CA1076729A - Primer for oily surfaces - Google Patents
Primer for oily surfacesInfo
- Publication number
- CA1076729A CA1076729A CA244,386A CA244386A CA1076729A CA 1076729 A CA1076729 A CA 1076729A CA 244386 A CA244386 A CA 244386A CA 1076729 A CA1076729 A CA 1076729A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- block
- weight
- conjugated diene
- rubbery
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S524/903—Aerosol compositions
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/901—Radial block
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/931—Blend of stated incompatibility
-
- 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]
- Y10T428/31855—Of addition polymer from unsaturated monomers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Abstract Oily or other difficultly adherable surfaces are rendered receptive to pressure-sensitive adhesives when sprayed or coated with an organic solvent solution or dispersion of certain rubbery block copolymers and an unusually large amount of thermoplastic resin, prefera-bly a blend in which at least one resin is compatible with each block of the copolymer.
Description
~12,o88 ~- iO7~7~9 PRIMER FOR OILY SURFACES
This invention relates to a method of rendering oily and other difficultly adherable surfaces receptive to pressure-sensitive adhesives and to a primer having parti-cular utility for that function.
In many fields of industry there are occasions when it is desired to apply a pressure-sensitive adhesive-coated sheet material to a greasy or oily surface. For example, filament tape is sometimes used ko bind pipes together to facilitate handling; since such pipes are often coated with oil during manufacture or storage, it is difficult to obtain a firm bond with the tape. In other instances, it is desired to adhere anti-slip sheet material to the floor surfaces around a lathe or other piece of machine shop equipment, where the floor is fre-quently slippery because of the presence of oil. Lanemarking tape is often adhered to factory floors to de-fine areas and indicate passageways, and many factory floors are contaminated by the presence of oil.
In all instances where a normally tacky and pressure-sensitive adhesive tape is applied over an oily surface, the oil tends to prevent the adhesive from form-ing an intimate contact with the substrate. Even where extreme pressure is applied to promote such contact, the oil tends to plasticize the adhesive and render it more or less ineffective. It is, of course, essential that the adhesive establish and maintain intimate contact with the substrate, since a bundling tape which slips or a nonslip floor marking which comes loose may generate a -misplaced confldence and hence be worse than none.
~$
~ 7672~
Recognizing the problem of obtaining adhesion to oily substrates, the prior art has resorted to such techniques as scrubbing the contami~nated surface vigor-ously with a steel brush, washing with solvent, or both.
Such techniques, whi~le effective to a degree, are tedious, time-consuming and expensive. The present invention pro-vides a unique, simple, and i-nexpensive alternative.
The present invention provides a means for obtain-ing excellent adhesion of normally tacky and pressure-sensitive adhesive-coated Products to oily and greasy substrates, greatly enhancing the bonding power of the ad-hesive thereto, both initially and after extended periods of contact. The invention eliminates the need for the tedious and expensive cleaning methods which were previously thought to be essential and thus widens the field of po-tential application for a variety of pressure-sens;tive adhesive-coated sheet materials.
In accordance with the invention, there is pro-vided an organic solvent solution or stable dispersion of a ;
blend of rubber and tackify-ing resin, the solids thereof con-sisting essentially of, on a weight basis, 15-35 parts of rubbery polymer consisting essentially of rubbery block co-polymer selected from the class consisting of (1) rubbery block copolymer having the general configuration A-B-A where-in each A is a thermoplastic polymer block which has a glasstransition temperature above 20Ct, which is relatively in-compatible with the B block and which has an average molec-ular weight between about 5,QQ0 and 125,000; B is an elastomeric polymer block of a conjugated diene, having an average molecular weight between about 15,0Q0 and 250,000, B
10 ~ 3 the total weight of the A block being less than about 80% of the weight of theblock copolymer, and (2) radial teleblock co-polymer consisting of several polystyrene-terminated elas-tomeric branches, each of said branches being a homopolymer of a conjugated diene extending from a central hub; and correspondingly 85-65 parts of tackifying resinous components.
A particularly preferred rubbery block copolymer for use in practicing the invention is a radial teleblock copolymer consisting of several polystyrene-terminated elastomeric branches formed from a conju~ated diene and extending from a central hub.
In block copolymers of the type described, the polydiene and polystyrene portions are compatible and form a two-phase system consisting of sub-micron sized "domains"
of glassy polystyrene interconnected by flexible polydiene chains. These "domains" serve to crosslink and reinforce the structure, giving rise to an elastomeric network which behaves as though it were filled and chemically crosslinked.
This network structure, in contrast with that of chemically crosslinked rubbers, is reversible, and either heating the polymer above the softening point of polystyrene or dis-solving it in a suitable solvent temporarily disrupts the structure, ~hich can be restored by either lowering the temperature or evaporating the solvent.
Solutions prepared in accordance with the inven-tion are used to prime oily surfaces so as to render them receptive to normally tacky and pressure-sensitive adhe-sive composistions by simply applying the solution to the oily substrate and allowing the solvent to evaporate.
Thereafter, normally tacky and pressure-sensitive adhesive ~.~
1076~Zg tape applied to the primed surface requlres a force of at least 900 (preferably at least 1300) grams per centimeter of width for removal. Similarly, the present invention provides a means for enhancing the adhesion of pressure-sensitive adhesive tape and related products to suchother dlfficultly adherable surfaces as green, pitch-covered or creosoted wood, uncured concrete, and cinder blocks.
