CA1127592A - Pressure sensitive hot melt adhesive curable by exposure to electron beam radiation - Google Patents
Pressure sensitive hot melt adhesive curable by exposure to electron beam radiationInfo
- Publication number
- CA1127592A CA1127592A CA348,858A CA348858A CA1127592A CA 1127592 A CA1127592 A CA 1127592A CA 348858 A CA348858 A CA 348858A CA 1127592 A CA1127592 A CA 1127592A
- Authority
- CA
- Canada
- Prior art keywords
- prepolymer
- pressure sensitive
- hot melt
- electron beam
- adhesive
- 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
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Classifications
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
ABSTRACT
PRESSURE SENSITIVE HOT MELT ADHESIVE CURABLE BY
EXPOSURE TO ELECTRON BEAM RADIATION
Hot melt pressure sensitive adhesives are prepared by free-radical copolymerization of at least one copolymerizable acrylic monomer with allyl acrylate or methacrylate to produce a prepolymer with an ethylenically saturated backbone containing pendant allylic unsaturation. This solid prepolymer is then heated to a temperature sufficient to render it fluid and is applied in fluid form to a substrate. The substrate is thereafter subjected to electron beam radiation to crosslink the prepolymer to provide a cured pressure sensitive adhesive.
PRESSURE SENSITIVE HOT MELT ADHESIVE CURABLE BY
EXPOSURE TO ELECTRON BEAM RADIATION
Hot melt pressure sensitive adhesives are prepared by free-radical copolymerization of at least one copolymerizable acrylic monomer with allyl acrylate or methacrylate to produce a prepolymer with an ethylenically saturated backbone containing pendant allylic unsaturation. This solid prepolymer is then heated to a temperature sufficient to render it fluid and is applied in fluid form to a substrate. The substrate is thereafter subjected to electron beam radiation to crosslink the prepolymer to provide a cured pressure sensitive adhesive.
Description
~27';i9Z
Stephen D. Pastor Stuart H. Ganslaw PRESSURE SENSITIVE HOT MELT ADHESIVE CURABLE BY EXPOSURE
TO ELECTRON BEAM RADIATION
This invention relates to improved pressure sensitive hot melt adhesives. More specifically, it relates to a novel process for the production of hot melt adhesives having pressure sensitive properties comprising the steps of free-radical copolymerizing an acrylic-based comonomer(s) with allyl acrylate or methacrylate to produce a prepolymer with an ethylenically saturated backbone containing pendant allylic unsaturation which is then applied in fluid form to a substrate and thereafter subjected to electron beam curing. The use of this prepolymer enables the material to be applied in hot melt form and, upon exposure to electron beam radiation, to cure to provide a high molecular weight pressure sensitive adhesive displaying improved tack, cohesive strength and end use performance now only obtainable from solvent systems.
Pressure sensitive adhesive compositions comprise a class of adhesives which when coated on a suitable substrate share the common characteristic of being aggressively and permanently tacky at room temperature and are thus able to adhere to surfaces by the application of nothing more than manual pressure.
Hot melt adhesives are solid materials at room temperature.
Application of heat melts the solid adhesive bringing it to the liquid or fluid state in which form it is applied to a substrate, on cooling, the adhesive then regains its solid form.
This invention is directed to a process for producing hot melt pressure sensitive adhesives, i.e., adhesives which are applied in the liquid or fluid state at elevated temperatures and, upon cooling, form ~~
1~275~2 solid coatings which are permanen-tly tacky and which adhere on mere contac-t with adhesive receptive surfaces to which they are applied.
Adhesives of this type may be applied to various substrates such as paper, cloth and plastic films and the resulting coated substrates may then be converted into tapes and labels which are especially useful in the packaging field for any number of applications involving marking, sealing, reinforcing or bonding or are useful in the pharmaceutical or health field for such applications as bandages.
In preparing a pressure sensitive hot melt adhesive, the desirable properties include a high cohesive strength at room temperature for good holding power, low shrinkage of the adhesive film on flexible plastic substrates and retention of pressure sensitive properties (i.e., tack retention) during storage and use together with a relative-ly fluid viscosity at commonly employed application temperatures of 120 to 180C.
Acrylic polymers and copolymers have found extensive use as the base polymers in pressure sensitive adhesive lacquers or water-based systems mainly because of their clarity, adhesion to non-primed sur-faces, good aging characteristics, as well as their excellent proper-ties of tack, peel and cohesive strength. Many attempts to utilizeacrylic polymers or copolymers in pressure sensitive hot melt adhesives have not proven successful because of difficulties associated with melt viscosity. In order to have a hot melt adhesive that is suffici-ently fluid at application temperatures, either a very low molecular weiqht polymer must be used or a high molecular weight polymer must be extended with a high proportion of low molecular weight oils or resins (tackifiers) to reduce the melt viscosity. Both of these alternatives ~Z7~92 are undesirable since low molecular weight polymers will produce adhe-sives which lack cohesive strength and the use of expensive additives will frequen-tly detract from the cohesion or tack of the resultant adhesive.
Previous a-ttempts to render acrylic polymers or monomer/oligomer systems useful for hot melt applied pressure sensitive adhesives by in-corporating therein photoinitiators and subjecting the compositions to actinic radiation have not been successful since it has been difficult to cure the compositions to the proper degree of tackiness. A usual result is an overcured, hard coating possessing little, if any, pres-sure sensitivity. Moreover, many of the photoinitiators were also sensi-tive to visible light wavelengths and this sensitivity caused further curing of the adhesive during storage or use thereof. Finally, for many applications such as surgical bandaging, it is necessary that any externally added components (e.g., photoinitiators) be fully bound into the final composition; many of the compositions of the prior art contained photoinitiators which leached out during use.
Hot melt pressure sensitive adhesives have been prepared (see U.S.
Pat. No. 4,052,527) by subjecting an acrylic prepolymer containing specific monomeric photoinitiators to ultraviolet radiation. The use of ultrviolet radiation to cure hot melt compositions is, however, limited by its penetrating power, being able to cure only relatively thin films since ultraviolet curing of thicker films results in undesirable stratification (layering) and consequent weakness of the final bond. Moreover, this method is unsatisfactory when curing of pigmented coatings is desired or when it is necessary to cure a coating through an opaque overlaying material, e.g., a release sheet.
.
75~
Electron beam curable acrylic hot melts have also been marketed but these composi-tions required such high levels of radiation (gener-ally on the order of 100,000 J/kg) in order to achieve curing, that the consequent cost and dangers associated therewiti- outweigh the advantages obtained thereby.
