WO2012026456A1 - 粘着剤組成物 - Google Patents
粘着剤組成物 Download PDFInfo
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- WO2012026456A1 WO2012026456A1 PCT/JP2011/068949 JP2011068949W WO2012026456A1 WO 2012026456 A1 WO2012026456 A1 WO 2012026456A1 JP 2011068949 W JP2011068949 W JP 2011068949W WO 2012026456 A1 WO2012026456 A1 WO 2012026456A1
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- meth
- weight
- pressure
- sensitive adhesive
- adhesive composition
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- PPVWWBVPIXPKLW-UHFFFAOYSA-N CC(C)c1ccc(C(C)(CCC2)C(CC3)C2(C)C(OCC(COc2ccc(C(C)(C)c(cc4)ccc4OCC(COC(C(C)(CCC4)C(CC5)C4(C)c4c5cc(C(C)C)cc4)=O)O)cc2)O)=O)c3c1 Chemical compound CC(C)c1ccc(C(C)(CCC2)C(CC3)C2(C)C(OCC(COc2ccc(C(C)(C)c(cc4)ccc4OCC(COC(C(C)(CCC4)C(CC5)C4(C)c4c5cc(C(C)C)cc4)=O)O)cc2)O)=O)c3c1 PPVWWBVPIXPKLW-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
- C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- 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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
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- 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
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
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- 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
- C09J2433/00—Presence of (meth)acrylic polymer
Definitions
- the present invention relates to an adhesive composition used when an optical film such as a polarizing film or a retardation film is attached to an adherend such as a liquid crystal cell. More specifically, the present invention relates to a pressure-sensitive adhesive composition that exhibits excellent durability even under high temperature and high humidity and is excellent in white spot suppression ability.
- a liquid crystal display device usually includes a liquid crystal cell in which a liquid crystal component oriented in a predetermined direction is sandwiched between two supporting substrates such as glass and an optical film such as a polarizing film, a retardation film, and a brightness enhancement film. It is configured. Adhesives are often used when laminating these optical films or attaching optical films to liquid crystal cells.
- Liquid crystal display devices are widely used as display devices for personal computers, televisions, car navigation systems, and the like. These may be used in harsh environments such as high temperature and high humidity. Accordingly, there is a demand for an adhesive that is excellent in durability and does not peel off or generate bubbles even after long-term use. In a severe environment such as high temperature and high humidity, the optical film undergoes large dimensional changes such as shrinkage and expansion. The conventional pressure-sensitive adhesive layer cannot relax the stress generated by such a dimensional change, and the residual stress of the optical film becomes non-uniform. As a result, there is a problem of so-called “white spots” in which light leaks from the periphery of the liquid crystal display device and becomes white.
- Patent Document 1 Japanese Patent Laid-Open No. 10-279907
- Patent Document 1 Japanese Patent Laid-Open No. 10-279907
- Patent Document 1 Japanese Patent Laid-Open No. 10-279907
- Patent Document 1 Japanese Patent Laid-Open No. 10-279907
- Patent Document 1 Japanese Patent Laid-Open No. 10-279907
- Patent Document 1 Japanese Patent Laid-Open No. 10-279907
- Patent Document 1 Japanese Patent Laid-Open No. 10-279907
- Patent Document 1 Japanese Patent Laid-Open No. 10-279907
- Patent Document 1 Japanese Patent Laid-Open No. 10-279907
- Patent Document 1 Japanese Patent Laid-Open No. 10-279907
- Patent Document 1 Japanese Patent Laid-Open No. 10-279907
- Patent Document 1 Japanese Patent Laid-Open No. 10-279907
- Patent Document 1 Japanese Patent Laid-Open No. 10-279907
- Patent Document 1 Japanese Patent Laid-Open No. 10-279907
- a method for suppressing white spots a method for preventing white spots from occurring by relaxing the stress concentration following the dimensional change of the polarizing film, as in the pressure-sensitive adhesive composition described in Patent Document 1, is the opposite.
- a method of suppressing the occurrence of white spots by using a pressure-sensitive adhesive composition having a high cohesive force and minimizing a region where stress is generated.
- Patent Document 2 Japanese Patent Application Laid-Open No. 2007-112839
- a peroxide 100 parts by weight of an acrylic copolymer
- isocyanate A pressure-sensitive adhesive composition comprising 0.02 to 2 parts by weight of a system cross-linking agent and 1 to 40 parts by weight of a tackifying resin having a softening point of 80 ° C. or higher is disclosed.
- Patent Document 2 has no description regarding white spots, and the ability to suppress white spots is insufficient only with the above configuration.
- an object of the present invention is to provide a pressure-sensitive adhesive composition that is excellent in white spot suppression ability and durability.
- the present invention provides a pressure-sensitive adhesive composition having the following constitution.
- a (meth) acrylic copolymer (A) containing a carboxyl group, a (meth) acrylic copolymer (B) containing a carboxyl group and a hydroxyl group, and the (meth) acrylic copolymer A pressure-sensitive adhesive composition containing 5 to 20 parts by weight of a tolylene diisocyanate compound (C) and an epoxy group-containing silane coupling agent (D) with respect to a total of 100 parts by weight of (A) and (B) .
