molecular weight of 2600 and a crystalline melting point of about 49 ° C. with diphenylmethane diisocyanate in proportions such that an NCO / OH ratio of 1.5 was achieved. The prepolymer obtained thereby had a melting point of about 54- ⁰ C and was flowable at a viscosity of about 8000 cP at 100 ⁰ O. The prepolymer was dissolved in a solvent mixture of 4 parts of methylene chloride and 1 part of toluene to form a solution with 60 wt .-%! Solids · The solution had a viscosity of about 1500 cP.

The solution was applied in the form of 0.127 mm thick coatings on the previously roughened surface of a shoe leather upper material and on the surface of an outsole material made from a vulcanized synthetic butadiene / styrene mixed polymer rubber, and the coatings were dried. The coatings were exposed to an atmosphere with high humidity in a heating cabinet at 70 ° C. for 15 minutes to allow the humidity to react with the NCO groups of the polymer in order to effect the chain extension. After this treatment, the material of the coatings became tough, it adhered firmly to the surfaces and could be softened at temperatures of about 65 ° to a tacky state in which it adhered to similar adhesive surfaces. The coatings were subjected to infrared heat activation for 20 seconds in a radiant heat activator with the thermal unit set at 55 % power. The surfaces are joined together and pressed to complete the bond. When tested after 7 days, the peel bond strength was 18.14 kg per 2.54-cm (linear inch) _o

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Example 8

A prepolymer solution was prepared as in Example 7, but contained 0.25 % dimethylpiperazine, based on the weight of the prepolymer. The solution was applied in the form of a layer to leather and to a vulcanized synthetic butadiene / styrene copolymer rubber and the coatings were dried as in Example 7. Chain extension was effected by exposing the coatings to an atmosphere with a relative humidity of only 18 to 20 % at 85 ° C for 15 minutes in order to render the coatings in a tough, firmly adhering state. The coatings were then heat activated and the leather and synthetic rubber were combined and pressed as in Example 7. The peel bond strength after 7 days was 18.14 kg per 2.54 cm (linear inch).

Example 9

A prepolymer terminated NGO was prepared by reaction of a polycaprolactone having a molecular weight of 2860 and a crystalline melting point of about 54 ⁰ C with diphenylmethane diisocyanate in proportions such that a free NCO G-ehalt scored by 2.18%. The prepolymer was dissolved in toluene to form a solution with a solids content of 60% by weight. “The solution had a viscosity of about 1600 cP.

The solution was applied in the form of 0.127 mm thick coatings to the previously roughened surface of a polyvinyl chloride shoe upper material provided with a backing and to the surface of an outsole material consisting of a styrene / butadiene / styrene block copolymer For minutes at 70 ⁰ G exposed to an atmosphere with a relative humidity of 90 ^c / o for the reaction of the moisture with the NCO

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Groups of the prepolymer to bring about the extension of the chain After this treatment, the material of the coatings was tough and adhered firmly to the surfaces and could be softened at temperatures of about 65 ° C to a tacky state in which it was similar Adhesive Surfaces Adhered ο The coatings were subjected to infrared heat activation in a radiant heat activator for 20 seconds, the thermal unit being set at 55%. The surfaces were joined together and pressed to complete the bond. The 7 day test showed the ^{peel bond strength to be 19.15 kg P 1} * ⁰ 2.54 cm (linear inch).

Patent claims:

609838/0978

Claims (1)