In a particularly preferred embodiment of the invention, the solution is provided in a pressurized aerosol-type container, thereby facilitating application.
As used throughout all subsequent discussions herein, all parts and percentages are by weight unless otherwise noted.
Priming Effectiveness Test. In order to eval-uate the effectiveness of the priming compositions of the invention, it has been found desirable to employ a test which simulates field conditions. In this test, tin-plated steel panels approximately 0.3 mm thick and 16.5 x 25.4 centimeters in area are coated on one side with 0.25 gram + -? gram of a viscous mineral base oil, similar to that employed in vacuum pumps. A sample formulation to be tested is then applied to the panel by brushing it on over a 5-centimeter wide path extending the entire length of the panel, so as to leave, after evaporation of the solvent, a primer coating of 0.25 gram + 0.06 gram. The solvent is allowed to evaporate over a l-l/2-hour period, after which a 12.7-mm wide strip of testing tape is applied to the primed surface, extending along the primed path. A light weight roller (approximately 400 grams) ls used to roll down the tape sample, whlch is then allowed to remain ln place for two hours. The tape ls then removed from the test panel by doubllng one end back on ltself and pulling it so that it extends over the opposite end of the panel. The ex-posed end of the panel ls then clamped in the upper jaws of a tensile testlng machlne and the free end of the tape grasped in the opposite ~aws, the ~aws then being separated at a rate of approximately 25 centimeters per mlnute whlle measuring the force required to strlp away the tape. The priming composition is deemed successful if the force re-quired to rembve the tape ls at least about 1100 grams, or approximately 900 grams per centlmeter of width.
Because it ls desirable for a primer to function effectively with a wide varlety of normally tacky and pressure-sensitive adhesive tapes, the foregoing test is preferably run with two test tapes having distinctly dlf-ferent rubber-resin pressure-sensitive adhesives, priming being deemed adequate if satisfactory adhesion of at least one tape is achieved. These tapes, hereinafter identified as "A" and "B", may be characterized as follows:
Tape t'A" -- a high adhesion tape having the ability to form firm bonds quickly. The backing is a smooth paper, having a basis weight of 32 lbs per paper-maker's ream (53 g/m2)? saturated with a rubber-resin blend. The pressure-sensitive adhesive is formed by com-pounding 100 parts of natural rubber, 52 parts of heat treated wood rosin, 27 parts of gum rosin, 3 parts calcium hydroxide and 0.95 part di-pentamethylene thiuram tetra-sulfide. This tape is commercially available from 107~;~Z9 Minnesota Mining and Manufacturing Company undër the tradedesignation "No. 254". Tape "B" -- a moderately high adhesion tape C having a firm ad~esive. The backing is 1.4-mil (35-~g,s~r e 6~ ~oG~e~ ~ f A~) 5 micron) cellophane~ and the adhesive is a "bakelized"
rubber-resin formed by compounding 100 parts of rubbery butadiene:styrene copolymer, 60 parts esterified gum rosln, 40 parts coumarone-indene resin, 12 parts phenol-formalde-hyde resin, and extenders, stabilizers, pigments, etc. as 10 desired.
For convenience, suitable components for prepar-ing effective primer compositions in accordance with the invention will now be indicated.
Rubbery Block Copolymer. The following styrene:
15 butadiene block copolymers have been found satisfactory:
styrene:butadiene:styrene rubbers having a styrene:rubber ratio of approximately 15:85 to 30:70; styrene:isoprene:
styrene copolymers having a styrene:rubber ratio of 14:86 and a solution viscosity of 1600 cps, and styrene:butadiene 20 radial teleblock copolymers having a styrene:butadiene ratio of 30:70 and an inherent viscosity in tetrahydro-furan of 1.50.
While it is essential for purposes of this in-vention that the primer composition contain a rubbery 25 block copolymer of the type previously described, it is possible to extend the composition by adding minor amounts of other types of rubbery materials, e.g., random buta-diene:acrylonitrile copolymers, random butadiene:styrene copolymers, crude rubber, polyisoprene, etc. Speaking in 30 general terms, these rubbery materials tend to reduce the `~ 107~7;~S~
effectiveness of the primer composition. They sh~uld be included, if at all, in limited quantlties Thermoplastic resins which are compatible with polystyrene and suitable for the practice of this lnven-tion include hydrocarbon resins, coumarone-indene reslns, polyalphamethyl styrene, polyalphamethyl styrene:vinyl toluene copolymers, polystyrene, dimerized rosin~ metal resinates, phenollc resln, copolymers of piperylene, etc.
Thermoplastic resins which are compatible wlth lO synthetic rubbers of the type described and suitable for ;
the practice of the invention include a wide variety of polymerized mixed olefins, glycerol esters of hydrogenated ros~n, pentaerythritol esters of hydrogenated rosin, glycerol esters of highly stabilized rosin, pentaerythritol esters of highly stabilized rosin, polyterpene resins, terpenephenolic resins, heat treated wood rosins, highly stable cycloaliphatic hydrocarbon resins, synthetic terpene polymers, tall oil resins, etc.