The invention herein provides a process for the production of pressure sensitive ho-t melt adhesives which display excellent properties of tack, tack retention and cohesive strength, yet which are characterized by relatively low melt viscosity for ease of application, and which are curable using low levels of electron beam radiation and useful in the curing of films regardless of thickness, pigmentation or the presence of overlay sheets.
Thus, acrylate-based pressure sensitive hot melt adhesives are prepared by copolymerizing allyl acryla-te or methacrylate with at least one copolymerizable acrylic monomer to obtain a prepolymer solid at ambient temperatures; heating the resultant solid allylic unsaturated prepolymer to a temperature sufficient to render it flowable and fluid;
coating the fluid prepolymer onto a substrate and thereafter exposing the adhesive coated substrate to electron beam radiation of 10,000-40,000 J/kg sufficient to crosslink the prepolymer, thereby providing a cured pressure sensitive adhesive.
27S~2 The resulting adhesive coated surFace possesses excellent tack, cohesive strength, and tack reten-tion upon stora~e and use, contains no unbound photoinitiator and yet is readily applied at low melt viscosity using conventional hot melt equipment. Moreover the adhesive may be coated on the surface regardless of -thickness, pigmentation or the presence of overlay sheets, yet will be uniforrnly cured throughout upon exposure to electron beam radiation.
Pressure sensitive adhesives based on acrylate ester homo- and co-polymers are well known to those skilled in the art. It is to be noted that the present process is adap-table to be used with all such pressure sensitive adhesives.
Thus, the acrylate-based copolymerizable monomers which may be used include those acrylate ester monomers selected from tile group con-sisting of the alkyl esters of acrylic and methacrylic acid wherein the alkyl groups contain 4 to 9 carbon atoms, preferably 4 to 8 carbon atoms. Such esters include n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, n-nonyl acrylate;
their correspondingly branched isomers such as 2-ethylhexyl acrylate, etc. as well as the corresponding methacrylate esters.
Optionally, the pressure sensitive adhesive may be prepared with one or more polymerizable comonomers selected from the groups consist-ing of vinyl esters, vinyl ethers, vinyl halides, vinylidene halides, nitriles of ethylenically unsaturated hydrocarbons as well as with other acrylate monomers such as methyl acrylate and methyl methacrylate which are not considered tacky or pressure sensitive. Examples of op-tional comonomers include vinyl acetate, t-octyl acrylamide, acrylic acid, vinyl e-thyl ether, vinyl chloride, vinylidene chloride, acrylo-ni-trile, maleic anhydride and styrene.
It is to be noted that the C4-Cg alkYl esters of acrylic acid will ordinarily constitute at least about 50% by weight of the total copolymer in order to ensure sufficient pressure sensitivity in the resultant adhesive. The relative amounts of the specific components making up -the acrylate-based adhesive are dependent upon the final properties desired and the end used contemplated; they are conventional and known in the art.
The allyl acrylate or methacryla-te component employed should be present in the copolymer in an amount of about 0.1 to 2, preferably 0.3 to 0.75 parts, by weight of the copolymer.
As will be recognized by those skilled in the art, the preparation of the interpolymer containing the acrylic copolymer and allyl acrylate or methacrylate component can be carried out using well-known free radical initiated polymerization procedures. Thus, the interpolymer can be prepared by solution, emulsion or bulk polymerization procedures formed into a hot melt by removal of the solvent, coagulation of the latex, etc. The adhesive interpolymer mày also comprise various other additives such as plasticizers, tackifiers, fillers, etc. which are conventionally used in the preparation of hot melt and/or pressure sensitive adhesives.
During use, the hot melt composition need only be heated to a temperature of about 120 to 180C. to render the composition fluid and flowable and to allow the composition to remain flowable for the time 3~L~7 ~t~
required for application thereof.
If the adhesive composition is to be applied to a backing or sub-strate, this procedure may be accomplished using any conventional means such as roller, slot orifice, spray or extrusion coating. The backing onto which the hot melt composition is applied may be selected from a variety of rnaterials including fabric, plastic film, nonwoven fiber sheets, metal sheets or foil, rubber or synthetic rubber, decorative sheets, plywood decals, etc. If the coated substrate is to be used in the form of a roll, the back of the tape is usually coa-ted with a release backsize or adhesive coating. Double sided coated adhesive articles may also be prepared and a strippable paper or other protec-tive means inserted if the article is to be rolled. Additionally, sub-strates may be laminated onto the adhesive-coating backing in situ, i.e.
the hot melt coating may be applied to the backing and the substrate placed over the adhesive. Alternatively, a pressure sensitive adhesive film may be formed by applying the hot melt to a release material such as silicone coated paper; then, after curing, it rnay then be stripped from the release material and used as a film.
After the hot composition is applied, it may be cured immediately or it may be allowed to cool to a temperature at which it is no longer flowable prior to the radiation step.
The resulting adhesive coatings are then crosslinked (cured) by exposure to electron beam radiation. While there is no upper limit to the radiation that can be applied, the curing effect desired in the practice of the process herein can be accomplished using radiation at a level of 10,000-40,000 J/kg which is sufficient to accomplish the desired amount of crosslinking, and preferably 30,000-40,000 J/kg.
The radiation level required will be dependent upon the nature and intensity of the radiation, the adhesive system, the thickness of the film, environmental factors, etc.
As the source of radiation, high energy beams from an electron accelerator are preferred since an adequate curing dosage is readily obtained and the rate of processing can be greatly increased. Other high energy radiation such as gamma rays, X-rays and beta rays may, how-ever, also be used. Various types of high power electron linear accelerators are available commercially. Since the radiation levels required herein are relatively low, small power units such as the Electrocurtain (registered trade mark) Processor available from Energy Sciences, Inc., Burlington, Mass. are suitable for use herein.
The unique adhesive compositions formed by the present process find application in a wide variety of products where non-leachable pressure sensitive ma-terials are required such as for bandages or other medical applications. The adhesives are also useful in the production of vinyl wall coverings, tapes, labels and decals, as well as in such other applications wherein solution acrylics are presently employed.