Claims Process for covering or adhesive bonding of surfaces, characterized in that: on the surface a molded body (object) applies a polymeric urethane which contains reactive NCO groups and consists of segments with a relatively low crystalline melting point, the reactive NCO groups in the urethane in such quantitative proportions are present that they form a polyurethane after the chain extension of the polymeric urethane, that is viscoelastic when heated to a temperature above its crystalline melting point, and that one a compound providing active hydrogen atoms with the Bringing urethane into contact, which react with the ECO groups to cause chain extension in the polymeric urethane. 2. The method according to claim 1, characterized in that the polymer urethane is a prepolymer with a terminal NCO is used, which has been produced by reacting a diisocyanate with a polymeric polyol in proportions such as that one obtains an NCO / OH ratio that is within of the range from about 1.25: 1 to about 3.0: 1 is one crystalline melting point within the range of about 40 up to about 90 ° 0 and a molecular weight within the range from about 1000 to about 10,000 and that is flowable in unity into the state and applied in the form of a coating β 5 ο method according to claim 2, characterized in that the polyurethane for application in the form of a coating converted into a flowable state by heating to a temperature above its crystalline melting point. 4. The method according to claim 2, characterized in that the prepolymer for application in the form of a coating 609838/0978 converted into a flowable state by dissolving in a volatile organic solvent Process according to Claim 2, characterized in that the polymeric polyol is a hydroxyl-terminated polyester from the group of polyeaprolactones and aliphatic. Polyester of dicarboxylic acids with 6 to 12 carbon atoms and glycols with 2 to 6 carbon atoms, wherein the polyol has a molecular weight of about 2000 to about 4000 and a crystalline melting point of about 40 to about 60 ⁰ C and wherein the diisocyanate and the polyol in such Quantitative ratios are reacted with one another that an NGO / OH ratio is achieved which is within the range of about 1.5 * 1 to about 2.5: 1, and that the prepolymer is converted into a flowable state and applied in the form of a coating will", 6, method according to claim 1, characterized in that as a compound containing active hydrogen atoms, water is used, which is in the form of a gas or in the form of water vapor is present when contacted with the polymeric urethane to effect chain extension, and that the chain extender treated polyurethane while still in a heat softened viscoelastic State is present at a temperature above its crystalline melting point, against a coating a heat activated adhesive made with the polyurethane treated with the chain extender on the adhesive surface of a second molded body (object) is compatible (compatible), is pressed and that then the polyurethane treated with the chain extender converted into a tough, solid state by cooling by firmly binding the second shaped body to the first-mentioned shaped body 809838/0978 7. The method according to claim 6, characterized in that the polymeric urethane is a prepolymer with terminal UCO that has been manufactured by. Reaction of a diisocyanate with a polymeric polyol in such amount ratios that an NCO / OH ratio is achieved which is within the range of about 1.25: 1 t> is about 3.0: 1 is that the prepolymer has a crystalline melting point within the range of about 4-0 to about 90 ° 0 and a molecular weight within the range of about 1000 to about 10,000 and converted into a flowable state and is applied in the form of a coating. 8ο The method according to claim 7 »characterized in that the polymeric polyol is a hydroxyl-terminated polyester from the group of polyeaprοlactones and the aliphatic polyesters of dicarboxylic acids with 6 to 12 carbon atoms and glycols with 2 to 6 carbon atoms, the polyol has a molecular weight of about 2000 to about 4000 and a crystalline melting point of about 4-0 to about 60 ⁰ O, that the diisocyanate and the polyol are reacted with one another in such proportions that an NCO / OH ratio is achieved which is within the In the range from about 1.5: 1 to about 2.5: 1, the prepolymer is converted into a flowable state for application in the form of a coating by heating it to a temperature above its crystalline melting point, and that with the chain extender treated polyurethane by heating to a temperature at least about 5 ° C above its crystalline The melting point before joining with the adhesive is converted into a viscoelastic state for train on the second molded body. 9 · The method according to claim 7 »characterized in that it the polymeric polyol is a hydroxyl-terminated polyester from the group of polycaprolactones and aliphatic Polyester of dicarboxylic acids with 6 to 12 carbon atoms and glycols with 2 to 6 carbon atoms, 609838/0978 that the polyol has a molecular weight of about 2000 to about 4000 and a crystalline melting point of about 40 to about 60 ° 0 has that the diisocyanate and the polyol in such Amount ratios with each other converts that an NCO / OH ratio is achieved which is within the range of about 1.5 * 1 up to about 2.5 * 1 is that you can apply the prepolymer converted into a flowable state in the form of a coating, by dissolving it in a volatile organic solvent and treating it with the chain extender Polyurethane by heating to a temperature which is at least about 5 ° C above its crystalline melting point lies, before combining with the adhesive coating on the second Molded body converted into a viscoelastic state, 10. The method according to claim 8, characterized in that it is the first-mentioned shaped body (object) the adhesive surface of a shoe sole part and in the The second molded body (object) is the adhesive surface of the upper of a shoe, the cover being in front of the chain extension is cooled to a temperature below the crystalline melting point of the polymeric urethane and that for the chain extension used water vapor has a temperature of about 32 to about 95 ° C. 11. The method according to claim 9 »characterized in that the first-mentioned shaped body (object) is the bonding surface of a shoe sole part and, in the case of the second molded body (object), around the bonding surface of a shoe upper, the volatile organic liquid evaporating from the cover before the chain is extended and the water vapor used for chain extension has a temperature of about 32 to about 95 ° C. 12. The method according to claim 10, characterized in that the prepolymer is a catalyst for the reaction between the prepolymer and the active water contain st of fat omen 609838/0978 13. The method according to claim 11, characterized in that that the prepolymer is a catalyst for the reaction between the prepolymer and the active hydrogen atoms contains. 14- "Method according to claim 10, characterized in that that the adhesive on the surface of the second molded body (article) is a polyurethane of the same class as that Polyurethane on the first-mentioned molded body (article) is. 15 · The method according to claim 11, characterized in that the adhesive on the surface of the second molded body (Object) a polyurethane of the same class as the polyurethane on the first-mentioned molded body (object) is. 8Ö9838 / 0978