As used herein, the term ~'compatible" is intended to refer to those resins which are structurally sufficiently similar to the block referred to that a solution containing a solute formed solely of equal parts of resin and block material will dry to a transparent film.
The solvents used in preparing compositions of the invention preferably constitute a blend of organic solvents, including at least some aromatic solvent.
~here, for example, the primer solution is to be applied by roller-coating, brushing, etc., a suitable combination of solvents lncludes 60% ketones (`e.g., 30% each of ace-tone and methyl ethyl ketone), 30% heptane, and 10%
10767~g toluene. For such applicatlons, the solvent may con-stitute about 2/3 the total weight of the solution.
Where primer compositions of the invention are to be applied from aerosol containers, the percent solids of the solution is typically somewhat lower than in the case of solutions applied from bulk, a solution containing 20-30% solids having been found quite satisfactory.
Aerosol packages must include as propellant low molecular weight compound which boils below 25C. In compositions to be dispensed from an aerosol package, it is preferred to employ as solvent a blend of about 5% toluene and 95%
of such halocarbons as trichloroethylene, methylene chloride, chloroform and the like. Such chlorocarbons are especially desirable, since they perform the addi-tional functions of solubilizing oil or grease and helping maintain the rubbery copolymer in solution. A
blend of low molecular weight aliphatic hydrocarbons (e.g., a 30:70 propane:isobutane) is effective as a propellant.
In addition to the components previously des-cribed for incorporation in the primer compositions of the invention, it may also be desirable to include various other components. It has been found, for example, that it is desirable to include a minor but effective amount of an anti-oxidant such as symmetrical dibeta-naphthol-p-phenylene diamine, polymerized 1,2-dihydro-2,2,4-tri-methyl quinoline, 1,3,5-trimethyl-2,4,6-tris(3,5-di tert-butyl-4-hydroxy-benzyl) benzene, modified hindered phenols, tetra-bis-methylene-3(3',5'-tert-butyl-4'-hydroxy phenyl propionate) methane, octadecyl-beta-(3,5-tert-butyl-4-10~i729 hydroxy phenyl) proplonate, 2,2'-methylene'bis(4-methyl-6-tert-butyl phenol), steryl thiodlpropionate, etc.
As a further aid to understanding the inventlon, a series of tabulated examples will be set forth below.
In each of these examples, the components descrlbed were blended, together with approximately 0.4% 1,3,5-trimethyl-
This invention relates to a method of rendering oily and other difficultly adherable surfaces receptive to pressure-sensitive adhesives and to a primer having parti-cular utility for that function.
In many fields of industry there are occasions when it is desired to apply a pressure-sensitive adhesive-coated sheet material to a greasy or oily surface. For example, filament tape is sometimes used ko bind pipes together to facilitate handling; since such pipes are often coated with oil during manufacture or storage, it is difficult to obtain a firm bond with the tape. In other instances, it is desired to adhere anti-slip sheet material to the floor surfaces around a lathe or other piece of machine shop equipment, where the floor is fre-quently slippery because of the presence of oil. Lanemarking tape is often adhered to factory floors to de-fine areas and indicate passageways, and many factory floors are contaminated by the presence of oil.
In all instances where a normally tacky and pressure-sensitive adhesive tape is applied over an oily surface, the oil tends to prevent the adhesive from form-ing an intimate contact with the substrate. Even where extreme pressure is applied to promote such contact, the oil tends to plasticize the adhesive and render it more or less ineffective. It is, of course, essential that the adhesive establish and maintain intimate contact with the substrate, since a bundling tape which slips or a nonslip floor marking which comes loose may generate a -misplaced confldence and hence be worse than none.
~$
~ 7672~
Recognizing the problem of obtaining adhesion to oily substrates, the prior art has resorted to such techniques as scrubbing the contami~nated surface vigor-ously with a steel brush, washing with solvent, or both.
Such techniques, whi~le effective to a degree, are tedious, time-consuming and expensive. The present invention pro-vides a unique, simple, and i-nexpensive alternative.
The present invention provides a means for obtain-ing excellent adhesion of normally tacky and pressure-sensitive adhesive-coated Products to oily and greasy substrates, greatly enhancing the bonding power of the ad-hesive thereto, both initially and after extended periods of contact. The invention eliminates the need for the tedious and expensive cleaning methods which were previously thought to be essential and thus widens the field of po-tential application for a variety of pressure-sens;tive adhesive-coated sheet materials.
In accordance with the invention, there is pro-vided an organic solvent solution or stable dispersion of a ;
blend of rubber and tackify-ing resin, the solids thereof con-sisting essentially of, on a weight basis, 15-35 parts of rubbery polymer consisting essentially of rubbery block co-polymer selected from the class consisting of (1) rubbery block copolymer having the general configuration A-B-A where-in each A is a thermoplastic polymer block which has a glasstransition temperature above 20Ct, which is relatively in-compatible with the B block and which has an average molec-ular weight between about 5,QQ0 and 125,000; B is an elastomeric polymer block of a conjugated diene, having an average molecular weight between about 15,0Q0 and 250,000, B
10 ~ 3 the total weight of the A block being less than about 80% of the weight of theblock copolymer, and (2) radial teleblock co-polymer consisting of several polystyrene-terminated elas-tomeric branches, each of said branches being a homopolymer of a conjugated diene extending from a central hub; and correspondingly 85-65 parts of tackifying resinous components.
