GB2102011A - Electron beam cured acrylic adhesive layer - Google Patents
Electron beam cured acrylic adhesive layer Download PDFInfo
- Publication number
- GB2102011A GB2102011A GB08118666A GB8118666A GB2102011A GB 2102011 A GB2102011 A GB 2102011A GB 08118666 A GB08118666 A GB 08118666A GB 8118666 A GB8118666 A GB 8118666A GB 2102011 A GB2102011 A GB 2102011A
- Authority
- GB
- United Kingdom
- Prior art keywords
- acrylate
- polymer
- methacrylate
- liquid
- asclaimed
- 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.)
- Granted
Links
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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/58—Adhesives
-
- 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
-
- 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
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
- Y10T428/2891—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof
Description
1 GB 2 102 011 A 1
SPECIFICATION
Cured pressure sensitive adhesive The present invention is concerned with a process for preparing cured acrylic pressure sensitive adhesive layers by applying an acrylate composition containing a cross-linking agentto a substrate and curing it by electron beam radiation and in particular a process of preparing cured pressure sensitive adhesive layers for surgical products and products of the process.
It is well known in the art that the cohesive properties of pressure sensitive adhesives can be improved by curing. Usually this is achieved by heating a pressure sensitive composition which contains a heat reactive cross-linking resin.
United States Specification No. 2,956,904 discloses a method of curing conventional acrylic pre- ssure sensitive adhesives on a substrate by high energy electron irradiation to at least double the cohesive properties of the adhesive. The specification discloses thatthe adhesives are normally applied to the backing as a solution in an organic solvent. The use of solvents for the manufacture of pressure sensitive adhesives is undesirable for economic and safety reasons. In addition conventional pressure sensitive adhesives which have been post cured are usually too hard for surgical adhesive dressings. The specification also discloses that low molecular weight acrylic polymers can be cured by electron irradiation to form cured pressure sensitive adhesive layers but does not disclose the use of a cross-linking agent. A cross-linking agent is necessary to reduce the irradiation energy required to cure the polymer.
British Patent Specification No. 1,298,019 discloses a process for preparing a pressure sensitive product which comprises applying to a backing mat- erial a monomeric layer of a liquid alkyl acrylate composition, optionally containing a polyfunctional acrylic monomer, having an adjusted viscosity of 100 centipoises and subjecting the layer to high energy particle radiation. However, a large amount of radiation energy is required to convert the liquid alkyl acrylate monomer layer into a cohesive cured pressure sensitive adhesive. In addition the adhesive may still contain residual monomer which is highly undesirable in adhesives required for surgical pro- ducts. The use of monomers in the process can also cause toxic and safety hazards.
United States Specification No. 3,897,295 discloses a method of forming a pressure sensitive adhesive by applying to a release paper a solvent- less syrup of an acrylic monomer or monomers and a homopolymer or copolymer of the same monomers optionally containing a polyfunctional acrylate and subjecting the coating to a high energy ionising radiation. The inclusion of a polymer into the monomer coating layer may reduce the radiation energy required to cure the layer but does not eliminate the safety and toxicity hazards of the monomers.
British Patent Specification No. 1,310,328 dis- closes a method of forming pressure sensitive adhesives by heating a solventless acrylic composition of one or moretacky low molecularweight polymersto a temperature sufficiently above the melting point to maintain it as a hot melt, applying the hot melt to a backing and subjecting the composition to ionising irradiation, the composition before irradiation having a Williams Plasticity of up to 1.5. A polyfunctional acrylic monomer can be present in the composition.
British Application No. 2048274A discloses a method of forming a pressure sensitive adhesive layer on a substrate by applying a layer of molten pressure sensitive adhesive material to the substrate comprising a copolymer of a major amount of one or more pressure sensitive adhesive forming acrylic monomers and a minor amount of allyl acrylate or allyl methacrylate and curing the copolymer in situ by electron beam radiation.
The methods disclosed in BP 1,310,328 and G.B. 2048274A avoid the use of solvents or liquid mono- mers by using a prepolymer for the pressure sensitive adhesive forming layer which is applied to the substrate as a hot melt. However both these patents disclose that the prepolymers need to be heated to a temperature of 120'C to 180'C to obtain a suitable low viscosity for coating. The use of hot melt prepolymers has the disadvantage of requiring special hot melt coating equipment which is more expensive to operate than conventional coating equipment and the elevated coating temperatures required limits the number of substrates to which the prepolymers can be directly applied.