- the above (6) or (6) comprising 1 to 20 parts by weight of the compound (F) having a hydroxyl group and a rosin skeleton with respect to a total of 100 parts by weight of the acrylic copolymers (A) and (B).
- the epoxy group-containing silane coupling agent (D) is contained in an amount of 0.02 to 1 part by weight based on 100 parts by weight of the total of the (meth) acrylic copolymers (A) and (B) ( 1) The pressure-sensitive adhesive composition according to any one of (8).
- the pressure-sensitive adhesive composition of the present invention has excellent durability even under high temperature and high humidity environments, and has excellent whiteout suppression ability.
- the optical film using the pressure-sensitive adhesive composition of the present invention has excellent whiteout suppression ability and does not peel off or generate bubbles even under high temperature and high humidity conditions. Therefore, personal computers, televisions, car navigation systems, etc.
- the display device can be suitably used.
- the pressure-sensitive adhesive composition of the present invention has little change over time in adhesive strength and is excellent in reworkability.
- reworkability means that when an optical film is stuck to an adherend using an adhesive, the optical film is peeled and removed from the adherend when a defect such as biting of a foreign matter occurs. This is the ease of re-applying the optical film.
- the (meth) acrylic copolymer is mainly composed of an acrylate monomer or a methacrylic acid ester monomer, at least an acrylate monomer or a methacrylic acid ester monomer, and a reactive functional group. It is a copolymer obtained by copolymerizing a monomer having a group.
- “(meth) acryl” is used to mean both “acryl” and “methacryl”.
- the (meth) acrylic acid ester monomer is not particularly limited as long as it has a (meth) acrylic acid ester structure.
- Examples of the monomer having a reactive functional group include a carboxyl group-containing monomer, a hydroxyl group-containing monomer, a glycidyl group-containing monomer, an amide group, an N-substituted amide group-containing monomer, and a tertiary amino acid.
- 1 type (s) or 2 or more types, such as a group containing monomer, can be used.
- carboxyl group-containing monomer examples include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, citraconic acid, cinnamic acid, monohydroxyethyl (meth) acrylate succinate, and maleic acid.
- Acid monohydroxyethyl (meth) acrylate, fumarate monohydroxyethyl (meth) acrylate, phthalate monohydroxyethyl (meth) acrylate, 1,2-dicarboxycyclohexane monohydroxyethyl (meth) acrylate, (meth) acrylic acid dimer , ⁇ -carboxy-polycaprolactone mono (meth) acrylate, and the like can be used, but are not limited thereto.
- hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-methyl- 3-hydroxybutyl (meth) acrylate, 1,1-dimethyl-3-butyl (meth) acrylate, 1,3-dimethyl-3-hydroxybutyl (meth) acrylate, 2,2,4-trimethyl-3-hydroxypentyl (Meth) acrylate, 2-ethyl-3-hydroxyhexyl (meth) acrylate, glycerin mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene Recall) mono (meth) acrylate, N- methylol acrylamide, allyl alcohol, can be used methallyl alcohol, but is not limited thereto.
- Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl vinyl ether, 3,4-epoxycyclohexyl vinyl ether, glycidyl (meth) allyl ether, 3,4 -Epoxycyclohexyl (meth) allyl ether or the like can be used, but is not limited thereto.
- Examples of the amide group and N-substituted amide group-containing monomer include acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, and N-ethoxy.
- Methyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-tert-butyl acrylamide, N-octyl acrylamide, diacetone acrylamide and the like can be used, but are not limited thereto. Is not to be done.
- dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and the like can be used, but are not limited thereto.
- the (meth) acrylic copolymer (A) used in the present invention contains a (meth) acrylic acid ester monomer and a carboxyl group-containing monomer as copolymer components.
- the proportion of the (meth) acrylic acid ester monomer as a copolymer component is 80% by weight with respect to the (meth) acrylic copolymer (A). % Or more is preferable.
- the proportion of the carboxyl group-containing monomer as a copolymer component is 0.5% relative to the (meth) acrylic copolymer (A). It is preferably ⁇ 5% by weight, more preferably 1 to 3% by weight. If the content of the carboxyl group-containing monomer is 0.5% by weight or more based on the (meth) acrylic copolymer (A), the cohesive force and durability of the pressure-sensitive adhesive composition may be increased. This is preferable because it is possible. On the other hand, if the content of the carboxyl group-containing monomer is 5% by weight or less with respect to the (meth) acrylic copolymer (A), it is preferable because reworkability is excellent.
- the weight average molecular weight (Mw) of the (meth) acrylic copolymer (A) used in the present invention is preferably 500,000 to 2,500,000, and more preferably 1,000,000 to 2,500,000. If the weight average molecular weight (Mw) of the (meth) acrylic copolymer (A) is 500,000 or more, it is preferable because sufficient cohesive force can be obtained and generation of bubbles can be suppressed. Moreover, if the weight average molecular weight (Mw) of a (meth) acrylic-type copolymer (A) is 2.5 million or less, since an adhesive composition can be easily applied to an optical film etc., it is preferable.
- the (meth) acrylic copolymer (B) used in the present invention contains a (meth) acrylic acid ester monomer, a carboxyl group-containing monomer, and a hydroxyl group-containing monomer as a copolymer component.
- the proportion of the (meth) acrylic acid ester monomer as a copolymer component is 80% by weight with respect to the (meth) acrylic copolymer (B). % Or more is preferable.