A particularly preferred rubbery block copolymer for use in practicing the invention is a radial teleblock copolymer consisting of several polystyrene-terminated elastomeric branches formed from a conju~ated diene and extending from a central hub.
In block copolymers of the type described, the polydiene and polystyrene portions are compatible and form a two-phase system consisting of sub-micron sized "domains"
of glassy polystyrene interconnected by flexible polydiene chains. These "domains" serve to crosslink and reinforce the structure, giving rise to an elastomeric network which behaves as though it were filled and chemically crosslinked.
This network structure, in contrast with that of chemically crosslinked rubbers, is reversible, and either heating the polymer above the softening point of polystyrene or dis-solving it in a suitable solvent temporarily disrupts the structure, ~hich can be restored by either lowering the temperature or evaporating the solvent.
Solutions prepared in accordance with the inven-tion are used to prime oily surfaces so as to render them receptive to normally tacky and pressure-sensitive adhe-sive composistions by simply applying the solution to the oily substrate and allowing the solvent to evaporate.
Thereafter, normally tacky and pressure-sensitive adhesive ~.~
1076~Zg tape applied to the primed surface requlres a force of at least 900 (preferably at least 1300) grams per centimeter of width for removal. Similarly, the present invention provides a means for enhancing the adhesion of pressure-sensitive adhesive tape and related products to suchother dlfficultly adherable surfaces as green, pitch-covered or creosoted wood, uncured concrete, and cinder blocks.
In a particularly preferred embodiment of the invention, the solution is provided in a pressurized aerosol-type container, thereby facilitating application.
As used throughout all subsequent discussions herein, all parts and percentages are by weight unless otherwise noted.
Priming Effectiveness Test. In order to eval-uate the effectiveness of the priming compositions of the invention, it has been found desirable to employ a test which simulates field conditions. In this test, tin-plated steel panels approximately 0.3 mm thick and 16.5 x 25.4 centimeters in area are coated on one side with 0.25 gram + -? gram of a viscous mineral base oil, similar to that employed in vacuum pumps. A sample formulation to be tested is then applied to the panel by brushing it on over a 5-centimeter wide path extending the entire length of the panel, so as to leave, after evaporation of the solvent, a primer coating of 0.25 gram + 0.06 gram. The solvent is allowed to evaporate over a l-l/2-hour period, after which a 12.7-mm wide strip of testing tape is applied to the primed surface, extending along the primed path. A light weight roller (approximately 400 grams) ls used to roll down the tape sample, whlch is then allowed to remain ln place for two hours. The tape ls then removed from the test panel by doubllng one end back on ltself and pulling it so that it extends over the opposite end of the panel. The ex-posed end of the panel ls then clamped in the upper jaws of a tensile testlng machlne and the free end of the tape grasped in the opposite ~aws, the ~aws then being separated at a rate of approximately 25 centimeters per mlnute whlle measuring the force required to strlp away the tape. The priming composition is deemed successful if the force re-quired to rembve the tape ls at least about 1100 grams, or approximately 900 grams per centlmeter of width.
Because it ls desirable for a primer to function effectively with a wide varlety of normally tacky and pressure-sensitive adhesive tapes, the foregoing test is preferably run with two test tapes having distinctly dlf-ferent rubber-resin pressure-sensitive adhesives, priming being deemed adequate if satisfactory adhesion of at least one tape is achieved. These tapes, hereinafter identified as "A" and "B", may be characterized as follows:
Tape t'A" -- a high adhesion tape having the ability to form firm bonds quickly. The backing is a smooth paper, having a basis weight of 32 lbs per paper-maker's ream (53 g/m2)? saturated with a rubber-resin blend. The pressure-sensitive adhesive is formed by com-pounding 100 parts of natural rubber, 52 parts of heat treated wood rosin, 27 parts of gum rosin, 3 parts calcium hydroxide and 0.95 part di-pentamethylene thiuram tetra-sulfide. This tape is commercially available from 107~;~Z9 Minnesota Mining and Manufacturing Company undër the tradedesignation "No. 254". Tape "B" -- a moderately high adhesion tape C having a firm ad~esive. The backing is 1.4-mil (35-~g,s~r e 6~ ~oG~e~ ~ f A~) 5 micron) cellophane~ and the adhesive is a "bakelized"
rubber-resin formed by compounding 100 parts of rubbery butadiene:styrene copolymer, 60 parts esterified gum rosln, 40 parts coumarone-indene resin, 12 parts phenol-formalde-hyde resin, and extenders, stabilizers, pigments, etc. as 10 desired.
For convenience, suitable components for prepar-ing effective primer compositions in accordance with the invention will now be indicated.
Rubbery Block Copolymer. The following styrene:
15 butadiene block copolymers have been found satisfactory:
styrene:butadiene:styrene rubbers having a styrene:rubber ratio of approximately 15:85 to 30:70; styrene:isoprene:
styrene copolymers having a styrene:rubber ratio of 14:86 and a solution viscosity of 1600 cps, and styrene:butadiene 20 radial teleblock copolymers having a styrene:butadiene ratio of 30:70 and an inherent viscosity in tetrahydro-furan of 1.50.