A simple and economic process has now been discovered for preparing cured acrylic pressure sensitive adhesive layers by electron beam radiation which process reduces or eliminates the need to use solvents, liquid monomers or heat to apply the layer to the substrate.
The present invention provides a process for the preparation of an adhesive layer on a substrate which comprises applying to the substrate a composition of an acrylate rendered curable by the presence of a cross-linking agent and curing it by electron beam radiation characterised in that the curable composition comprises a liquid alkyl acry- late polymer having a K value of less than 30.
A liquid alkyl acrylate polymer means an alkyl acrylate polymerwhich does not undergo a phase change when heated. Suitable alkyl acrylate polymers are liquid at ambient room or slightly elevated temperatures for example attemperatures of 20T to WC and more suitably Wto 70'C. The preferred liquid alkyl acrylate polymers have a K value of 10 to 30. K values are determined according to H. Kikentscher, Cellulose Chemie 13 58, (1932).
To enable the liquid polymers to be applied to a substrate by conventional coating equipment, the polymers should have a viscosity of less than 1500 poise, at a 20 sec shear rate and preferably a viscosity of 1000 poise at 20 sec71 at 1 O'C to WC.
The liquid polymer will be a polymer of one or more alkyl acrylate monomers normally present in This print embodies corrections made under Section 117(1) of the Patents Act 1977.
2 acrylic pressure sensitive adhesives. Suitable monomers are alkyl esters of acrylic acid in which the alkyl groups have 4 to 12 carbon atoms and preferably have 4 to 18 carbon atoms. Preferred alkyl acrylates are nbutyl acrylate, 2-ethyl hexyl acrylate and iso-octyl acrylate.
The alkyl acrylate component of the polymer can be from 84% to 98% and preferably can be from 87% to 95% by weight of the polymer. Other monofunc- tional monomer units may be present in the polymer. Preferred monomer is acrylic acid. Acrylic acid component of the polymer can be present in amounts up to 10% by weight of the polymer, desirably in amounts of 4% to 8% and preferably in amounts of 5% to 7% by weight of the polymer.
One or more crosslinking agent may be present in the curable composition. Preferred crosslinking agents are polyfunctional acrylates or methacrylates. In a preferred aspect of the invention the crosslinking agent is part of the liquid polymer. Preferred liquid polymers consist of a major amount of one or more alkyl acrylates and a minor amount of a copolymerisable polyfunctional acrylate or methacrylate.
Suitable copolymerisable polyfunctional acrylates or methacrylates have functional groups with differ ent reactivities. Desirably the faster reacting func tional groups will take part in the polymerisation reaction leaving the slower reacting functional groups as unreacted pendant groups which can be available to crosslinkthe polymer on irradiation.
However it is important to avoid extensive crosslink ing in the liquid prepolymer as this would lead to undesirable gel formation. Suitable copolymerisable crosslinking agents include difunctional acrylates or methacrylates of allyl, vinyl and 1,2-disubstituted unsaturated compounds. Preferred crosslinking agents are allyl acrylate and allyl methacrylate. In the absence of other crosslinking agents the difunctional copolymerisable acrylate or methacrylate can be 105 present in the liquid polymer in amounts up to 6% by weight of the polymer, desirably in amounts of 2% to 4% and preferably in amounts of 2.5% to 3.5% by weight of the polymer.
In another aspect of the invention the curable composition can consist of a liquid polymer and a polyfunctional acrylate or methacrylate crosslinking agent. Preferred polyfunctional acrylate or methacrylate crosslinking agents have functional groups of equal reactivity.
Suitable polyfunctional acrylate or methacrylate crosslinking agents forthe liquid polymer include the diacrylate or dimethacrylate esters of ethane diol, butane diol, hexane diol, polyethylene glycol and propylene glycol, trimethylol propane triacrylate 120 and trimethacrylate and pentaethythritol tetraacrylate and tetra methacryl ate.
In the absence of a copolymerisable crosslinking agent in the liquid polymer, the added polyfunc- tional acryiate or methacrylate crosslinking agent can be present in amounts up to. 10% and preferably in amounts of 5%to 10% by weight of the polymer. When both crosslinking agents are used in the liquid curable composition then it is preferred that the copolymerisable polyfunctional acrylate or GB 2 102 011 A 2 methacrylate should be present in amounts of up to 4% by weight of the polymer and the added polyfunctional acrylate or methacrylate should be present in amounts of up to 5% by weight of the polymer.
Suitable liquid curable compositions can comprise a liquid copolymer of butyl acrylate, 2-ethylhexyl acrylate, acrylic acid and allyl methacrylate or mixtures thereof with a polyfunctional acrylate or methacrylate.
A preferred liquid curable composition is a liquid polymer of butyl acrylate (45%), 2-ethyl hexyl acryate (45%), acrylic acid (6%) and ally] methacrylate (^). Another preferred liquid curable composition con- sists of a liquid polymer of butyl acrylate (46%), 2-ethylhexyl acrylate (46%), acrylic acid (6%) and allyl methacrylate (2%) mixed with butane diol diacrylate (5%).
The liquid polymers can be prepared by polymerising the monomers in a heated reaction vessel with a stirrer under reflux in the presence of a solvent with a high chain transfer coefficient and a catalyst with a short half life. Suitable solvents include isopropyl alcohol, industrial methylated spirit, chlorinated hydrocarbons and the like. Suitable catalysts are peroxides such as peroxydicarbonates. A preferred catalyst is dicyclohexyl peroxydicarbonate. The catalyst is preferably added as a solution gradually to the reaction mixture in aliquot parts during a period of polymerisation reaction. This procedure ensures the resultant polymer has a low molecular weight that is a K value of 10 to 30.
A polymerisation inhibitor can be added to the liquid polymer to prevent further polymerisation taking place during the processing of the liquid polymer, for example during a purification process, which may involve a heating step. Suitable polymerisation inhibitors include butylated hydroxy toluene methoxyhydroquinone, phenol thiazine and spiroindene. Preferably the polymerisation inhibitor is also an antioxidant. A favoured combined polymerisation inhibitor and antioxidant is a phenolic derivative known as Permanax WSL avail- able from Vulnax Limited. The polymerisation inhibitor can be present in the liquid polymer in amounts of up to 2% and preferably in amounts up to 1 % by weight of the polymer. The solvent can be stripped from the liquid polymer using a suitable film evaporator for example a rotary film evaporator or a white wall evaporator. Optionally steam stripping may be used to remove residual monomer from the liquid polymer to produce an odourless product.
The polyfunctional acrylate or methacrylate if required can be added to the liquid polymer by simply mixing the two materials by stirring in a suitable container.
To prepare a cured pressure sensitive layerthe liquid curable composition is applied to a substrate and cured by electron beam radiation.
The liquid curable composition can be applied to a substrate by a conventional coating process including doctor blade over flat bed, doctor blade over roller and reverse roller techniques.
Depending on the rheological properties of the 3 GB 2 102 011 A 3 liquid polymer composition it may be convenientto heatthe composition to a temperature of upto 70'C before or during its application to the substrate.
The substrate can be a release surface such as silicone coated paper orfilm or the like from which the adhesive can be transferred to another substrate such as a woven, knitted or non woven fabric. Alternatively the substrata can be a continuous, microporous or macroporous film or sheet which is suitable as a backing for adhesive tape or surgical adhesive dressing. Suitable backings include films of plasticised polyvinyl chloride, microporous polyvinyl chloride, polyurethane, polyethylene terephthalate and unplasticised polyvinyl chloride.
The liquid composition can be cured by passage under electron beam radiation at a dose level of 2.5 to 10 megarads and preferably at a dose level of 4 to 6 megarads.
A convenient source of electron neam radiation is an'Elecron Curtain'equipment made by Energy Sci- 85 ence Inc. Typical curing conditions using this equipment are voltage 150Kv beam current 2.5 milli-amps at processing speed of 50 feet/minute to give a total radiation dose of 5 megarads.
The resultant cured pressure sensitive adhesive 90 can be used on surgical dressings.'The adhesives have good adhesion to skin and do not fail cohe sively when removed from the wound site.
For surgical dressings the coating weight of a cured acrylic pressure sensitive adhesive made by the method of the invention can be 10 to 250 glm', desir ably 200 to 100 glm' and preferably 30 to 50 g/M2.
The cured pressure sensitive adhesives may also be used for industrial tapes.
In a further aspectthe present invention provides 100 surgical dressings and industrial adhesive tapes carrying a cured acrylic pressure sensitive adhesive made by the process of the invention.
Preparation of Liquid Curable Compositions.
(a) n-butylacrylate (1 88g), 2-ethyl hexyl acryl ate (188g), acrylic acid (24g) and ally] methacrylate (16g) monomers together with isopropanol (360g) were added to a reactor vessel and heated under reflux until the mixture reached a temperature of 80T. A solution of dicyclohexyl peroxydicarbonate catalyst 110 (0.28g) in isopropyl alcohol (40g) was added in five aliquots over a period of 50 minutes. The reaction mixture was heated under reflux with stirring for a further period of 2 hours. The reaction mixture was then stripped of solvent by a rotary evaporator. The 115 resultant liquid polymer had a K value of 21 and a viscosity of 4300 poise at 25T and 20 sec7' shear rate. (b) A liquid polymer was made in the same manner as that in (a) described above except that 8g of ally] methacrylate monomer was used instead of 16g. The resultant liquid polymer had a K value of 27 and a viscosity of 5000 poise at 25T at a 20 sec shear rate. Hexane diol diacrylate (20g) was mixed into the liquid composition. (c) n-butylacrylate(23.5),2-ethyihexylacrylate (23. 5g) acrylic acid (3g) and ally[ methacrylate (2g) were pre-mixed and added over a 20 minute period together with a solution of dicyclohexyl peroxydicarbonate (0.023g) in isopropyl alcohol to a reaction vessel containing isopropyl alcohol (200g) refluxing at8TC. After addition of all the monomers a further 0.047g of dicyclohexyl peroxydicarbonate dissolved in isopropyl alcohol was added over 70 minutes to the refluxing reaction mixture. Reflux was continued for a further 30 minutes bringing the total reaction time to 2 hours. A phenolic antioxidant (0.6% by weight of polymer of Permanax WSL) was added and the product stripped on a rotary evaperator to remove solvent and unreacted monomer. The resultant liquid polymer had a K value of 14 and a viscosity of a 1,200 poise at 250C and 200 sec-' shear rate. Example 1 The liquid curable composition (a) as prepared above was heated to 40T and coated onto a silicone release coated paper (Steralease 15 from Sterling Coated Papers Ltd.) by a doctor blade overflat bed coating unit to give a mass weight of 40g/rn'. The coated composition was then cured by exposure to 5 megarads of electron beam radiation (Electric Curtain equipment made by Energy Science Inc.) to give a crosslinked pressure sensitive adhesive. Example 2 The curable liquid composition (b) was coated onto a silicone coated release paper and cured by exposure to electron beam radiation in the same manner as Example 1 to form a crosslinked pressure sensitive adhesive.
Example 3
Claims (21)
1. Process for the preparation of an adhesive layer on a substrate which comprises applying to a substrate a composition of an acrylate rendered cur- able by the presence of a cross-linking agent and curing it by electron beam radiation characterised in thatthe curable composition comprises a liquid alkyl acrylate polymer having a K value of less than 30.
2. A process as claimed in claim 1 in which the liquid alkyl acrylate polymer has a K value of not less than 10.
3. A process as claimed in either of claims 1 or 2 in which the liquid alkyl acrylate polymer contains one or more alkyl esters of acrylic acid in which the alkyl groups have 4 to 12 carbon atoms.
4. A process asclaimed in anyof claims 1 to3 in which the liquid alkyl acrylate polymer contains acrylic acid monomer units.
5. A process asclaimed in an claim 4 in which the liquid acrylate polyer contains ^to 8% by weight of the polymer of acrylic acid monomer units.
6. Aprocess asclaimed in any of claims 1 to 5 in which the cross-linking agent is a polyfunctional acrylate or methacrylate.
7. Aprocess asclaimed in anyof claims 1 to 6 in which the liquid alkyl acrylate polymer contains copolymerisable polyfunctional acrylate or methacrylate monomer units.
8. A process as claimed in claim 7 in which the liquid alkyl acrylate polymer contains 2% to 4% by 4 weight of the polymer of copolymerisable polyfunctional acrylate or methaerylate monomer units.
9. A process as claimed in eitherof claims7 or8 in which the copolymerisable polyfunctional acrylate or methacrylate is ally] acrylate or allyl methacrylate.
10. A process asclaimed in anyof claims 1 to 6 in which the curable composition comprises a liquid alkyl acrylate polymer and a polyfunctional acrylate or methacrylate cross linking agent.
0
11. A process as claimed in claim 10 in which the curable composition contains 5% to 10% by weight of the polymer of a polyfunctional acrylate or methacrylate cross linking agent.
12. A process asclaimed in anyof claims 1 to 9 in which the curable composition comprises a liquid alkyl acrylate polymer containing copolymerisable polyfunctional acrylate or methacrylate monomer units and a polyfunctional acrylate or methacrylate cross linking agent.
13. A process as claimed in claim 12 in which the liquid alkyl acrylate polymer contains up to 5% by weight of the polymer of copolymerisable polyfunc tional acrylate or methacrylate monomer units.
14. A process as claimed in claim 12 in which the liquid alkyl acrylate polymer contains up to 5% by weight of the polymer of a polyfunctional acrylate or methacrylate cross linking agent.
15. A process asclaimed in anyof claims 1 to 14 in which the liquid alkyl acrylate polymer is a copolymer of butyl acrylate 2-ethylhexyl acrylate, acrylic and ally] methacrylate.
16. A process asclaimed in anyof claims 1 to 15 in which the liquid alkyl acrylate polymer is prepared by polymerising the monomers in the presence of a solvent with a high chain transfer coefficient.
17. A process asclaimed in anyof claims 1 to 16 in which the curable composition is cured by passage under electron beam radiation at a dose level of 4 to 6 megarads.
18. A process as claimed in any of claims 1-17 in which the adhesive is a pressure sensitive adhesive.
19. An industrial tape carrying a cured acrylate pressure sensitive adhesive made by the process of any of claims 1-18.
20. A surgical dressing carrying a cured acrylic pressure sensitive adhesive made by the process of any of claims 1-18.
21. A surgical dressing as claimed in claim 20 in which the weight per unit area of the cured acrylic pressure sensitive adhesive layer is20to 100 g/m'.
Printed for Her Majesty's Stationery Office by The Tweeddale Press Ltd., Berwick-upon-Tweed, 1983. Published atthe Patent Office, 25 Southampton Buildings, London, WC2A lAY, from which copies may be obtained.
GB 2 102 011 A 4
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08118666A GB2102011B (en) | 1981-06-17 | 1981-06-17 | Electron beam cured acrylic adhesive layer |
| DE8282303050T DE3266520D1 (en) | 1981-06-17 | 1982-06-11 | Cured pressure sensitive adhesives |
| EP82303050A EP0068696B1 (en) | 1981-06-17 | 1982-06-11 | Cured pressure sensitive adhesives |
| US06/389,009 US4438177A (en) | 1981-06-17 | 1982-06-16 | Cured pressure sensitive adhesives |
| JP57104649A JPS582371A (en) | 1981-06-17 | 1982-06-16 | Curable pressure sensitive adhesive and manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08118666A GB2102011B (en) | 1981-06-17 | 1981-06-17 | Electron beam cured acrylic adhesive layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2102011A true GB2102011A (en) | 1983-01-26 |
| GB2102011B GB2102011B (en) | 1984-12-19 |
Family
ID=10522577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08118666A Expired GB2102011B (en) | 1981-06-17 | 1981-06-17 | Electron beam cured acrylic adhesive layer |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4438177A (en) |
| EP (1) | EP0068696B1 (en) |
| JP (1) | JPS582371A (en) |
| DE (1) | DE3266520D1 (en) |
| GB (1) | GB2102011B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2312214A (en) * | 1996-04-19 | 1997-10-22 | Lintec Corp | Energy beam curable pressure sensitive adhesive composition and use thereof |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5714029A (en) * | 1984-03-12 | 1998-02-03 | Nitto Electric Industrial Co., Ltd. | Process for working a semiconductor wafer |
| JPH0616524B2 (en) * | 1984-03-12 | 1994-03-02 | 日東電工株式会社 | Adhesive thin plate for fixing semiconductor wafers |
| JPS60250601A (en) * | 1984-05-25 | 1985-12-11 | 松下電器産業株式会社 | Method of producing self temperature control resistor |
| US4810523A (en) * | 1985-05-06 | 1989-03-07 | Neutron Products, Inc. | Pressure-sensitive adhesives |
| US5549924A (en) * | 1987-07-17 | 1996-08-27 | Robin Renee Thill Shlenker | Method of forming a membrane, especially a latex or polymer membrane, including a deactivating barrier and indicating layer |
| US5679399A (en) * | 1987-07-17 | 1997-10-21 | Bio Barrier, Inc. | Method of forming a membrane, especially a latex or polymer membrane, including multiple discrete layers |
| DE3817452A1 (en) * | 1988-05-21 | 1989-11-30 | Basf Ag | MELT-ADHESIVE GLUE ADHESIVE IN THE AIR WITH ULTRAVIOLET RAYS |
| GB8907740D0 (en) * | 1989-04-06 | 1989-05-17 | Beam Tech Ltd | Porous articles |
| 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 |
| JPH0419487U (en) * | 1990-06-04 | 1992-02-18 | ||
| DE4233886C1 (en) * | 1992-10-08 | 1994-03-31 | Heraeus Kulzer Gmbh | Conditioning agents and methods for pretreatment of plastic surfaces and use of the conditioning agent |
| US6162511A (en) * | 1996-05-20 | 2000-12-19 | Ballina Pty. Ltd. | Method of coating and compositions for use therein |
| US5888650A (en) * | 1996-06-03 | 1999-03-30 | Minnesota Mining And Manufacturing Company | Temperature-responsive adhesive article |
| US6066394A (en) * | 1997-04-09 | 2000-05-23 | Solutia Inc. | Plasticizer resistant emulsion acrylic pressure sensitive adhesive |
| US6232365B1 (en) | 1998-07-17 | 2001-05-15 | 3M Innovative Properties Company | Low temperature electron beam polymerization |
| DE19846901A1 (en) * | 1998-10-12 | 2000-04-13 | Beiersdorf Ag | Process for the production of adhesive tapes, adhesive tapes coated on one side being subjected to radiation-chemical crosslinking, and use of the adhesive tapes |
| DE10008844A1 (en) * | 2000-02-25 | 2001-09-06 | Beiersdorf Ag | Process for the crosslinking of polyacrylates by electron beams |
| US20030031802A1 (en) * | 2001-05-11 | 2003-02-13 | 3M Innovative Properties Company | Pulsed electron beam polymerization |
| JP5408640B2 (en) * | 2006-09-04 | 2014-02-05 | 日東電工株式会社 | Ultraviolet curable adhesive composition, ultraviolet curable adhesive sheet and method for producing the same |
| JP5000321B2 (en) * | 2007-02-05 | 2012-08-15 | 日東電工株式会社 | Method for producing pressure-sensitive adhesive layer |
| JP5087414B2 (en) | 2008-01-22 | 2012-12-05 | 日東電工株式会社 | Photocurable acrylic viscoelastic material composition, acrylic viscoelastic material, acrylic viscoelastic material layer tape or sheet, and production method thereof |
| JP6047928B2 (en) * | 2012-05-30 | 2016-12-21 | 大日本印刷株式会社 | Adhesive and method for producing the same |
| EP3191544A1 (en) * | 2014-09-12 | 2017-07-19 | 3M Innovative Properties Company | Allyl acrylate crosslinkers for psas |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1252418B (en) * | 1965-05-15 | 1967-10-19 | Badische Anilin &. Soda Fabrik Aktiengesellschaft, Ludwigshafen/Rhem | Process for the production of butadiene polymers |
| US4234662A (en) * | 1979-04-26 | 1980-11-18 | National Starch And Chemical Corporation | Pressure sensitive hot melt adhesive curable by exposure to electron beam radiation |
-
1981
- 1981-06-17 GB GB08118666A patent/GB2102011B/en not_active Expired
-
1982
- 1982-06-11 DE DE8282303050T patent/DE3266520D1/en not_active Expired
- 1982-06-11 EP EP82303050A patent/EP0068696B1/en not_active Expired
- 1982-06-16 JP JP57104649A patent/JPS582371A/en active Granted
- 1982-06-16 US US06/389,009 patent/US4438177A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2312214A (en) * | 1996-04-19 | 1997-10-22 | Lintec Corp | Energy beam curable pressure sensitive adhesive composition and use thereof |
| US5942578A (en) * | 1996-04-19 | 1999-08-24 | Lintec Corp. | Energy beam curable pressure sensitive adhesive composition and use thereof |
| GB2312214B (en) * | 1996-04-19 | 1999-12-29 | Lintec Corp | Energy beam curable pressure sensitive adhesive composition and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0216787B2 (en) | 1990-04-18 |
| US4438177A (en) | 1984-03-20 |
| EP0068696A2 (en) | 1983-01-05 |
| JPS582371A (en) | 1983-01-07 |
| DE3266520D1 (en) | 1985-10-31 |
| EP0068696B1 (en) | 1985-09-25 |
| EP0068696A3 (en) | 1983-10-05 |
| GB2102011B (en) | 1984-12-19 |
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| PCNP | Patent ceased through non-payment of renewal fee |