This process therefore offers an advantage to the previously employed solution acrylics by eliminating the need for solvent removal after application of the adhesive while providing a composition possessing superior cohesive and adhesive properties. Furthermore, the resultant crosslinked adhesives are characterized by resistance to solvents in which they would ordinarily dissolve or soften, by increased Williams plasticity values and by superior pressure sensitive properties. Thus, the hot melt adhesives herein have melt viscosities between about 4000 and 100,000 cps., preferably from about 5000 to 25,000 cps ~lZ ~,2 at 180C. The interpolymers employed herein may have a negligible or unmeasurable low standard Williams plasticity number before exposure to electron beam radiation. Plasticity may be defined as the property of a polymeric material which enables it to be deformed permanently and continuously without rupture, upon the application of a force thereto.
This property is measured by the use of a William's Plastometer which is manufactured by Scott Testers, Inc. and is designed to conform to the standards set by ASTM Method D-926. In some cases, it is preferred -that the interpolymer have negligible (0.4-1.3) plasticity before exposure and at least about 1.8 after exposure. Thus, an advantage of the method herein is that it allows the use of essentially fluid, low cohesive materials or materials with no or low plasticity to be transformed into useful elastomeric adhesives of higher plasticity.
The final plasticity of the adhesive is usually between 2-3 although where the plasticity is above this level, some added tackifiers may be provided to produce the desired properties.
The examples set forth below serve to illustrate the process of the invention in certain of its embodiments. All parts and percentages in these examples as well as throughout the specification are by weight and temperatures in degrees Celsius unless otherwise specified.
In the examples the following testing procedures are employed to measure the comparative properties of the various adhesives.
180 Peel Adhesion Test (ASTM Method D-1000) This test consists of measuring the force necessary to strip or delaminate the adhesive film test sample (2.5 cm x 15 cm x 0.038 mm) coated on 0.05 mm polyester film from a stainless steel panel at a rate of pull, or withdrawal, of 30 cm per minute. An Instron (trademark) ~lZ759Z
Tensile Tester was used to provide the pulling force. Thus, the force necessary to effect delamination is recorded as the "180 Peel Adhesion" value. Tests were taken after only 20 minutes and then again after standing for various periods of time at the temperatures noted in the examples. Values are shown in k~/cm with the higher values indicating the best results. It is noted that the adhesives prepared by the present process suffer a reduction in peel; however, the values obtained after irradiation are still commercially acceptable and are more than compensated by the improvements in Williams plasticity and cohesive strength.
Shear Adhesion Test (PSTC Method 7) The shear strength is measured by transferring the adhesive onto a 0.05 mm thick polyethylene terephthalate (Mylar is the trademark there-for) or vinyl sheet (as noted in the example) at a dry weight of 0.0028 - 0.0034 g/cm2. The coated sample is then applied to a steel panel with a 1.3 cm overlap joint. A 0.45 kg weight is suspended from the sample with the steel panel maintained vertically and the time until separation occurs is measured. The test is carried out at 23C. and 50% relative humidity. The test is a measure of the cohesive strength and ability to maintain cohesive strength over a period of time. Thus, the adhesives showing the longest times are preferred.
EXAMPLE I
This example illustrates a process for the preparation of a hot melt, pressure sensitive adhesive in accordance with the procedures herein described.
A three liter flask equipped with a thermometer, a reflex condenser, a source of mechanical agitation and slow addition funnels was initially ~Z75~Z
charged with 50 grams methyl acrylate, 50 grams 2-ethylhexyl acrylate, 250 grams methyl alcohol, 75 grams isopropyl alcohol and 1 gram t-butyl peroxypivalate.
The mixture was brought to reflux after which the following monomer and catalyst charges were added simultaneously in increments over a three-hour period: a rnonomer charge of 150 grams methyl acrylate, 550 grams 2-ethylhexyl acrylate, 200 grams rnethyl methacrylate and 5 grams allyl methacrylate, and a catalyst charge of 280 grams methyl alcohol and 11.5 grams -t-butyl peroxypivalate.
After completion of the addition, the reaction mixture was held at reflux for two hours, cooled and 5 grams Irganox 1010 (trademark for high molecular weight stabilizer containing multifunctional chemical group-ings) post added. The solvent was removed by distillation and heated to 110C. for one hour at 15 mm Hg to produce the resultant saturated polymer designated composition A.
As a comparison, three compositions containing the functional monomers 3-(pentachlorophenoxy-)-2-hydroxypropyl methacrylate (3-PCP-
Stephen D. Pastor Stuart H. Ganslaw PRESSURE SENSITIVE HOT MELT ADHESIVE CURABLE BY EXPOSURE
TO ELECTRON BEAM RADIATION
This invention relates to improved pressure sensitive hot melt adhesives. More specifically, it relates to a novel process for the production of hot melt adhesives having pressure sensitive properties comprising the steps of free-radical copolymerizing an acrylic-based comonomer(s) with allyl acrylate or methacrylate to produce a prepolymer with an ethylenically saturated backbone containing pendant allylic unsaturation which is then applied in fluid form to a substrate and thereafter subjected to electron beam curing. The use of this prepolymer enables the material to be applied in hot melt form and, upon exposure to electron beam radiation, to cure to provide a high molecular weight pressure sensitive adhesive displaying improved tack, cohesive strength and end use performance now only obtainable from solvent systems.
Pressure sensitive adhesive compositions comprise a class of adhesives which when coated on a suitable substrate share the common characteristic of being aggressively and permanently tacky at room temperature and are thus able to adhere to surfaces by the application of nothing more than manual pressure.
Hot melt adhesives are solid materials at room temperature.
Application of heat melts the solid adhesive bringing it to the liquid or fluid state in which form it is applied to a substrate, on cooling, the adhesive then regains its solid form.
This invention is directed to a process for producing hot melt pressure sensitive adhesives, i.e., adhesives which are applied in the liquid or fluid state at elevated temperatures and, upon cooling, form ~~
1~275~2 solid coatings which are permanen-tly tacky and which adhere on mere contac-t with adhesive receptive surfaces to which they are applied.
Adhesives of this type may be applied to various substrates such as paper, cloth and plastic films and the resulting coated substrates may then be converted into tapes and labels which are especially useful in the packaging field for any number of applications involving marking, sealing, reinforcing or bonding or are useful in the pharmaceutical or health field for such applications as bandages.
In preparing a pressure sensitive hot melt adhesive, the desirable properties include a high cohesive strength at room temperature for good holding power, low shrinkage of the adhesive film on flexible plastic substrates and retention of pressure sensitive properties (i.e., tack retention) during storage and use together with a relative-ly fluid viscosity at commonly employed application temperatures of 120 to 180C.