While it is essential for purposes of this in-vention that the primer composition contain a rubbery 25 block copolymer of the type previously described, it is possible to extend the composition by adding minor amounts of other types of rubbery materials, e.g., random buta-diene:acrylonitrile copolymers, random butadiene:styrene copolymers, crude rubber, polyisoprene, etc. Speaking in 30 general terms, these rubbery materials tend to reduce the `~ 107~7;~S~
effectiveness of the primer composition. They sh~uld be included, if at all, in limited quantlties Thermoplastic resins which are compatible with polystyrene and suitable for the practice of this lnven-tion include hydrocarbon resins, coumarone-indene reslns, polyalphamethyl styrene, polyalphamethyl styrene:vinyl toluene copolymers, polystyrene, dimerized rosin~ metal resinates, phenollc resln, copolymers of piperylene, etc.
Thermoplastic resins which are compatible wlth lO synthetic rubbers of the type described and suitable for ;
the practice of the invention include a wide variety of polymerized mixed olefins, glycerol esters of hydrogenated ros~n, pentaerythritol esters of hydrogenated rosin, glycerol esters of highly stabilized rosin, pentaerythritol esters of highly stabilized rosin, polyterpene resins, terpenephenolic resins, heat treated wood rosins, highly stable cycloaliphatic hydrocarbon resins, synthetic terpene polymers, tall oil resins, etc.
As used herein, the term ~'compatible" is intended to refer to those resins which are structurally sufficiently similar to the block referred to that a solution containing a solute formed solely of equal parts of resin and block material will dry to a transparent film.
The solvents used in preparing compositions of the invention preferably constitute a blend of organic solvents, including at least some aromatic solvent.
~here, for example, the primer solution is to be applied by roller-coating, brushing, etc., a suitable combination of solvents lncludes 60% ketones (`e.g., 30% each of ace-tone and methyl ethyl ketone), 30% heptane, and 10%
10767~g toluene. For such applicatlons, the solvent may con-stitute about 2/3 the total weight of the solution.
Where primer compositions of the invention are to be applied from aerosol containers, the percent solids of the solution is typically somewhat lower than in the case of solutions applied from bulk, a solution containing 20-30% solids having been found quite satisfactory.
Aerosol packages must include as propellant low molecular weight compound which boils below 25C. In compositions to be dispensed from an aerosol package, it is preferred to employ as solvent a blend of about 5% toluene and 95%
of such halocarbons as trichloroethylene, methylene chloride, chloroform and the like. Such chlorocarbons are especially desirable, since they perform the addi-tional functions of solubilizing oil or grease and helping maintain the rubbery copolymer in solution. A
blend of low molecular weight aliphatic hydrocarbons (e.g., a 30:70 propane:isobutane) is effective as a propellant.
In addition to the components previously des-cribed for incorporation in the primer compositions of the invention, it may also be desirable to include various other components. It has been found, for example, that it is desirable to include a minor but effective amount of an anti-oxidant such as symmetrical dibeta-naphthol-p-phenylene diamine, polymerized 1,2-dihydro-2,2,4-tri-methyl quinoline, 1,3,5-trimethyl-2,4,6-tris(3,5-di tert-butyl-4-hydroxy-benzyl) benzene, modified hindered phenols, tetra-bis-methylene-3(3',5'-tert-butyl-4'-hydroxy phenyl propionate) methane, octadecyl-beta-(3,5-tert-butyl-4-10~i729 hydroxy phenyl) proplonate, 2,2'-methylene'bis(4-methyl-6-tert-butyl phenol), steryl thiodlpropionate, etc.
As a further aid to understanding the inventlon, a series of tabulated examples will be set forth below.
In each of these examples, the components descrlbed were blended, together with approximately 0.4% 1,3,5-trimethyl-
2,4,6-tris(3,5-di tert-butyl-4-hydroxy benzyl) benzene anti-oxidant (based on the amount of rubbery copolymer present) and sufficient solvent to reduce the solids con-tent to approximately 20%. Test procedures were as des-cribed previously.
In the table, the following abbreviations~are used in the interest of simplicity:
Rubbery coPolymers K-llOl -- 70:30 butadiene:styrene block copolymer, having a solution viscosity (25% in toluene, 23C.) of 4,000 cps K 1107 -- 86:14 isoprene:styrene block copolymer, having a solution viscosity (25% in toluene, 23C.) of 1,600 cps S 411 -- 70:30 butadiene:styrene radial teleblock copolymer Polystyrene-com~atible resins A-135 -- Alpha-pinene S-115 -- synthetic terpene polymer having a ball and ring softening point of 115C.
T -- X-grade wood rosin U-85 -- piperylene copolymer having a softening point of 85C.
WT 95 -- polymerized mixed olefins, having a softening point of approximately 95C.
XA-125 -- highly stable cycloaliphatic hydro-carbon resin, having a ring and ball soften-ing point of 130C.
., .', ' 107~7~
Polydlene-compatible resins EG -- Rosin ester F85 -- highly stabilized ester rosin, having a softening point of about 80C., an acld number of 9, and a specific gravity of 1.07 H -- rosin ester having a softening point of 104C.
N -- gum rosin T -- X-grade wood rosin It will be noted that some resins are compatible wlth both polystyrene and polydienes, apparently associating with the block for which the other resin present has the less affinity.