- the proportion of the carboxyl group-containing monomer as the copolymer component is 0.1% with respect to the (meth) acrylic copolymer (B). It is preferably ⁇ 5% by weight, more preferably 0.5-3% by weight. If the content of the carboxyl group-containing monomer is 0.1% by weight or more with respect to the (meth) acrylic copolymer (B), the durability of the pressure-sensitive adhesive composition can be increased, which is preferable. . On the other hand, if the content of the carboxyl group-containing monomer is 5% by weight or less based on the (meth) acrylic copolymer (B), it is preferable because reworkability is excellent.
- the proportion of the hydroxyl group-containing monomer as a copolymer component is 0.01 to about (meth) acrylic copolymer (B).
- the content is preferably 2% by weight, more preferably 0.1 to 1% by weight. If the content of the hydroxyl group-containing monomer is 0.01% by weight or more with respect to the (meth) acrylic copolymer (B), the white spot suppression ability is high and preferable. On the other hand, if the content of the hydroxyl group-containing monomer is 2% by weight or less with respect to the (meth) acrylic copolymer (B), it is preferable because peeling of the pressure-sensitive adhesive can be suppressed.
- the weight average molecular weight (Mw) of the (meth) acrylic copolymer (B) used in the present invention is preferably 500,000 to 2,500,000, and more preferably 1,000,000 to 2,500,000.
- a weight average molecular weight (Mw) of the (meth) acrylic copolymer (B) of 500,000 or more is preferable because sufficient cohesive force can be obtained and the generation of bubbles can be suppressed.
- the weight average molecular weight (Mw) of a (meth) acrylic-type copolymer (B) is 2.5 million or less, since an adhesive composition can be easily applied to an optical film etc., it is preferable.
- the weight average molecular weight (Mw) of the (meth) acrylic copolymer is a value measured by the following method.
- GPC HLC-8220 GPC [manufactured by Tosoh Corporation] Column: 4 TSK-GEL GMHXL used Mobile phase solvent: Tetrahydrofuran Standard sample: Standard polystyrene Flow rate: 0.6 ml / min, Column temperature: 40 ° C
- the polymerization method of the (meth) acrylic copolymers (A) and (B) used in the present invention is not particularly limited, and methods such as solution polymerization, emulsion polymerization, and suspension polymerization can be used. .
- a process process is comparatively simple and can be performed in a short time, it is preferable to superpose
- a predetermined organic solvent, a monomer, a polymerization initiator, and a chain transfer agent used as needed are generally charged in a polymerization tank, and stirred in a nitrogen stream or under reflux of the organic solvent.
- a method such as heating reaction for several hours can be used.
- the weight average molecular weights of the (meth) acrylic copolymers (A) and (B) used in the present invention are adjusted to the desired molecular weight by adjusting the reaction temperature, time, solvent amount, and type and amount of the catalyst. can do.
- the pressure-sensitive adhesive composition of the present invention contains a tolylene diisocyanate compound (C).
- tolylene diisocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and dimers, trimers, and trimethylolpropane adducts thereof.
- the content of the tolylene diisocyanate compound (C) in the pressure-sensitive adhesive composition of the present invention is 5 to 20 parts by weight with respect to a total of 100 parts by weight of the (meth) acrylic copolymers (A) and (B). It is preferable to do. If the content of the tolylene diisocyanate compound (C) is 5 parts by weight or more with respect to a total of 100 parts by weight of the (meth) acrylic copolymer (A) and (B), the white spot suppression ability is excellent. preferable.
- the content of the tolylene diisocyanate compound (C) is 20 parts by weight or less with respect to a total of 100 parts by weight of the (meth) acrylic copolymer (A) and (B), the (meth) acrylic system
- the compatibility with the copolymers (A) and (B) can be ensured, and a sufficient tack as an adhesive is obtained, which is preferable.
- the pressure-sensitive adhesive composition of the present invention can be used in combination with a crosslinking agent other than the tolylene diisocyanate compound (C) as desired.
- the pressure-sensitive adhesive composition of the present invention contains an epoxy group-containing silane coupling agent (D).
- epoxy group-containing silane coupling agent (D) that can be used in the present invention include 3-glycidides such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane.
- 3-glycidoxypropylalkyldialkoxysilanes such as xylpropyltrialkoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, methyltri (glycidyl) silane, 2- (3 2- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, such as 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane And tetraethoxy Examples include, but are not limited to, a silicone alkoxy oligomer containing an epoxy group and a hydrolyzable alkoxy group in one molecule, such as a copolymer of orchid and a copolymer of 3-glycidoxypropyl
- the epoxy group-containing silane coupling agent (D) in the present invention is one having at least one of a methoxy group or an ethoxy group in the molecule, the adhesive strength and reworkability can be easily adjusted. preferable.
- an oligomer is used as the epoxy group-containing silane coupling agent (D) in the present invention, performance such as adhesive strength, durability, reworkability and the like can be stably obtained for a long period of time because of low volatility. preferable.
- Examples of the epoxy group-containing silane coupling agent (D) that can be used in the present invention include product names KBM-303, KBM-403, KBE-402, KBE-403, X-41-1053 manufactured by Shin-Etsu Chemical Co., Ltd. Examples thereof include, but are not limited to, X-41-1056 and X-41-1095A.
- the compounding amount of the epoxy group-containing silane coupling agent (D) in the pressure-sensitive adhesive composition of the present invention is 0.02 to the total of 100 parts by weight of the (meth) acrylic copolymers (A) and (B).
- the amount is preferably 1 part by weight, more preferably 0.1 to 0.7 part by weight.
- the amount of the epoxy group-containing silane coupling agent (D) is 0.02 parts by weight or more, the adhesive force and the reworkability can be sufficiently adjusted, which is preferable.
- the compounding quantity of an epoxy-group-containing silane coupling agent (D) shall be 1 weight part or less, adhesive force will not become high too much or rework property will not worsen, and it is preferable.
- the pressure-sensitive adhesive composition of the present invention may contain amino-modified silicone (E).
- the pressure-sensitive adhesive composition of the present invention can easily control the adhesive strength and reworkability by adjusting the content of amino-modified silicone (E). Moreover, the time-dependent change of adhesive force can be suppressed by making the adhesive composition of this invention contain amino modified silicone (E).
- amino-modified silicone (E) it is more preferable to use one having an amino group in the side chain.
- Examples of the amino-modified silicone (E) that can be used in the present invention include the product names KF-868, KF-865, KF-864, KF-859, KF-393, KF-860, KF- manufactured by Shin-Etsu Chemical Co., Ltd. 880, KF-8004, KF-8002, KF-8005, KF-867, X-22-3820W, KF-869, KF-861, X-22-3939A, KF-877 and the like.
- the amino-modified silicone (E) that can be used in the present invention is not limited to the above examples.
- the compounding amount of the amino-modified silicone (E) in the pressure-sensitive adhesive composition of the present invention is 0.05 to 1 part by weight with respect to a total of 100 parts by weight of the (meth) acrylic copolymers (A) and (B).
- the content is 0.1 to 0.7 parts by weight.
- the compounding amount of the amino-modified silicone (E) is 0.05 parts by weight or more, the adhesive strength and the reworkability can be easily controlled, and the change with time of the adhesive strength can be suppressed.
- the compounding amount of the amino-modified silicone (E) is 1 part by weight or less, it is preferable because the adhesive strength is not significantly reduced.
- the pressure-sensitive adhesive composition of the present invention can optionally contain a compound (F) having a hydroxyl group and a rosin skeleton. It is preferable that the pressure-sensitive adhesive composition of the present invention contains a compound (F) having a hydroxyl group and a rosin skeleton because white spots can be further suppressed.
- the compound (F) having a hydroxyl group and a rosin skeleton that can be used in the present invention, for example, a reaction product of rosin and a polyhydric alcohol, a reaction product of rosin and an epoxy compound, or rosin phenol can be used.
- the rosin include wood rosin, gum rosin, hydrogenated rosin, disproportionated rosin, tall oil rosin and wood polymer rosin, gum polymer rosin, polymer oil rosin such as tall oil polymer rosin, and mixtures thereof. Can be used.
- the polyhydric alcohol is not particularly limited as long as it is divalent or higher.
- trihydric alcohols such as 1,5-triol and glycerin
- tetrahydric alcohols such as diglycerin and pentaerythritol, but alcohols having a valence of 5 or more may also be used.
- the reaction between the rosin and the polyhydric alcohol is not particularly limited, and various known means can be used. Specifically, rosin and polyhydric alcohol are charged into a reaction vessel (preferably under an inert gas stream such as nitrogen or a rare gas), and the system is usually heated to about 150 to 300 ° C. under atmospheric pressure. What is necessary is just to make it react, removing the water to do out of the system.
- an esterification catalyst may be used.
- acid catalysts such as acetic acid and p-toluenesulfonic acid
- alkali metal hydroxides such as lithium hydroxide
- alkaline earth metal hydroxides such as calcium hydroxide
- calcium oxide, magnesium oxide and the like A metal oxide etc.
- epoxy compound various known diepoxy compounds can be used. Specifically, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene Acyclic aliphatic diglycidyl ethers such as glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether; 2,2-bis (4-hydroxyphenyl) propane diglycidyl ether, bis ( 4-hydroxyphenyl) methanediglycidyl ether, 1,1-bis (4-hydroxyphenyl) ethanedigly Diethyl ether, 2,2-bis (4-hydroxycyclohexyl) propane diglycidyl
- the reaction between the rosin and the epoxy compound is not particularly limited, and various known means can be used.
- the ring-opening addition reaction may be continued in the presence of a catalyst of 1 mole of diepoxy compound and 2 moles of rosin at 120 to 200 ° C. until the acid value is 5 or less, preferably 3 or less.
- the catalyst include amine catalysts such as trimethylamine, triethylamine, tributylamine, benzyldimethylamine, pyridine, 2-methylimidazole, quaternary ammonium salts such as benzyltrimethylammonium chloride, Lewis acids, boric acid esters, organometallic compounds.
- Organic metal salts can be used.
- the reaction product obtained by this method is a diol compound having a narrow molecular weight distribution having two rosin skeletons and two hydroxyl groups in the molecule.
- polymers obtained by ring-opening polymerization of ethylene oxide, propylene oxide, or ⁇ -caprolactone using the diol compound as an initiator can be used in the same manner.
- rosin phenol what is obtained by addition reaction of phenols with rosin, or so-called rosin phenol obtained by reacting rosin with a resol type phenol resin obtained by addition reaction of phenols and formaldehyde in the presence of an alkali catalyst.
- rosin-modified phenol Any phenol can be used as long as it can be added to rosin. Specific examples include phenol, cresol, ⁇ -naphthol, para t-butylphenol, paraoctylphenol, paranonylphenol, and the like.
- the compound (F) having a hydroxyl group and a rosin skeleton for example, “Pine Crystal D-6011”, “Pine Crystal KE-615-3”, “Pine Crystal D-6240”, “Pinecrytal KE-359” "Arakawa Chemical Industries, Ltd.”, “Neotor 125P”, “Neotor 150P” [Harima Kasei Co., Ltd.] and other commercial products can be suitably used.
- a compound represented by the following formula (II) is particularly preferable.
- the compounding amount of the compound (F) having a hydroxyl group and a rosin skeleton in the pressure-sensitive adhesive composition of the present invention is 1 to 20 weights with respect to a total of 100 parts by weight of the meth) acrylic copolymers (A) and (B). Part, preferably 5 to 15 parts by weight.
- the amount of the compound (F) having a hydroxyl group and a rosin skeleton is 1 part by weight or more, white spots can be suppressed, which is preferable.
- skeleton is 20 parts weight or less, since adhesive force does not become high too much and rework property does not fall, it is preferable.
- the pressure-sensitive adhesive composition of the present invention can be appropriately blended with various additives, solvents, weathering stabilizers, plasticizers, softeners, dyes, pigments, inorganic fillers and the like as desired.
- the range of blending amounts of weathering stabilizer, plasticizer, softener, dye, pigment, inorganic filler, etc. is 30 parts by weight or less with respect to 100 parts by weight of the total of the acrylic copolymers (A) and (B). More preferably, it is 20 parts by weight or less, and most preferably 10 parts by weight or less.
- the pressure-sensitive adhesive composition can appropriately maintain the balance of the adhesive strength, wettability, heat resistance, and paste transferability of the pressure-sensitive adhesive composition, and exhibits a variety of good physical properties. can get.
- a polarizing film was used as an example of the optical film, and a polarizing film having an adhesive layer was produced.
- the pressure-sensitive adhesive composition was applied onto a release film surface-treated with a silicone release agent so that the coating amount after drying was 25 g / cm 2 .
- it was dried with a hot air circulation dryer at 100 ° C. for 90 seconds to form an adhesive layer.
- the pressure-sensitive adhesive layer surface is bonded to the back surface of a polarizing base film (a cellulose triacetate (TAC) film laminated on both sides of a polarizer mainly composed of a polyvinyl alcohol (PVA) film; about 190 ⁇ m), and then applied to a pressure nip roll. Crimped through.
- the film was cured at 23 ° C. and 65% RH for 10 days to obtain a polarizing film having an adhesive layer.
- the pressure-sensitive adhesive solution prepared in each of the following examples was applied to the release treatment surface of a polyethylene terephthalate (PET) film P (thickness: 10 ⁇ m) that had been subjected to release treatment on one side, and the thickness after drying was about
- the pressure-sensitive adhesive layer was formed by casting to have a thickness of 25 ⁇ m and drying by heating at 100 ° C. for 1 minute.
- a polyethylene terephthalate (PET) film Q (thickness: 50 ⁇ m) having a release treatment on one side is prepared, and the surface of the adhesive layer of the PET film P is prepared.
- the PET film Q was overlapped so that the release treatment surface was in contact with each other and pressed through a pressure nip roll, and bonded together. Thereafter, curing was performed for 7 days under conditions of a temperature of 23 ° C. and a relative humidity of 50%, thereby obtaining a double-sided PSA sheet having a PET film on both sides of the PSA layer via a release treatment.
- This double-sided pressure-sensitive adhesive sheet is a pressure-sensitive adhesive sheet made of a pressure-sensitive adhesive layer itself without a base material by peeling off two PET films provided through a release treatment.
- the PET film Q with a thickness of 38 ⁇ m provided on one side of the obtained double-sided pressure-sensitive adhesive sheet is peeled off, and the PET film with a thickness of 100 ⁇ m that is not subjected to a release treatment so as to come into contact with the surface of the exposed pressure-sensitive adhesive layer
- a test sheet was prepared by stacking R [trade name: A4100, manufactured by Toyobo Co., Ltd.], pressing through a pressure nip roll, and bonding.
- test sheet described above was cut into 25 mm ⁇ 150 mm to obtain a sample piece, and the PET film P having a thickness of 100 ⁇ m was peeled off, and the surface of the exposed pressure-sensitive adhesive layer was formed on a 2 mm thick glass plate.
- a test sample was prepared by pressure bonding using a table laminating machine. The obtained test sample was allowed to stand for 24 hours under the conditions of 23 ° C. and 50% RH, and then one end of the PET film R was oriented in the direction of 180 ° with a desktop material testing machine STA-1225 (Orientec Co., Ltd.). Tensile strength and adhesive strength at 180 ° peeling (peeling speed: 300 mm / min) were measured. Evaluation was performed according to the following evaluation criteria.
- Example 1 506 parts by weight of the acrylic copolymer solution synthesized in Production Example 1 as the acrylic copolymer (A) (85 parts by weight as the acrylic copolymer (A)), and the production example as the acrylic copolymer (B) 76 parts by weight of the acrylic copolymer solution synthesized in 2 (15 parts by weight as the acrylic copolymer (B)), 17 parts by weight of coronate L as the tolylene diisocyanate compound (C) (manufactured by Nippon Polyurethane Co., Ltd., 13 parts by weight of active ingredient), 0.02 part by weight of TETRAD-X as an epoxy crosslinking agent (epoxy compound manufactured by Mitsubishi Gas Chemical Co., Ltd., 0.02 part by weight of active ingredient), a compound having a hydroxyl group and a rosin skeleton (F ) D-6011 as 5 parts by weight (rosin-containing diol manufactured by Arakawa Chemical Industries, active ingredient 5 parts by weight), and epoxy group-containing silane coupling agent (
- a pressure-sensitive adhesive composition was obtained by sufficiently stirring and mixing the amino-modified silicone manufactured and 0.1 part by weight of the active ingredient. Using the obtained pressure-sensitive adhesive composition, a test optical film was prepared by the above-described test optical film preparation method, and the above-described various measurements were performed.
- the optical film of Example 1 showed durability (80 ° C. DRY, 105 ° C. DRY, 60 ° C. ⁇ 90% RH), and the evaluation standard of the white-out item was “ ⁇ ”. That is, it was shown that the optical film of Example 1 was excellent in durability and white spot suppression ability even in a high temperature or high temperature and high humidity environment.
- test optical films of Examples 2 to 17 and Comparative Examples 1 to 5 were prepared in the same manner as in Example 1, and the performance was improved. evaluated.
- Coronate L Made by Nippon Polyurethane, 75% active ingredient X-41-1053: Shin-Etsu Chemical Co., Ltd., 100% active ingredient, alkoxy oligomer system, alkoxy group is methoxy / ethoxy X-41-1056: Shin-Etsu Chemical Co., Ltd., 100% active ingredient, alkoxy oligomer system, alkoxy group is methoxy KBM-403: Shin-Etsu Chemical Co., active ingredient 100%, alkoxy monomer system, alkoxy group is methoxy, chemical name is 3-glycidoxypropyltrimethoxysilane KBM-803: Shin-Etsu Chemical Co., Ltd., active ingredient 100%, alkoxy Monomer system, alkoxy group is methoxy, chemical name is 3-mercaptopropyltrimethoxysilane KF-859: manufactured by Shin-Etsu Chemical Co., Ltd., 100% active ingredient, amino-modified KF-353: manufactured by Shin-Ets
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Abstract
Description
(1)カルボキシル基を含有する(メタ)アクリル系共重合体(A)と、カルボキシル基及び水酸基を含有する(メタ)アクリル系共重合体(B)と、前記(メタ)アクリル系共重合体(A)及び(B)の合計100重量部に対して、トリレンジイソシアネート系化合物(C)を5~20重量部と、エポキシ基含有シランカップリング剤(D)と、を含む粘着剤組成物。
(2)前記エポキシ基含有シランカップリング剤(D)が、分子内に少なくともメトキシ基またはエトキシ基の何れかを有することを特徴とする上記(1)に記載の粘着剤組成物。
(3)前記エポキシ基含有シランカップリング剤(D)が、オリゴマーであることを特徴とする上記(1)または(2)に記載の粘着剤組成物。
(4)更に、アミノ変性シリコーン(E)を含む上記(1)~(3)の何れか一つに記載の粘着剤組成物。
(5)前記(メタ)アクリル系共重合体(A)及び(B)の合計100重量部に対して、前記アミノ変性シリコーン(E)を0.05~1重量部含む上記(4)に記載の粘着剤組成物。
(6)更に、水酸基とロジン骨格とを有する化合物(F)を含む上記(1)~(5)の何れか一つに記載の粘着剤組成物。
(7)前記水酸基とロジン骨格とを有する化合物(F)が、分子内に下記式(I)で示す骨格を有する化合物である上記(6)に記載の粘着剤組成物。
(9)前記(メタ)アクリル系共重合体(A)及び(B)の合計100重量部に対して、前記エポキシ基含有シランカップリング剤(D)を0.02~1重量部含む上記(1)~(8)の何れか一つに記載の粘着剤組成物。
下記(1)~(3)に従って測定する。
(1)アクリル系共重合体溶液を剥離紙に塗布し、100℃で2分間乾燥し、フィルム状のアクリル系共重合体を得る。
(2)前記(1)で得られたフィルム状のアクリル系共重合体をテトラヒドロフランにて固形分0.2%になるように溶解させる。
(3)下記条件にて、ゲルパーミエーションクロマトグラフィー(GPC)を用いて、アクリル系共重合体の重量平均分子量(Mw)を測定する。
(条件)
GPC:HLC-8220 GPC〔東ソー(株)製〕
カラム:TSK-GEL GMHXL4本使用
移動相溶媒:テトラヒドロフラン
標準試料:標準ポリスチレン
流速:0.6ml/min、カラム温度:40℃
光学フィルムの一例として偏光フィルムを使用し、粘着剤層を有する偏光フィルムを作製した。シリコーン系離型剤で表面処理された剥離フィルム上に、乾燥後の塗工量が25g/cm2となるように、粘着剤組成物を塗布した。次に、100℃で90秒間熱風循環式乾燥機にて乾燥して粘着剤層を形成した。続いて、偏光ベースフィルム〔ポリビニルアルコール(PVA)フィルムを主体とする偏光子の両面にセルローストリアセテート(TAC)フィルムをラミネートしたもの;約190μm〕の裏面に粘着剤層面を貼り合せ、加圧ニップロールに通して圧着した。圧着後、23℃、65%RHで10日間養生させて粘着剤層を有する偏光フィルムを得た。
「(1)試験用光学フィルムの作製」において作製した偏光フィルムを、光の吸収軸に対して長辺が45゜になるようにカットした140mm×260mm(長辺)の試験片を用い、0.7mmコーニング社製無アルカリガラス板「#1737」の片面にラミネーターを用いて貼付した。次に、このサンプルにオートクレーブ処理(50℃、5kg/cm2、20分)を施し、23℃、65%RHの条件下で24時間放置した。その後、80℃DRYで500時間、及び60℃90%RHの環境で500時間放置し、発泡、剥れの状態を目視観察にて評価した。評価基準は次の通りである。
a)耐熱試験(80℃DRYで500時間放置後、発泡の有無を評価)
◎:発泡が全くない
○:1つのコーナーに発泡があるが実用可能
○△:2つのコーナーに発泡があるが実用可能
△:2つ以上のコーナーに発泡があり実用不可能
×:顕著な発泡があり実用不可能
◎:スジ、剥がれが全くない
○:1つのコーナーにスジがあるが実用可能
○△:2つのコーナーにスジまたは剥がれがあるが実用可能
△:2つ以上のコーナーにスジまたは剥がれがあり実用不可能
×:顕著なスジまたは剥がれがあり実用不可能
「(2)耐久性の評価」と同様のサイズの粘着剤層を有する偏光フィルムを0.7mmコーニング社製無アルカリガラス板「#1737」の両面に、偏光軸が互いに直交するように貼付した試験サンプルを作製した。次に、このサンプルにオートクレーブ処理(50℃、5kg/cm2、20分)を施し、23℃、50%RHの条件下で24時間放置した。その後、80℃DRYの条件下に500時間、放置した。放置後、23℃、50%RHの条件下で均一光源(株式会社アイ・システム製)を使用し、EyeScale-3W(株式会社アイ・システム製)にて白抜けを目視にて確認した。ムラ測定システムEyeScale-3WのCCDカメラは、試験片から200cm離れた位置に設置し、白抜けを評価した。
(白抜け評価基準)
◎:白抜けが全くない
○:僅かな白抜けがある
○△:白抜けがあるが実用可能
△:白抜けがあり実用不可能
×:輝度の高い白抜けがあり実用不可能
片面に離型処理が施されているポリエチレンテレフタレート(PET)フィルムP(厚さ:10μm)の離型処理面に、以下の各実施例で調製した粘着剤溶液を、乾燥後の厚さが約25μmとなるように流延塗布し、100℃で1分間加熱乾燥させて粘着剤層を形成した。PETフィルムPとは別に、片面に離型処理が施されている(軽剥離性の)ポリエチレンテレフタレート(PET)フィルムQ(厚さ:50μm)を用意し、PETフィルムPの粘着材層の表面に、PETフィルムQをその離型処理面が接触するように重ねて加圧ニップロ-ルを通して圧着し、貼り合わせた。その後、温度23℃、相対湿度50%の条件下で7日間養生を行なうことで、粘着剤層の両面にそれぞれ離型処理を介してPETフィルムを有する両面粘着シートを得た。この両面粘着シートは、離型処理を介して設けられている2枚のPETフィルムを剥がすことで、基材のない粘着材層自体からなる粘着シートである。
得られた両面粘着シートの一方に設けられている厚さ38μmのPETフィルムQを剥離し、露出した粘着剤層の表面に接するように、離型処理が施されていない厚さ100μmのPETフィルムR〔商品名:A4100、東洋紡績(株)製〕を重ね、加圧ニップロ-ルを通して圧着し、貼り合わせることで試験用シートを作製した。
上述した試験用シートを25mm×150mmにカットしてサンプル片とし、得られたサンプル片の厚さ100μmのPETフィルムPを剥離し、露出した粘着剤層の表面を厚さ2mmのガラス板に、卓上ラミネート機を用いて圧着し、試験サンプルとした。得られた試験サンプルを23℃、50%RHの条件下で24時間放置した後、卓上型材料試験機STA-1225((株)オリエンテック製)によりPETフィルムRの一端を180゜の方向に引っ張り、180゜剥離における粘着力(剥離速度:300mm/min)を測定した。評価は、下記の評価基準にしたがって行なった。
<リワーク性評価基準>
○:23℃×1時間後、及び50℃4時間後の何れも2~12N/25mmの範囲内
×:23℃×1時間後、及び50℃4時間後の何れかが2~12N/25mmの範囲外
(製造例1)
温度計、攪拌機、窒素導入管、及び還流冷却管を備えた反応器内に、n-ブチルアクリレート(BA)99重量部、アクリル酸(AA)1重量部、酢酸エチル(EAc)100重量部、及びアゾビスイソブチロニトリル(AIBN)0.1重量部を入れ、反応容器の空気を窒素ガスで置換した。その後、攪拌下、窒素雰囲気中で、反応容器の内容物温度を65℃に昇温させて8時間反応させた。反応終了後、反応混合物を酢酸エチルで希釈し、固形分16.8重量%のアクリル系共重合体溶液を得た。アクリル系重合体の重量平均分子量は167万であった。
温度計、攪拌機、窒素導入管、及び還流冷却管を備えた反応器内に、n-ブチルアクリレート(BA)83.5重量部、t-ブチルアクリレート(t-BA)15重量部、2-ヒドロキシエチルアクリレート(2HEA)0.5重量部、アクリル酸(AA)1重量部、酢酸エチル(EAc)100重量部、及びアゾビスイソブチロニトリル(AIBN)0.1重量部を入れ、反応容器の空気を窒素ガスで置換した。その後、攪拌下、窒素雰囲気中で、反応容器の内容物温度を65℃に昇温させて8時間反応させた。反応終了後、反応混合物を酢酸エチルで希釈し、固形分19.7重量%のアクリル系共重合体溶液を得た。アクリル系重合体の重量平均分子量は146万であった。
アクリル系共重合体(A)として製造例1で合成したアクリル共重合体溶液を506重量部(アクリル系共重合体(A)として85重量部)、アクリル系共重合体(B)として製造例2で合成したアクリル系共重合体溶液を76重量部(アクリル共重合体(B)として15重量部)、トリレンジイソシアネート系化合物(C)として、コロネートLを17重量部(日本ポリウレタン社製、有効成分13重量部)、エポキシ系架橋剤としてTETRAD-Xを0.02重量部(三菱瓦斯化学社製のエポキシ化合物、有効成分0.02重量部)、水酸基とロジン骨格とを有する化合物(F)としてD-6011を5重量部(荒川化学工業社製のロジン含有ジオール、有効成分5重量部)、エポキシ基含有シランカップリング剤(D)としてX-41-1053を0.2重量部(信越化学工業社製シランカップリング剤、有効成分0.2重量部)、及びアミノ変性シリコーン(E)としてKF-859を0.1重量部(信越化学工業社製アミノ変性シリコーン、有効成分0.1重量部)を十分に攪拌混合して粘着剤組成物を得た。得られた粘着剤組成物を使用して、前記の試験用光学フィルムの作製方法により試験用光学フィルムを作製し、前記の各種測定を行った。
X-41-1053:信越化学社製、有効成分100%、アルコキシオリゴマー系でアルコキシ基はメトキシ/エトキシ
X-41-1056:信越化学社製、有効成分100%、アルコキシオリゴマー系でアルコキシ基はメトキシ
KBM-403:信越化学社製、有効成分100%、アルコキシモノマー系でアルコキシ基はメトキシ、化学名は3-グリシドキシプロピルトリメトキシシラン
KBM-803:信越化学社製、有効成分100%、アルコキシモノマー系でアルコキシ基はメトキシ、化学名は3-メルカプトプロピルトリメトキシシラン
KF-859:信越化学社製、有効成分100%、アミノ変性
KF-353:信越化学社製、有効成分100%、ポリエーテル変性
D-6011:荒川化学社製、有効成分100%
Claims (9)
- カルボキシル基を含有する(メタ)アクリル系共重合体(A)と、
カルボキシル基及び水酸基を含有する(メタ)アクリル系共重合体(B)と、
前記(メタ)アクリル系共重合体(A)及び(B)の合計100重量部に対して、トリ
レンジイソシアネート系化合物(C)を5~20重量部と、
エポキシ基含有シランカップリング剤(D)と、
を含む粘着剤組成物。 - 前記エポキシ基含有シランカップリング剤(D)が、分子内に少なくともメトキシ基またはエトキシ基の何れかを有することを特徴とする請求項1に記載の粘着剤組成物。
- 前記エポキシ基含有シランカップリング剤(D)が、オリゴマーであることを特徴とする請求項1または2に記載の粘着剤組成物。
- 更に、アミノ変性シリコーン(E)を含む請求項1~3の何れか一項に記載の粘着剤組成物。
- 前記(メタ)アクリル系共重合体(A)及び(B)の合計100重量部に対して、前記アミノ変性シリコーン(E)を0.05~1重量部含む請求項4に記載の粘着剤組成物。
- 更に、水酸基とロジン骨格とを有する化合物(F)を含む請求項1~5の何れか一項に記載の粘着剤組成物。
- 前記アクリル系共重合体(A)及び(B)の合計100重量部に対して、前記水酸基とロジン骨格とを有する化合物(F)を1~20重量部含む請求項6または7に記載の粘着剤組成物。
- 前記(メタ)アクリル系共重合体(A)及び(B)の合計100重量部に対して、前記エポキシ基含有シランカップリング剤(D)を0.02~1重量部含む請求項1~8の何れか一項に記載の粘着剤組成物。
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WO2014156200A1 (ja) * | 2013-03-29 | 2014-10-02 | 東洋インキScホールディングス株式会社 | 粘着剤およびそれを用いた粘着シート |
JP2014234419A (ja) * | 2013-05-31 | 2014-12-15 | 日本カーバイド工業株式会社 | 光学部材用粘着剤組成物及び光学フィルム |
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