Acrylic polymers and copolymers have found extensive use as the base polymers in pressure sensitive adhesive lacquers or water-based systems mainly because of their clarity, adhesion to non-primed sur-faces, good aging characteristics, as well as their excellent proper-ties of tack, peel and cohesive strength. Many attempts to utilizeacrylic polymers or copolymers in pressure sensitive hot melt adhesives have not proven successful because of difficulties associated with melt viscosity. In order to have a hot melt adhesive that is suffici-ently fluid at application temperatures, either a very low molecular weiqht polymer must be used or a high molecular weight polymer must be extended with a high proportion of low molecular weight oils or resins (tackifiers) to reduce the melt viscosity. Both of these alternatives ~Z7~92 are undesirable since low molecular weight polymers will produce adhe-sives which lack cohesive strength and the use of expensive additives will frequen-tly detract from the cohesion or tack of the resultant adhesive.
Previous a-ttempts to render acrylic polymers or monomer/oligomer systems useful for hot melt applied pressure sensitive adhesives by in-corporating therein photoinitiators and subjecting the compositions to actinic radiation have not been successful since it has been difficult to cure the compositions to the proper degree of tackiness. A usual result is an overcured, hard coating possessing little, if any, pres-sure sensitivity. Moreover, many of the photoinitiators were also sensi-tive to visible light wavelengths and this sensitivity caused further curing of the adhesive during storage or use thereof. Finally, for many applications such as surgical bandaging, it is necessary that any externally added components (e.g., photoinitiators) be fully bound into the final composition; many of the compositions of the prior art contained photoinitiators which leached out during use.
Hot melt pressure sensitive adhesives have been prepared (see U.S.
Pat. No. 4,052,527) by subjecting an acrylic prepolymer containing specific monomeric photoinitiators to ultraviolet radiation. The use of ultrviolet radiation to cure hot melt compositions is, however, limited by its penetrating power, being able to cure only relatively thin films since ultraviolet curing of thicker films results in undesirable stratification (layering) and consequent weakness of the final bond. Moreover, this method is unsatisfactory when curing of pigmented coatings is desired or when it is necessary to cure a coating through an opaque overlaying material, e.g., a release sheet.
.
75~
Electron beam curable acrylic hot melts have also been marketed but these composi-tions required such high levels of radiation (gener-ally on the order of 100,000 J/kg) in order to achieve curing, that the consequent cost and dangers associated therewiti- outweigh the advantages obtained thereby.
The invention herein provides a process for the production of pressure sensitive ho-t melt adhesives which display excellent properties of tack, tack retention and cohesive strength, yet which are characterized by relatively low melt viscosity for ease of application, and which are curable using low levels of electron beam radiation and useful in the curing of films regardless of thickness, pigmentation or the presence of overlay sheets.
Thus, acrylate-based pressure sensitive hot melt adhesives are prepared by copolymerizing allyl acryla-te or methacrylate with at least one copolymerizable acrylic monomer to obtain a prepolymer solid at ambient temperatures; heating the resultant solid allylic unsaturated prepolymer to a temperature sufficient to render it flowable and fluid;
coating the fluid prepolymer onto a substrate and thereafter exposing the adhesive coated substrate to electron beam radiation of 10,000-40,000 J/kg sufficient to crosslink the prepolymer, thereby providing a cured pressure sensitive adhesive.
27S~2 The resulting adhesive coated surFace possesses excellent tack, cohesive strength, and tack reten-tion upon stora~e and use, contains no unbound photoinitiator and yet is readily applied at low melt viscosity using conventional hot melt equipment. Moreover the adhesive may be coated on the surface regardless of -thickness, pigmentation or the presence of overlay sheets, yet will be uniforrnly cured throughout upon exposure to electron beam radiation.
Pressure sensitive adhesives based on acrylate ester homo- and co-polymers are well known to those skilled in the art. It is to be noted that the present process is adap-table to be used with all such pressure sensitive adhesives.
Thus, the acrylate-based copolymerizable monomers which may be used include those acrylate ester monomers selected from tile group con-sisting of the alkyl esters of acrylic and methacrylic acid wherein the alkyl groups contain 4 to 9 carbon atoms, preferably 4 to 8 carbon atoms. Such esters include n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, n-nonyl acrylate;
their correspondingly branched isomers such as 2-ethylhexyl acrylate, etc. as well as the corresponding methacrylate esters.
Optionally, the pressure sensitive adhesive may be prepared with one or more polymerizable comonomers selected from the groups consist-ing of vinyl esters, vinyl ethers, vinyl halides, vinylidene halides, nitriles of ethylenically unsaturated hydrocarbons as well as with other acrylate monomers such as methyl acrylate and methyl methacrylate which are not considered tacky or pressure sensitive. Examples of op-tional comonomers include vinyl acetate, t-octyl acrylamide, acrylic acid, vinyl e-thyl ether, vinyl chloride, vinylidene chloride, acrylo-ni-trile, maleic anhydride and styrene.
It is to be noted that the C4-Cg alkYl esters of acrylic acid will ordinarily constitute at least about 50% by weight of the total copolymer in order to ensure sufficient pressure sensitivity in the resultant adhesive. The relative amounts of the specific components making up -the acrylate-based adhesive are dependent upon the final properties desired and the end used contemplated; they are conventional and known in the art.
The allyl acrylate or methacryla-te component employed should be present in the copolymer in an amount of about 0.1 to 2, preferably 0.3 to 0.75 parts, by weight of the copolymer.
As will be recognized by those skilled in the art, the preparation of the interpolymer containing the acrylic copolymer and allyl acrylate or methacrylate component can be carried out using well-known free radical initiated polymerization procedures. Thus, the interpolymer can be prepared by solution, emulsion or bulk polymerization procedures formed into a hot melt by removal of the solvent, coagulation of the latex, etc. The adhesive interpolymer mày also comprise various other additives such as plasticizers, tackifiers, fillers, etc. which are conventionally used in the preparation of hot melt and/or pressure sensitive adhesives.
During use, the hot melt composition need only be heated to a temperature of about 120 to 180C. to render the composition fluid and flowable and to allow the composition to remain flowable for the time 3~L~7 ~t~
required for application thereof.
If the adhesive composition is to be applied to a backing or sub-strate, this procedure may be accomplished using any conventional means such as roller, slot orifice, spray or extrusion coating. The backing onto which the hot melt composition is applied may be selected from a variety of rnaterials including fabric, plastic film, nonwoven fiber sheets, metal sheets or foil, rubber or synthetic rubber, decorative sheets, plywood decals, etc. If the coated substrate is to be used in the form of a roll, the back of the tape is usually coa-ted with a release backsize or adhesive coating. Double sided coated adhesive articles may also be prepared and a strippable paper or other protec-tive means inserted if the article is to be rolled. Additionally, sub-strates may be laminated onto the adhesive-coating backing in situ, i.e.
the hot melt coating may be applied to the backing and the substrate placed over the adhesive. Alternatively, a pressure sensitive adhesive film may be formed by applying the hot melt to a release material such as silicone coated paper; then, after curing, it rnay then be stripped from the release material and used as a film.
After the hot composition is applied, it may be cured immediately or it may be allowed to cool to a temperature at which it is no longer flowable prior to the radiation step.
The resulting adhesive coatings are then crosslinked (cured) by exposure to electron beam radiation. While there is no upper limit to the radiation that can be applied, the curing effect desired in the practice of the process herein can be accomplished using radiation at a level of 10,000-40,000 J/kg which is sufficient to accomplish the desired amount of crosslinking, and preferably 30,000-40,000 J/kg.
The radiation level required will be dependent upon the nature and intensity of the radiation, the adhesive system, the thickness of the film, environmental factors, etc.
As the source of radiation, high energy beams from an electron accelerator are preferred since an adequate curing dosage is readily obtained and the rate of processing can be greatly increased. Other high energy radiation such as gamma rays, X-rays and beta rays may, how-ever, also be used. Various types of high power electron linear accelerators are available commercially. Since the radiation levels required herein are relatively low, small power units such as the Electrocurtain (registered trade mark) Processor available from Energy Sciences, Inc., Burlington, Mass. are suitable for use herein.
The unique adhesive compositions formed by the present process find application in a wide variety of products where non-leachable pressure sensitive ma-terials are required such as for bandages or other medical applications. The adhesives are also useful in the production of vinyl wall coverings, tapes, labels and decals, as well as in such other applications wherein solution acrylics are presently employed.
This process therefore offers an advantage to the previously employed solution acrylics by eliminating the need for solvent removal after application of the adhesive while providing a composition possessing superior cohesive and adhesive properties. Furthermore, the resultant crosslinked adhesives are characterized by resistance to solvents in which they would ordinarily dissolve or soften, by increased Williams plasticity values and by superior pressure sensitive properties. Thus, the hot melt adhesives herein have melt viscosities between about 4000 and 100,000 cps., preferably from about 5000 to 25,000 cps ~lZ ~,2 at 180C. The interpolymers employed herein may have a negligible or unmeasurable low standard Williams plasticity number before exposure to electron beam radiation. Plasticity may be defined as the property of a polymeric material which enables it to be deformed permanently and continuously without rupture, upon the application of a force thereto.
This property is measured by the use of a William's Plastometer which is manufactured by Scott Testers, Inc. and is designed to conform to the standards set by ASTM Method D-926. In some cases, it is preferred -that the interpolymer have negligible (0.4-1.3) plasticity before exposure and at least about 1.8 after exposure. Thus, an advantage of the method herein is that it allows the use of essentially fluid, low cohesive materials or materials with no or low plasticity to be transformed into useful elastomeric adhesives of higher plasticity.
The final plasticity of the adhesive is usually between 2-3 although where the plasticity is above this level, some added tackifiers may be provided to produce the desired properties.
The examples set forth below serve to illustrate the process of the invention in certain of its embodiments. All parts and percentages in these examples as well as throughout the specification are by weight and temperatures in degrees Celsius unless otherwise specified.
In the examples the following testing procedures are employed to measure the comparative properties of the various adhesives.
180 Peel Adhesion Test (ASTM Method D-1000) This test consists of measuring the force necessary to strip or delaminate the adhesive film test sample (2.5 cm x 15 cm x 0.038 mm) coated on 0.05 mm polyester film from a stainless steel panel at a rate of pull, or withdrawal, of 30 cm per minute. An Instron (trademark) ~lZ759Z
Tensile Tester was used to provide the pulling force. Thus, the force necessary to effect delamination is recorded as the "180 Peel Adhesion" value. Tests were taken after only 20 minutes and then again after standing for various periods of time at the temperatures noted in the examples. Values are shown in k~/cm with the higher values indicating the best results. It is noted that the adhesives prepared by the present process suffer a reduction in peel; however, the values obtained after irradiation are still commercially acceptable and are more than compensated by the improvements in Williams plasticity and cohesive strength.
Shear Adhesion Test (PSTC Method 7) The shear strength is measured by transferring the adhesive onto a 0.05 mm thick polyethylene terephthalate (Mylar is the trademark there-for) or vinyl sheet (as noted in the example) at a dry weight of 0.0028 - 0.0034 g/cm2. The coated sample is then applied to a steel panel with a 1.3 cm overlap joint. A 0.45 kg weight is suspended from the sample with the steel panel maintained vertically and the time until separation occurs is measured. The test is carried out at 23C. and 50% relative humidity. The test is a measure of the cohesive strength and ability to maintain cohesive strength over a period of time. Thus, the adhesives showing the longest times are preferred.
EXAMPLE I
This example illustrates a process for the preparation of a hot melt, pressure sensitive adhesive in accordance with the procedures herein described.
A three liter flask equipped with a thermometer, a reflex condenser, a source of mechanical agitation and slow addition funnels was initially ~Z75~Z
charged with 50 grams methyl acrylate, 50 grams 2-ethylhexyl acrylate, 250 grams methyl alcohol, 75 grams isopropyl alcohol and 1 gram t-butyl peroxypivalate.
The mixture was brought to reflux after which the following monomer and catalyst charges were added simultaneously in increments over a three-hour period: a rnonomer charge of 150 grams methyl acrylate, 550 grams 2-ethylhexyl acrylate, 200 grams rnethyl methacrylate and 5 grams allyl methacrylate, and a catalyst charge of 280 grams methyl alcohol and 11.5 grams -t-butyl peroxypivalate.
After completion of the addition, the reaction mixture was held at reflux for two hours, cooled and 5 grams Irganox 1010 (trademark for high molecular weight stabilizer containing multifunctional chemical group-ings) post added. The solvent was removed by distillation and heated to 110C. for one hour at 15 mm Hg to produce the resultant saturated polymer designated composition A.
As a comparison, three compositions containing the functional monomers 3-(pentachlorophenoxy-)-2-hydroxypropyl methacrylate (3-PCP-
2-HPMA), glycidyl methacrylate, and a straight nonfunctional acrylic monomer were made using the method described above. The components and amounts are as follows:
Monomer Composition (g) B C D
2-Ethylhexyl Acrylate 58.5 60 60 Methyl Acrylate 20 20 20 Methyl Methacrylate 16.5 15 20
Monomer Composition (g) B C D
2-Ethylhexyl Acrylate 58.5 60 60 Methyl Acrylate 20 20 20 Methyl Methacrylate 16.5 15 20
3-PCP-2-llPMA 5.0 Glycidyl Methacrylate - 5 1~275~Z
The resultant compositions (A-D) were heated to 180C., applied to release paper in an amount of 7.2 kg/ream or 0.025 mm (dry) and allowed to cool. The coated paper was then exposed to electron beam radiation ranging from 10,000-40,000 J/kg. Each sample was then tested for peel strength and shear s-trength and the following results were obtained.
Exposure (J/kg) 0 10,00020,000 30,00040,000 Sample A
180 Peel (kg/cm) 0.71 0.67 0.57 0.55 0.53 0.3 kg/cm2 llold 16 min. 5 hrs.7 hrs. 9 hrs.>20 hrs.
Sample B
180 Peel (kg/cM) 0.83 0.80 0.80 0.74 0.73 0.3 kg/cm2 I-lold 7 min. 9 min.10 min. 12 min .14 min.
Sample C
180 Peel (kg/cm) 0.90 0.90 0.90 0.87 0.78 0.3 kg/cm2 Hold 10 min. 10 min.10 min. 11 min .15 min.
Sample D
180 Peel (kg/cm) 0.73 0.73 0.73 0.71 0.69 0.3 kg/cm2 Hold 10 min. 10 min.12 min. 13 min .14 min.
The results presented above indicate the dramatic improvernent in shear strength obtained using allyl methacrylate in accordance with the present process and contrasted with only minimal loss in peel when compared with compositions containing ottler initiators.
EXAMPLE II
Using the procedure, catalyst and solvent employed in Example I, pressure sensitive hot melt adhesives were prepared by coating inter-polymers having the following composi-tions onto the desired substrates ~275~Z
and exposing to electron beam radiation of 20,000 J/kg. The resultant adhesives were tested for shear strength (0.3 kg/cm2 hold) as described in Example I.
Monomer Compositions (9) E F G
2-Ethylhexyl Acrylate 60 60 60 Methyl Methacrylate 19.75 19.6 19.25 Methyl Acrylate 20 20 20 Allyl Methacrylate 0.25 0.4 0.75 0.3 kg/cm2 I-lold 1 hr. 5 hrs. 7 hrs.
EXAMPLE III
Using the procedure, catalysts and solvents described in Example I, pressure sensitive hot melt adhesives may be prepared by coating the resultant copolymers (prepolymers) formed from the ingredients listed in Table I onto the desired substrates and exposing to electron beam radiation.
Monomer Compositions (g) H J K L M
2-Ethylhexyl Acrylate 60 59.5 - - 60 Butyl Acrylate - - 60 60 Methyl Methacrylate - 10 20 19.5 19.6 Methyl Acrylate 9.5 - 19.5 - 20 Vinyl Acetate 30 - - 10 Ethyl Acrylate - 30 - 10 Allyl Methacrylate 0.5 0.5 0.5 0.5 Allyl Acrylate - - - - 0.4 The resultant irradiated compositions will possess excellent adhesive properties even after storage for extended periods of time and are readily removable from any substrate to which they are adhered.
~ , llZ759Z
Summarizing, it is seen tha-t the addition of allyl acrylate or methacrylate into the backbone of acrylate-based hot melt adhesives resul-ts in the production of prepolymeric adhesives which, when cured by exposure to electron beam radiation, are characterized by superior pressure sensitive properties.
The resultant compositions (A-D) were heated to 180C., applied to release paper in an amount of 7.2 kg/ream or 0.025 mm (dry) and allowed to cool. The coated paper was then exposed to electron beam radiation ranging from 10,000-40,000 J/kg. Each sample was then tested for peel strength and shear s-trength and the following results were obtained.
Exposure (J/kg) 0 10,00020,000 30,00040,000 Sample A
180 Peel (kg/cm) 0.71 0.67 0.57 0.55 0.53 0.3 kg/cm2 llold 16 min. 5 hrs.7 hrs. 9 hrs.>20 hrs.
Sample B
180 Peel (kg/cM) 0.83 0.80 0.80 0.74 0.73 0.3 kg/cm2 I-lold 7 min. 9 min.10 min. 12 min .14 min.
Sample C
180 Peel (kg/cm) 0.90 0.90 0.90 0.87 0.78 0.3 kg/cm2 Hold 10 min. 10 min.10 min. 11 min .15 min.
Sample D
180 Peel (kg/cm) 0.73 0.73 0.73 0.71 0.69 0.3 kg/cm2 Hold 10 min. 10 min.12 min. 13 min .14 min.
The results presented above indicate the dramatic improvernent in shear strength obtained using allyl methacrylate in accordance with the present process and contrasted with only minimal loss in peel when compared with compositions containing ottler initiators.
EXAMPLE II
Using the procedure, catalyst and solvent employed in Example I, pressure sensitive hot melt adhesives were prepared by coating inter-polymers having the following composi-tions onto the desired substrates ~275~Z
and exposing to electron beam radiation of 20,000 J/kg. The resultant adhesives were tested for shear strength (0.3 kg/cm2 hold) as described in Example I.
Monomer Compositions (9) E F G
2-Ethylhexyl Acrylate 60 60 60 Methyl Methacrylate 19.75 19.6 19.25 Methyl Acrylate 20 20 20 Allyl Methacrylate 0.25 0.4 0.75 0.3 kg/cm2 I-lold 1 hr. 5 hrs. 7 hrs.
EXAMPLE III
Using the procedure, catalysts and solvents described in Example I, pressure sensitive hot melt adhesives may be prepared by coating the resultant copolymers (prepolymers) formed from the ingredients listed in Table I onto the desired substrates and exposing to electron beam radiation.
Monomer Compositions (g) H J K L M
2-Ethylhexyl Acrylate 60 59.5 - - 60 Butyl Acrylate - - 60 60 Methyl Methacrylate - 10 20 19.5 19.6 Methyl Acrylate 9.5 - 19.5 - 20 Vinyl Acetate 30 - - 10 Ethyl Acrylate - 30 - 10 Allyl Methacrylate 0.5 0.5 0.5 0.5 Allyl Acrylate - - - - 0.4 The resultant irradiated compositions will possess excellent adhesive properties even after storage for extended periods of time and are readily removable from any substrate to which they are adhered.
~ , llZ759Z
Summarizing, it is seen tha-t the addition of allyl acrylate or methacrylate into the backbone of acrylate-based hot melt adhesives resul-ts in the production of prepolymeric adhesives which, when cured by exposure to electron beam radiation, are characterized by superior pressure sensitive properties.
Claims (10)
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method for the production of a hot melt adhesive composition having pressure sensitive properties comprising the steps of a) copolymerizing allyl acrylate or methacrylate with at least one copolymerizable acrylic monomer, obtaining thereby a prepolymer solid at ambient temperature;
b) heating the resultant solid allylic unsaturated prepolymer to a temperature sufficient to render it fluid and flowable;
c) coating the fluid prepolymer onto a substrate; and d) exposing the coated substrate to electron beam radiation of 10,000-40,000 J/kg sufficient to crosslink the prepolymer, thereby providing a cured pressure sensitive adhesive.
b) heating the resultant solid allylic unsaturated prepolymer to a temperature sufficient to render it fluid and flowable;
c) coating the fluid prepolymer onto a substrate; and d) exposing the coated substrate to electron beam radiation of 10,000-40,000 J/kg sufficient to crosslink the prepolymer, thereby providing a cured pressure sensitive adhesive.
2. The method of Claim 1 wherein the prepolymer comprises a cam-position of allyl methacrylate and a copolymerizable acrylic monomer.
3. The method of Claim 1 wherein the prepolymer contains at least one monomer selected from the group consisting of the C4-C9 alkyl esters of acrylic and methacrylic acid.
4. The method of Claim 1 wherein the copolymerizable acrylic monomer is selected from the group consisting of the C4-C9 alkyl esters of acrylic acid and is present in the prepolymer in an amount of at least about 50% by weight of the prepolymer.
5. The method of Claim 1 wherein the allyl acrylate or methacry-late is present in an amount of 0.1 to 2 parts by weight of the prepolymer.
6. The method of Claim 1 wherein the allyl acrylate or methacry-late is present in an amount of 0.3 to 0.75 parts by weight of the prepolymer.
7. The method of Claim 1 wherein the allylic unsaturated pre-polymer is heated to a temperature of 120-180°C. to render it fluid and flowable.
8. The method of Claim 1 wherein the coated prepolymer is exposed to an electron beam source of 30,000-40,000 J/kg.
9. A crosslinked pressure sensitive adhesive composition prepared by the method of Claim 1.
10. A crosslinked pressure sensitive adhesive-coated article com-prising a substrate having thereon a layer of the adhesive prepared by the method of Claim 1.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/033,199 US4234662A (en) | 1979-04-26 | 1979-04-26 | Pressure sensitive hot melt adhesive curable by exposure to electron beam radiation |
US033,199 | 1979-04-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1127592A true CA1127592A (en) | 1982-07-13 |
Family
ID=21869048
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA348,858A Expired CA1127592A (en) | 1979-04-26 | 1980-03-31 | Pressure sensitive hot melt adhesive curable by exposure to electron beam radiation |
Country Status (8)
Country | Link |
---|---|
US (1) | US4234662A (en) |
JP (1) | JPS5846235B2 (en) |
BE (1) | BE882894A (en) |
CA (1) | CA1127592A (en) |
DE (1) | DE3015463C2 (en) |
FR (1) | FR2455073A1 (en) |
GB (1) | GB2048274B (en) |
NL (1) | NL180118C (en) |
Families Citing this family (34)
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GB2102011B (en) * | 1981-06-17 | 1984-12-19 | Smith & Nephew Ass | Electron beam cured acrylic adhesive layer |
US5057366A (en) * | 1982-09-16 | 1991-10-15 | Minnesota Mining And Manufacturing Company | Acrylate copolymer pressure-sensitive adhesive coated sheet material |
JPS5956471A (en) * | 1982-09-24 | 1984-03-31 | Nitto Electric Ind Co Ltd | Preparation of double-faced adhesive tape |
JPS59113691A (en) * | 1982-12-20 | 1984-06-30 | 松下電器産業株式会社 | Method of mounting electronic part |
US4810523A (en) * | 1985-05-06 | 1989-03-07 | Neutron Products, Inc. | Pressure-sensitive adhesives |
US5011867A (en) * | 1987-09-28 | 1991-04-30 | Avery International Corporation | Electron-beam cured emulsion pressure-sensitive adhesives |
DE3942232A1 (en) * | 1989-12-21 | 1991-06-27 | Beiersdorf Ag | MELT ADHESIVE ON ACRYLIC BASE |
US5266400A (en) * | 1990-04-20 | 1993-11-30 | Minnesota Mining And Manufacturing Company | Low voltage electron beam radiation cured elastomer-based pressure sensitive adhesive tape |
CA2039586A1 (en) * | 1990-05-02 | 1991-11-03 | Marian R. Appelt | Crosslinked pressure-sensitive adhesives tolerant of alcohol-based excipients used in transdermal delivery devices and method of preparing same |
US5382451A (en) * | 1992-04-06 | 1995-01-17 | Minnesota Mining And Manufacturing | Method for coating adhesive polymers |
US5416127A (en) * | 1993-01-28 | 1995-05-16 | National Starch And Chemical Investment Holding Corporation | Radiation curable hot melt pressure sensitive adhesives |
DE4316317C2 (en) * | 1993-05-15 | 1996-09-05 | Lohmann Gmbh & Co Kg | Strapless pressure-sensitive adhesive tapes with different adhesion on both sides and process for their preparation and their use |
US5391406A (en) * | 1994-03-25 | 1995-02-21 | National Starch And Chemical Investment Holding Corporation | Process of preparing hot melt pressure sensitive adhesives on a substrate |
US5989377A (en) * | 1994-07-08 | 1999-11-23 | Metallized Products, Inc. | Method of protecting the surface of foil and other thin sheet materials before and during high-temperature and high pressure laminating |
CA2211130A1 (en) * | 1995-02-10 | 1996-08-15 | The Minnesota Mining & Manufacturing Company | Process for the production of an article coated with a crosslinked pressure sensitive adhesive |
US6099682A (en) | 1998-02-09 | 2000-08-08 | 3M Innovative Properties Company Corporation Of Delaware | Cold seal package and method for making the same |
CN1261471C (en) * | 1999-10-19 | 2006-06-28 | 阿克佐诺贝尔公司 | Radiation curable hot melt composition and process for application thereof |
DE19961402A1 (en) * | 1999-12-20 | 2001-07-05 | Basf Coatings Ag | Process for the production of coatings from coating materials curable thermally and with actinic radiation |
DE10012580A1 (en) * | 2000-03-15 | 2001-09-27 | Basf Coatings Ag | Photoinitiator free (meth)acrylate copolymer based coating agent, adhesive or sealant, comprises a (meth)acrylate copolymer or a compound that is activated by actinic radiation |
DE10029554A1 (en) | 2000-06-15 | 2002-01-03 | Beiersdorf Ag | Process for the preparation of crosslinkable acrylic PSAs |
DE10049669A1 (en) * | 2000-10-06 | 2002-04-11 | Tesa Ag | Process for the production of crosslinked acrylic hotmelt PSAs |
DE10145229A1 (en) | 2001-09-13 | 2004-08-12 | Tesa Ag | Processing of acrylic hotmelts using reactive extrusion |
FR2832595B1 (en) * | 2001-11-26 | 2004-03-19 | Lainiere De Picardie Bc | METHOD FOR MANUFACTURING A THERMOCOLLATING WEAR WITH POINTS OF THERMOFUSIBLE POLYMER AND THERMOFUSIBLE POLYMER SPECIALLY DESIGNED FOR CARRYING OUT SAID METHOD |
US7744991B2 (en) * | 2003-05-30 | 2010-06-29 | 3M Innovative Properties Company | Thermally conducting foam interface materials |
US7229683B2 (en) * | 2003-05-30 | 2007-06-12 | 3M Innovative Properties Company | Thermal interface materials and method of making thermal interface materials |
US9475967B2 (en) | 2013-04-15 | 2016-10-25 | 3M Innovative Properties Company | Adhesives comprising crosslinker with (meth)acrylate group and olefin group and methods |
US9657191B2 (en) | 2014-01-03 | 2017-05-23 | Dur-A-Flex, Inc. | Low odor reactive methacrylate composition for fast room temperature curing floor coating formulations |
US10100237B2 (en) | 2014-09-02 | 2018-10-16 | 3M Innovative Properties Company | Acrylate adhesive with vinylsilane crosslinking agents |
WO2016040773A1 (en) | 2014-09-12 | 2016-03-17 | 3M Innovative Properties Company | Allyl acrylate crosslinkers for psas |
DE102015217131A1 (en) | 2015-09-08 | 2017-03-09 | Tesa Se | Adhesive resin-modified pressure-sensitive adhesive |
KR102443987B1 (en) | 2017-12-27 | 2022-09-20 | 주식회사 엘지화학 | Light-curable acryl-based resin, adhesive composition comprising the same and adhesive film prepared by using the same |
US11795348B2 (en) * | 2017-12-27 | 2023-10-24 | Lg Chem, Ltd. | Adhesive composition and protective film produced using same |
CN111372956B (en) * | 2017-12-27 | 2022-05-17 | 株式会社Lg化学 | Photocurable acrylic resin, adhesive composition comprising the same, and adhesive film formed using the adhesive composition |
CN114921191A (en) * | 2022-01-28 | 2022-08-19 | 沧州临港弘达新材料制造有限公司 | High-performance environment-friendly radiation curing type hot-melt pressure-sensitive adhesive and preparation method thereof |
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US2052527A (en) * | 1931-01-26 | 1936-08-25 | Casco Products Corp | Combined windshield heater and defroster |
US2278637A (en) * | 1939-11-09 | 1942-04-07 | Du Pont | Resin of interpolymerized substances comprising acrylic or methacrylic anhydride |
US2456647A (en) * | 1944-07-15 | 1948-12-21 | Chessie E Rehberg | Acrylic esters of olefinic alcohols and polymers thereof and method for making them |
US2643991A (en) * | 1949-01-28 | 1953-06-30 | Us Rubber Co | Interpolymers of selected 2-alkenyl 2-alkenoates of like esters with selected 2-alkenyl or like chlorides, ethers or esters with or without a different copolymerizable monoolefinic compound |
US3219610A (en) * | 1961-08-10 | 1965-11-23 | Henry C Tillson | Coating composition comprising a terpolymer of an alkyl acrylate, an alkyl methacrylate and an ester of a beta,gamma-unsaturated alcohol with methacrylic acid |
US4151055A (en) * | 1976-04-05 | 1979-04-24 | Union Carbide Corporation | Radiation curable adhesive compositions |
US4052527A (en) * | 1977-02-07 | 1977-10-04 | National Starch And Chemical Corporation | Radiation polymerized hot melt pressure sensitive adhesives |
US4165266A (en) * | 1977-03-30 | 1979-08-21 | Union Carbide Corporation | Radiation curable pressure sensitive adhesive compositions |
-
1979
- 1979-04-26 US US06/033,199 patent/US4234662A/en not_active Expired - Lifetime
-
1980
- 1980-03-31 CA CA348,858A patent/CA1127592A/en not_active Expired
- 1980-04-17 NL NL8002256A patent/NL180118C/en not_active IP Right Cessation
- 1980-04-21 BE BE0/200311A patent/BE882894A/en not_active IP Right Cessation
- 1980-04-21 FR FR8008854A patent/FR2455073A1/en active Granted
- 1980-04-22 DE DE3015463A patent/DE3015463C2/en not_active Expired
- 1980-04-24 GB GB8013554A patent/GB2048274B/en not_active Expired
- 1980-04-25 JP JP55054437A patent/JPS5846235B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
FR2455073B1 (en) | 1985-03-29 |
BE882894A (en) | 1980-08-18 |
DE3015463A1 (en) | 1980-10-30 |
FR2455073A1 (en) | 1980-11-21 |
NL180118C (en) | 1987-01-02 |
JPS55145778A (en) | 1980-11-13 |
NL180118B (en) | 1986-08-01 |
DE3015463C2 (en) | 1984-07-19 |
GB2048274B (en) | 1983-03-09 |
JPS5846235B2 (en) | 1983-10-14 |
US4234662A (en) | 1980-11-18 |
GB2048274A (en) | 1980-12-10 |
NL8002256A (en) | 1980-10-28 |
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