1076'7Z9 ~ o o o o o o oo oooo (~ ~o ~J L~ o o L~ o o~ o~ J ~'U
R r~ D ~ J L~ rl J CO Lt~ O Lr~
0~ ~
0 ~
O o o o O o O O O O O
~ bO a) I L~ ~ ~ ~ o ao o o ~ oo Cl P I r-1 0 3 0 J L~ 3 ~O J o~
(d ~ ,~
E~
. O O O cr~ J o~ J
J~ J = - ~ ) O L~ o tU O O J =
~ J
I a~
a~ ~1 Q~-rl 2) L
~1 ~3 0 Q ~ = = - - Z = X ~ Z P~ Z = E~
o o C~ h E~ 1~
. J ~ ~O O ~ ~ J 0'.
= ~ ~ CO Lr~ O L~ L~`\ O =
~1 ~1 ~I ~I t\J (\I ~
~ ., .
H ~ P
J~Lr~
~d ~ ~ Ln Lt~ Lr m ~ ~ ~ ~ L~ ~ ~
¢ ~1 ~ Q I = = - - ,~ oo ~-~ = = - E-~
E~ O O a~ ~ ~ I I I E~
E~ X ~ p ~ ~2 .
J~ O _ _ =_ _=_=
In the table, the following abbreviations~are used in the interest of simplicity:
Rubbery coPolymers K-llOl -- 70:30 butadiene:styrene block copolymer, having a solution viscosity (25% in toluene, 23C.) of 4,000 cps K 1107 -- 86:14 isoprene:styrene block copolymer, having a solution viscosity (25% in toluene, 23C.) of 1,600 cps S 411 -- 70:30 butadiene:styrene radial teleblock copolymer Polystyrene-com~atible resins A-135 -- Alpha-pinene S-115 -- synthetic terpene polymer having a ball and ring softening point of 115C.
T -- X-grade wood rosin U-85 -- piperylene copolymer having a softening point of 85C.
WT 95 -- polymerized mixed olefins, having a softening point of approximately 95C.
XA-125 -- highly stable cycloaliphatic hydro-carbon resin, having a ring and ball soften-ing point of 130C.
., .', ' 107~7~
Polydlene-compatible resins EG -- Rosin ester F85 -- highly stabilized ester rosin, having a softening point of about 80C., an acld number of 9, and a specific gravity of 1.07 H -- rosin ester having a softening point of 104C.
N -- gum rosin T -- X-grade wood rosin It will be noted that some resins are compatible wlth both polystyrene and polydienes, apparently associating with the block for which the other resin present has the less affinity.
1076'7Z9 ~ o o o o o o oo oooo (~ ~o ~J L~ o o L~ o o~ o~ J ~'U
R r~ D ~ J L~ rl J CO Lt~ O Lr~
0~ ~
0 ~
O o o o O o O O O O O
~ bO a) I L~ ~ ~ ~ o ao o o ~ oo Cl P I r-1 0 3 0 J L~ 3 ~O J o~
(d ~ ,~
E~
. O O O cr~ J o~ J
J~ J = - ~ ) O L~ o tU O O J =
~ J
I a~
a~ ~1 Q~-rl 2) L
~1 ~3 0 Q ~ = = - - Z = X ~ Z P~ Z = E~
o o C~ h E~ 1~
. J ~ ~O O ~ ~ J 0'.
= ~ ~ CO Lr~ O L~ L~`\ O =
~1 ~1 ~I ~I t\J (\I ~
~ ., .
H ~ P
J~Lr~
~d ~ ~ Ln Lt~ Lr m ~ ~ ~ ~ L~ ~ ~
¢ ~1 ~ Q I = = - - ,~ oo ~-~ = = - E-~
E~ O O a~ ~ ~ I I I E~
E~ X ~ p ~ ~2 .
J~ O _ _ =_ _=_=
3 ~
~ O ~> o ~ - = _ _ = o t~ O Q ~ 3 ~1 C~ ~ ~
E~ ~
~ ~ ~ a~ ~ ~ ~ ~ ~ L~ Lr~ Lr~ Ln L~ Lr~ L~
O ~ ~ (~) ~) ~ J 3 3 3 J 3 3 3 ~ a~
a~ ~
o a~ a~ a~ a) a~ ~ ~a) ~a~ ~ a) a~
U~
~ ~ ~ ~ ~ S ~ ~
~ :r: o :~ o :~ o ~ o :q o ~ c) a~ ~ o o a) o a) o E~ v ~ ~ '~ ~ S J~ S ~
Q
~3 ~ ~ ~ ~ ~ ~D ~ CO a~ o ~1 ~:1
~ O ~> o ~ - = _ _ = o t~ O Q ~ 3 ~1 C~ ~ ~
E~ ~
~ ~ ~ a~ ~ ~ ~ ~ ~ L~ Lr~ Lr~ Ln L~ Lr~ L~
O ~ ~ (~) ~) ~ J 3 3 3 J 3 3 3 ~ a~
a~ ~
o a~ a~ a~ a) a~ ~ ~a) ~a~ ~ a) a~
U~
~ ~ ~ ~ ~ S ~ ~
~ :r: o :~ o :~ o ~ o :q o ~ c) a~ ~ o o a) o a) o E~ v ~ ~ '~ ~ S J~ S ~
Q
~3 ~ ~ ~ ~ ~ ~D ~ CO a~ o ~1 ~:1
Claims (8)
1. A primer composition for rendering oily and greasy surfaces capable of establishing firm bonds with normally tacky and pressure-sensitive adhesives, comprising in combination an organic solvent solution or stable dispersion of a blend of rubber and tackifying resin, the solids thereof consisting essentially of, on a weight basis, a. 15-35 parts of rubbery polymer consisting essentially of rubbery block copolymer selected from the class consisting of (1) rubbery block copolymer having the general configuration A-B-A wherein (a) each A is a thermoplastic polymer block which has a glass transition temperature above 20°C., which is relatively incompatible with the B block and which has an average molecular weight between about 5,000 and 125,000; B is an elastomeric polymer block of a conjugated diene, having an average molecular weight between about 15,000 and 250,000;
(b) the total weight of the A block is less than about 80% of the weight of the block copolymer and (2) radial teleblock copolymer consisting of several polystyrene-terminated elastomeric branches, each of said branches being a homopolymer of a conjugated diene extending from a central hub; and b. correspondingly 85-65 parts of tackifying resinous components.
(b) the total weight of the A block is less than about 80% of the weight of the block copolymer and (2) radial teleblock copolymer consisting of several polystyrene-terminated elastomeric branches, each of said branches being a homopolymer of a conjugated diene extending from a central hub; and b. correspondingly 85-65 parts of tackifying resinous components.
2. The composition of claim 1, wherein the tackifying resinous components consist of a first resinous component compatible with a homopolymer of the conjugated diene and a second resinous component compatible with poly-styrene.
3. The compositions of claim 2, wherein the A
blocks are polystyrene and the conjugated diene of the B
block is butadiene or isoprene.
blocks are polystyrene and the conjugated diene of the B
block is butadiene or isoprene.
4. The composition of claim 3, wherein the weight ratio of the first resinous component to the second resinous component is in the range of 70:30 to 30:70.
5. The composition of claim 4 wherein an effective amount of anti-oxidant is present.
6. The composition of claim 2, 3, or 4 wherein the solution is packaged in an aerosol container, together with propellants selected from the class consisting of low molecular weight hydrocarbon and halogenated hydrocarbon having a boiling point below about 25°C., to facilitate application.
7. The composition of claim 2, 3, or 4 wherein the solution is packaged in an aerosol container, the solids present constituting about 20% of the weight of the composition, the balance of said composition being made up of organic solvents and propellants.
8. The method of priming an oily surface to which tacky and pressure-sensitive adhesives do not normally bond firmly comprising applying to said surface the compo-sition of claim 3, 4, or 5 and allowing the solvent to evaporate.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/551,611 US3991002A (en) | 1975-02-21 | 1975-02-21 | Primer for oily surfaces |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1076729A true CA1076729A (en) | 1980-04-29 |
Family
ID=24201976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA244,386A Expired CA1076729A (en) | 1975-02-21 | 1976-01-28 | Primer for oily surfaces |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3991002A (en) |
| JP (1) | JPS6048555B2 (en) |
| AU (1) | AU503861B2 (en) |
| CA (1) | CA1076729A (en) |
| DE (1) | DE2607488A1 (en) |
| FR (1) | FR2301566A1 (en) |
| GB (1) | GB1502548A (en) |
| IT (1) | IT1053883B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4128984A (en) * | 1978-01-18 | 1978-12-12 | Minnesota Mining And Manufacturing Company | Method of constructing a sloped roof |
| US4432301A (en) * | 1979-06-06 | 1984-02-21 | Diesel Nelson P | Apparatus for affixing marker to fabric |
| US4363683A (en) * | 1979-06-06 | 1982-12-14 | Diesel Nelson P | Process for affixing marker to fabric |
| AU568236B2 (en) * | 1985-02-05 | 1987-12-17 | Toyoda Gosei Co. Ltd. | Halogen containing rubber solutions or dispersions |
| US4801346A (en) * | 1986-07-30 | 1989-01-31 | The Kendall Company | Protective coatings |
| EP0641370B1 (en) * | 1992-05-18 | 1997-09-24 | Minnesota Mining And Manufacturing Company | New block polymers and oil-contamination tolerant adhesive compositions |
| ES2123061T3 (en) * | 1992-06-20 | 1999-01-01 | Minnesota Mining & Mfg | PRIMING COMPOSITION FOR WET AND DRY ROAD SURFACES. |
| US5885269A (en) * | 1992-09-24 | 1999-03-23 | Minnesota Mining And Manufacturing Co. | Oil-tolerant reinforcement strip |
| US6121508A (en) * | 1995-12-29 | 2000-09-19 | 3M Innovative Properties Company | Polar, lipophilic pressure-sensitive adhesive compositions and medical devices using same |
| US6191055B1 (en) | 1996-12-18 | 2001-02-20 | 3M Innovative Properties Company | Oil-tolerant reinforcement strip |
| US7459494B2 (en) * | 2002-07-31 | 2008-12-02 | The Procter & Gamble Company | Phase change solvents for thermoplastic elastomers |
| DE10320581A1 (en) * | 2003-05-07 | 2004-12-02 | Klebchemie M.G. Becker Gmbh & Co. Kg | Preparation process for bonding |
| US8557349B2 (en) * | 2009-06-12 | 2013-10-15 | Apex Materials Corporation | Elastomeric paint with protective coating upon styrenic block copolymer articles |
| US9346080B2 (en) | 2004-03-01 | 2016-05-24 | Yuh-Jye Uang | Printing ink composition and method for printing |
| KR100682359B1 (en) * | 2004-11-16 | 2007-02-15 | 엘지.필립스 엘시디 주식회사 | Flat display pannel and fabricating method thereof |
| EP3569669A1 (en) | 2018-05-14 | 2019-11-20 | 3M Innovative Properties Company | Method of manufacturing an electronic control device |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3239478A (en) * | 1963-06-26 | 1966-03-08 | Shell Oil Co | Block copolymer adhesive compositions and articles prepared therefrom |
| GB1211244A (en) * | 1966-11-07 | 1970-11-04 | Minnesota Mining & Mfg | High strength adhesive compositions, films and tapes |
| CH513964A (en) * | 1968-04-12 | 1971-10-15 | Johnson & Johnson | Tape sticking due to pressure |
| US3630980A (en) * | 1968-06-25 | 1971-12-28 | Flintkote Co | Pressure-sensitive hot melt adhesives |
| US3658740A (en) * | 1969-12-05 | 1972-04-25 | Phillips Petroleum Co | Pressure sensitive adhesives |
| US3676386A (en) * | 1970-01-05 | 1972-07-11 | Grace W R & Co | Gasket-forming solvent-based compositions containing styrene-butadiene block copolymers |
| US3753936A (en) * | 1970-02-18 | 1973-08-21 | Phillips Petroleum Co | Branched rubbery block copolymer adhesive |
| US3792005A (en) * | 1972-02-07 | 1974-02-12 | Shell Oil Co | Low molecular weight block copolymers and coating compositions thereof |
-
1975
- 1975-02-21 US US05/551,611 patent/US3991002A/en not_active Expired - Lifetime
-
1976
- 1976-01-28 CA CA244,386A patent/CA1076729A/en not_active Expired
- 1976-02-20 JP JP51017821A patent/JPS6048555B2/en not_active Expired
- 1976-02-20 IT IT4821076A patent/IT1053883B/en active
- 1976-02-20 AU AU11299/76A patent/AU503861B2/en not_active Expired
- 1976-02-20 FR FR7604730A patent/FR2301566A1/en active Granted
- 1976-02-20 DE DE19762607488 patent/DE2607488A1/en active Granted
- 1976-02-20 GB GB684776A patent/GB1502548A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6048555B2 (en) | 1985-10-28 |
| FR2301566B3 (en) | 1978-11-10 |
| AU1129976A (en) | 1977-08-25 |
| AU503861B2 (en) | 1979-09-27 |
| JPS51109033A (en) | 1976-09-27 |
| FR2301566A1 (en) | 1976-09-17 |
| IT1053883B (en) | 1981-10-10 |
| US3991002A (en) | 1976-11-09 |
| GB1502548A (en) | 1978-03-01 |
| DE2607488A1 (en) | 1976-09-02 |
| DE2607488C2 (en) | 1987-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1076729A (en) | Primer for oily surfaces | |
| KR930009214B1 (en) | Pressure sensitive adhesive | |
| CA2036038C (en) | Hot-melt silicone pressure sensitive adhesive composition and related methods and articles | |
| JP2832589B2 (en) | Paint film protection sheet | |
| Comyn | What are adhesives and sealants and how do they work? | |
| JP2018502176A (en) | Rubber based multilayer pressure sensitive adhesive assembly | |
| EP1290099B1 (en) | Adhesive compositions and constructions with improved cutting performance | |
| JPH01115913A (en) | Emulsion polymerization secondary-butylacrylate latex suitable for pressure-sensitive adhesive and preparation thereof | |
| AU618208B2 (en) | Plasticizer resistant pressure sensitive adhesive | |
| US20180171191A1 (en) | Adhesive compound | |
| US5290564A (en) | Method and device for delivering a bioactive agent | |
| CA2423075A1 (en) | Adhesive composition | |
| US4432848A (en) | Radiation cured, high temperature pressure-sensitive adhesive | |
| WO2000005291A1 (en) | Low noise unwind pressure-sensitive adhesive tape | |
| US5462780A (en) | Pipe coating compositions | |
| US3553051A (en) | Self-supporting adhesive tape comprising synthetic trans - 1,4 polyisoprene and method of using said tape | |
| Temin | Pressure-sensitive adhesives for tapes and labels | |
| JPS60223880A (en) | Pressure-sensitive adhesive composition | |
| JPS60226579A (en) | Pressure-sensitive adhesive composition | |
| JP4396998B2 (en) | Pressure sensitive adhesive and surface protective material | |
| JP4285616B2 (en) | Method for forming pressure-sensitive adhesive tape and pressure-sensitive adhesive layer | |
| JPH10140113A (en) | Sheet for protecting coating film | |
| JPH09241596A (en) | Surface protective sheet | |
| JP4409647B2 (en) | Surface protection film | |
| JPH07278509A (en) | Production of rubber-based tacky tape |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |