WO2014156200A1 - 粘着剤およびそれを用いた粘着シート - Google Patents
粘着剤およびそれを用いた粘着シート Download PDFInfo
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- WO2014156200A1 WO2014156200A1 PCT/JP2014/001858 JP2014001858W WO2014156200A1 WO 2014156200 A1 WO2014156200 A1 WO 2014156200A1 JP 2014001858 W JP2014001858 W JP 2014001858W WO 2014156200 A1 WO2014156200 A1 WO 2014156200A1
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- WIPO (PCT)
- Prior art keywords
- pressure
- sensitive adhesive
- acrylic polymer
- compound
- meth
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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
- C09J133/06—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
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
-
- 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
- C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- 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
- 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
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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
- C09J7/30—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
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
Definitions
- This invention relates to the adhesive which can be used for members, such as a plastic and glass.
- Display devices such as liquid crystal displays used in various devices such as home and commercial appliances such as electronic calculators, electronic watches, mobile phones, and televisions are becoming larger, especially liquid crystal televisions and plasma televisions. The increase in size is remarkable.
- touch panel type liquid crystal displays such as smartphones and tablets are rapidly spreading, and a large market expansion is expected in the future.
- liquid crystal displays are also used in in-vehicle devices such as car navigation systems, and are required to have durability that can be used in harsh interior environments such as high-temperature and high-humidity atmospheres.
- the liquid crystal display uses polarizing plates and retardation plates having various optical functions, and these are attached to an adherend such as a liquid crystal cell using glass or transparent plastic via an adhesive. Affixed.
- the polarizing plate is generally a laminate having a structure in which a polyvinyl alcohol film is sandwiched between a triacetyl cellulose film or a cycloolefin film. These films have different mechanical properties and therefore have different dimensional change rates during heating. Therefore, when placed in a high temperature atmosphere, the laminate often warps.
- the pressure-sensitive adhesive is required to have a function (reworkability) capable of re-peeling the polarizing plate from the liquid crystal cell after a lapse of time since sticking.
- Patent Document 1 in order to solve the problem of light leakage, by adding a plasticizer or the like to the pressure-sensitive adhesive, a technique for softening the pressure-sensitive adhesive layer and imparting stress relaxation properties. Is disclosed.
- Patent Document 2 discloses a technique for improving the stress relaxation property of a coating film and preventing light leakage by including an acrylic copolymer using an aromatic ring-containing monomer in order to impart stress relaxation property. ing.
- Patent Document 3 in order to impart removability, a high molecular weight acrylic polymer having a weight average molecular weight of 500,000 or more has a high acid value and a low molecular weight having a weight average molecular weight of 0.2 to 100,000. Techniques for blending acrylic polymers are disclosed.
- Patent Document 4 discloses a technique for improving stress relaxation by using together an acrylic polymer having a carboxyl group and a weight average molecular weight of 700,000 or more and an acrylic polymer having a weight average molecular weight of 800 to 50,000. Is disclosed.
- the pressure-sensitive adhesive using the aromatic ring-containing monomer has a problem that white spots are generated and optical properties are inferior in light leakage evaluation.
- a pressure-sensitive adhesive using a peroxide and a copolymer having a different weight average molecular weight is not practical because the drying conditions of the pressure-sensitive adhesive are limited.
- the pressure-sensitive adhesive using a copolymer having a different weight average molecular weight without using a peroxide has a problem that the cohesive force is remarkably lowered by the low molecular weight copolymer.
- the pressure-sensitive adhesive in which a high-Tg copolymer is blended with a general copolymer has good cohesive strength, but has a problem that white spots occur due to insufficient stress relaxation properties. .
- the present invention when used for an adhesive film, has excellent releasability, and is less likely to float or peel off from the adherend even after being exposed to a high temperature environment or a high temperature and high humidity environment. It aims at providing the adhesive which can create not only the impression layer at the time of adhesive film production but also the adhesive layer which can be produced.
- the present invention relates to an acrylic polymer (A) having no hydroxyl group and having a carboxyl group, an acrylic polymer (B) having no carboxyl group and having a hydroxyl group, an epoxy compound, a metal chelate compound, and an aziridine compound It is the adhesive containing at least 1 compound chosen from these, and a polyisocyanate compound.
- the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive is composed of at least one compound selected from the carboxyl group of the acrylic polymer (A), the epoxy compound, the metal chelate compound, and the aziridine compound.
- the acrylic polymer (B) is crosslinked with the polyisocyanate compound. Since the pressure-sensitive adhesive layer does not impair the cohesive force and is excellent in stress relaxation, when left in a high-temperature atmosphere or high-temperature and high-humidity atmosphere, it does not easily float or peel off, and does not easily leak light. It has the effect that it does not easily occur.
- the present invention it is excellent in removability, and after being exposed to a high temperature environment or a high temperature and high humidity environment, for example, glass and plastics are unlikely to float or peel off from the adherend, and light leakage does not easily occur. It was possible to provide a pressure-sensitive adhesive capable of producing a pressure-sensitive adhesive sheet that hardly causes indentation.
- the pressure-sensitive adhesive of the present invention includes an acrylic polymer (A) having no carboxyl group and a carboxyl group, an acrylic polymer (B) having no carboxyl group and a hydroxyl group, an epoxy compound, a metal chelate compound, And at least one compound selected from aziridine compounds and a polyisocyanate compound.
- the pressure-sensitive adhesive of the present invention is preferably used as a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer formed by coating and drying.
- the pressure-sensitive adhesive tape is preferably used for an optical member, particularly for bonding a liquid crystal display member.
- the acrylic polymer (A) and the acrylic polymer (B) are copolymers of monomers containing (meth) acrylic acid esters.
- the acrylic polymer (A) and the acrylic polymer (B) each form a polymer network by a cross-linking reaction, thereby obtaining an effect of suppressing floating, peeling, light leakage, and indentation.
- (meth) acrylic acid ester includes acrylic acid ester and methacrylic acid ester.
- an acrylic polymer (A) is a polymer which does not have a hydroxyl group but has a carboxyl group. Specifically, it is necessary to copolymerize a monomer mixture containing a monomer having a carboxyl group and not a monomer having a hydroxyl group as a reactive functional group.
- Monomers containing a carboxyl group include, for example, (meth) acrylic acid, monohydroxyethyl acrylate phthalate, p-carboxybenzyl acrylate, ethylene oxide-modified (added moles: 2 to 18) phthalate acrylic acid Ester, monohydroxypropyl acrylate, phthalate, monohydroxyethyl acrylate, succinate ⁇ -carboxyethyl, 2- (4-benzoyl-3-hydroxyphenoxy) ethyl acrylate, maleic acid, monoethylmaleic acid , Itaconic acid, citraconic acid, fumaric acid and the like. These can be used alone or in combination of two or more.
- the polymer having a carboxyl group is preferably contained in an amount of 0.01 to 20% by weight, more preferably 0.5 to 15% by weight in 100% by weight of the monomer mixture.
- the content is 0.01% or more, the cohesive force is further improved. Moreover, it becomes easy to make cohesion force and stress relaxation property compatible because content will be 20 weight% or less.
- the acrylic polymer (B) of the present invention is a polymer having no carboxyl group and having a hydroxyl group. Specifically, it is necessary to copolymerize a monomer mixture that does not include a monomer having a carboxyl group as a reactive functional group but includes a monomer having a hydroxyl group.
- Examples of the monomer containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate.
- (Meth) acrylic acid hydroxyalkyl esters such as 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl (meth) acrylate
- glycol mono (meth) acrylate such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, caprolactone modified ( Meta)
- Acrylic acid esters such as hydroxyethyl acrylamide.
- 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferred. These can be used alone or in combination of two or more.
- the hydroxyl group-containing monomer is preferably contained in an amount of 0.01 to 20% by weight, more preferably 0.2 to 15% by weight, in 100% by weight of the monomer mixture.
- the content is 0.01% or more, the cohesive force is further improved. Moreover, it becomes easy to make cohesion force and stress relaxation property compatible because content will be 20 weight or less.
- Monomers that can be used for copolymerization of the acrylic polymer (A) and the acrylic polymer (B) are preferably (meth) acrylic acid alkyl esters and other vinyl monomers.
- the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth) Hexyl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, (meth ) Hexadecyl acrylate, octadecyl (meth) acryl
- the (meth) acrylic acid alkyl ester is preferably contained in an amount of 5 to 50% by weight, more preferably 10 to 30% by weight, in 100% by weight of the monomer mixture.
- the content is 5% or more, the cohesive force is further improved.
- the other vinyl monomers include an amide bond-containing monomer, an epoxy group-containing monomer, an amino group-containing monomer, a monomer having an alkylene oxide unit, vinyl acetate, and crotonic acid.
- Vinyl, styrene, acrylonitrile and the like are preferable, but are not particularly limited as long as they can be copolymerized.
- Examples of the monomer containing an amide bond include (meth) acrylamide, N-methylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dimethylaminopropyl (meth) ) (Meth) acrylamide compounds such as acrylamide, diacetone acrylamide, N- (hydroxymethyl) acrylamide, N- (butoxymethyl) acrylamide, heterocycles such as N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine , N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide and the like.
- Examples of the monomer containing an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 6-methyl- (meth) acrylate. Examples include 3,4-epoxycyclohexylmethyl.
- Examples of the monomer containing an amino group include monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, and monoethylaminopropyl (meth) acrylate. And (meth) acrylic acid monoalkylamino esters.
- the monomer having an alkylene oxide unit preferably has units such as ethylene oxide and propylene oxide.
- examples include glycol (meth) acrylic acid ester, ethoxy polypropylene glycol (meth) acrylic acid ester, phenoxypolyethylene glycol (meth) acrylic acid ester, and phenoxypolypropylene glycol (meth) acrylic acid ester.
- the other vinyl monomer is preferably contained in an amount of 5 to 30% by weight in 100% by weight of the monomer mixture, and more preferably 10 to 25% by weight.
- the content is 5% or more, the cohesive force is further improved.
- the mixing ratio of the acrylic polymer (A) and the acrylic polymer (B) is important, and the acrylic polymer (A) and the acrylic polymer (B) are (A) / (B) Mixing at a weight ratio of 95/5 to 5/95 makes it possible to suppress light leakage and to suppress the floating and peeling of the polarizing plate.
- the weight average molecular weight of the acrylic polymer (A) is preferably 500,000 to 2,000,000. When it is in the range of 500,000 to 2,000,000, the cohesive force and the like are further improved, so that floating and peeling can be further suppressed, and the stress relaxation property is further improved.
- the weight average molecular weight of the acrylic polymer (B) is preferably 100,000 to 1,000,000. When it is in the range of 100,000 to 1,000,000, the cohesive force and the like are further improved, so that floating and peeling can be further suppressed, and the stress relaxation property is further improved.
- the molecular weight distribution (molecular weight distribution (Mw / Mn) representing the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn)) is 2 to 20 is preferred.
- Mw / Mn molecular weight distribution
- the said weight average molecular weight and number average molecular weight are the values of polystyrene conversion measured by the gel permeation chromatography (GPC) method. Details of the GPC measurement method are described in the Examples.
- the acrylic polymer (A) and the acrylic polymer (B) can be obtained by radical polymerization of a monomer mixture with a radical polymerization initiator.
- the radical polymerization may be a known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, etc.
- solution polymerization is preferred.
- Solvents that can be used in solution polymerization are preferably acetone, methyl acetate, ethyl acetate, toluene, xylene, anisole, methyl ethyl ketone, cyclohexanone, and the like.
- the polymerization temperature is preferably a boiling point reaction of 60 to 120 ° C., and the polymerization time is preferably 5 to 12 hours.
- the radical polymerization initiator is not particularly limited as long as it is a compound capable of generating radicals at the polymerization temperature, and known compounds such as peroxides and azo compounds can be used.
- the peroxide include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, ⁇ , ⁇ ′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5- Dialkyl peroxides such as di (t-butylperoxy) hexyne-3; Peroxyesters such as t-butyl peroxybenzoate, t-butyl peroxyacetate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane; Ketone peroxides such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide; 2,2-bis
- Examples of the azo compound include 2,2′-azobisbutyronitrile such as 2,2′-azobisisobutyronitrile (abbreviation: AIBN) and 2,2′-azobis (2-methylbutyronitrile). ; 2,2′-azobisvaleronitriles such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile); 2,2′-azobispropionitriles such as 2,2′-azobis (2-hydroxymethylpropionitrile); 1,1′-azobis-1-alkanenitriles such as 1,1′-azobis (cyclohexane-1-carbonitrile) can be used.
- the radical polymerization initiators can be used alone or in combination of two or more.
- the radical polymerization initiator is preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the monomer mixture.
- the pressure-sensitive adhesive of the present invention uses a curing agent that reacts with the reactive functional group of the acrylic polymer (A), and a curing agent that reacts with the reactive functional group of the acrylic polymer (B). It is preferable to use it.
- the cross-linking network of the acrylic polymer (A) and the cross-linking network of the acrylic polymer (B) each have an intertwined part, a part that exists independently, and a part that interpenetrates. Force and good stress relaxation are obtained.
- the curing agent that reacts with the acrylic polymer (A) having a carboxyl group is preferably an epoxy compound, a metal chelate compound, an aziridine compound, an acid anhydride group-containing compound, a carbodiimide compound, an N-methylol group-containing compound, or the like.
- the curing agent that reacts with the acrylic polymer (B) having a hydroxyl group is preferably a polyisocyanate compound.
- the curing agent for the acrylic polymer (A) is preferably an epoxy compound, a metal chelate compound, or an aziridine compound because the cohesive force and stress relaxation properties are further improved.
- epoxy compound examples include bisphenol A-epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether.
- Trimethylolpropane triglycidyl ether diglycidyl aniline, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, N , N, N ′, N′-tetraglycidylaminophenylmethane and the like.
- metal chelate compounds include coordination compounds of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium, and acetylacetone or ethyl acetoacetate. It is done. Specific examples include aluminum ethyl acetoacetate / diisopropylate, aluminum trisacetylacetonate, aluminum bisethylacetoacetate / monoacetylacetonate, and aluminum alkylacetoacetate / diisopropylate.
- polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium
- acetylacetone or ethyl acetoacetate acetylacetone or ethyl acetoacetate. It is done. Specific examples include aluminum ethyl acetoacetate / diisopropylate, aluminum trisace
- aziridine compound examples include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1-aziridinecarboxite), bisisophthalo Yl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxite), 2,2′-bishydroxymethyl Butanol-tris [3- (1-aziridinyl) propionate], trimethylolpropane tri- ⁇ -aziridinylpropionate, tetramethylolmethane tri- ⁇ -aziridinylpropionate, tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, 4,4'-bis (ethyleneiminocarbonylamino) diphenyl Examples include methane.
- carbodiimide compound examples include high molecular weight polycarbodiimide produced by decarboxylation condensation reaction of a diisocyanate compound in the presence of a carbodiimidization catalyst.
- high molecular weight polycarbodiimides examples include Nisshinbo's Carbodilite series. Of these, Carbodilite V-01, 03, 05, 07, and 09 are preferable because of their excellent compatibility with organic solvents.
- the acid anhydride group-containing compound is a compound having two or more carboxylic acid anhydride groups and is not particularly limited, but includes tetracarboxylic dianhydride, hexacarboxylic dianhydride, hexacarboxylic dianhydride. And a maleic anhydride copolymer resin.
- polycarboxylic acid, polycarboxylic acid ester, polycarboxylic acid half ester, and the like that can be converted into an anhydride via a dehydration reaction during the reaction are included in the “acid anhydride group-containing compound” of the present invention.
- tetracarboxylic dianhydride examples include pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenylsulfonetetracarboxylic dianhydride, diphenylsulfidetetracarboxylic Examples thereof include acid dianhydride, butanetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride and the like.
- the polyisocyanate compound is an isocyanate monomer having two or more isocyanate groups, specifically an isocyanate monomer such as an aromatic polyisocyanate, an aliphatic polyisocyanate, an araliphatic polyisocyanate, an alicyclic polyisocyanate, and the like.
- an isocyanate monomer such as an aromatic polyisocyanate, an aliphatic polyisocyanate, an araliphatic polyisocyanate, an alicyclic polyisocyanate, and the like.
- a burette body, a nurate body, and an adduct body are preferred.
- aromatic polyisocyanate examples include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6 -Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', And 4 ′′ -triphenylmethane triisocyanate.
- aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene diisocyanate. , Dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.
- Examples of the araliphatic polyisocyanate include ⁇ , ⁇ ′-diisocyanate-1,3-dimethylbenzene, ⁇ , ⁇ ′-diisocyanate-1,4-dimethylbenzene, ⁇ , ⁇ ′-diisocyanate-1,4-diethylbenzene. 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.
- Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI, isophorone diisocyanate), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1, Examples include 4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane, and the like. .
- the burette body refers to a self-condensate having a burette bond in which the isocyanate monomer is self-condensed. Specific examples include a burette of hexamethylene diisocyanate.
- the nurate body refers to a trimer of the isocyanate monomer, and examples thereof include a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate, and a trimer of tolylene diisocyanate.
- the adduct body is a bifunctional or higher functional isocyanate compound obtained by reacting the isocyanate monomer with a bifunctional or higher molecular weight active hydrogen-containing compound.
- a compound obtained by reacting trimethylolpropane and hexamethylene diisocyanate trimethylolpropane.
- bifunctional or higher functional low molecular active hydrogen-containing compound examples include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, and 3,3′-dimethylol.
- Tetrafunctional or higher functional polyols such as pentaerythritol, dipentaerythritol, sorbitol, xylitol; Ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine, diaminodicyclohexylmethane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1, Aliphatic polyamines such as 3-bis (aminomethyl) cyclohexane, triethylenetetramine, diethylenetriamine, triaminopropane; Aromatic polyamines such as phenylenediamine, tolylenediamine, diaminodiphenylmethane, diaminodiphenyl ether; Ethylenedithiol, propylenedithiol,
- the polyisocyanate compound is preferably a trifunctional isocyanate compound from the viewpoint of forming a sufficient crosslinked structure, and more preferably an adduct that is a reaction product of an isocyanate monomer and a trifunctional low-molecular active hydrogen-containing compound.
- a trimethylolpropane adduct of hexamethylene diisocyanate, a trimethylolpropane adduct of tolylene diisocyanate, a trimethylolpropane adduct of isophorone diisocyanate, a nurate of isophorone diisocyanate, and a trimethylolpropane adduct of xylylene diisocyanate are preferred.
- an adduct body of tolylene diisocyanate trimethylolpropane and a nurate body of isophorone diisocyanate are preferable.
- the curing agent that reacts with the reactive functional group of the acrylic polymer (A) is preferably used in an amount of 0.05 to 5% by weight based on 100 parts by weight of the acrylic polymer (A). 0.1 to 3% by weight is more preferred.
- the curing agent that reacts with the reactive functional group of the acrylic polymer (B) is preferably used in an amount of 1 to 50% by weight based on 100 parts by weight of the acrylic polymer (B). 35% by weight is more preferred.
- the pressure-sensitive adhesive of the present invention preferably contains a silane coupling agent. Since the adhesive force is further improved by using the silane coupling agent, the floating and peeling can be further suppressed.
- silane coupling agent examples include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltripropoxysilane, 3- (meth) Alkoxysilane compounds having a (meth) acryloxy group, such as acryloxypropyltributoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3- (meth) acryloxypropylmethyldiethoxysilane; Alkoxysilane compounds having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltripropoxysilane
- the silane coupling agent is preferably used in an amount of 0.01 to 2 parts by weight with respect to a total of 100 parts by weight of the acrylic copolymer (A) and the acrylic copolymer (A). A range of ⁇ 1 part by weight is more preferred.
- tackifying resins various resins, oils, softeners, dyes, pigments, antioxidants, ultraviolet absorbers, weathering stabilizers are optional components.
- Plasticizers, fillers, antiaging agents, antistatic agents, and the like may be blended.
- the pressure-sensitive adhesive of the present invention is suitable as a pressure-sensitive adhesive for optical members, as well as various plastic sheets, general labels and seals, paints, elastic wall materials, waterproof coating materials, flooring materials, tackifiers, pressure-sensitive adhesives, and laminates.
- Structural adhesives sealing agents, molding materials, surface modification coating agents, binders (magnetic recording media, ink binders, casting binders, fired brick binders, graft materials, microcapsules, glass fiber sizing, etc.), urethane foam ( (Hard, semi-rigid, soft), urethane RIM, UV / EB curable resin, high solid paint, thermosetting elastomer, microcellular, textile processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant, gel coat agent, Resin for artificial marble, impact resistance agent for artificial marble, resin for ink, film (laminate adhesive, protective film) Lum, etc.), laminated glass resin, reactive diluent, various molding materials, elastic fiber, artificial leather, as a raw material for synthetic leather, can also very effectively used as various resin additives and a raw material thereof or the like.
- binders magnetic recording media, ink binders, casting binders, fired brick binders, graft materials, microcapsul
- the pressure-sensitive adhesive sheet of the present invention includes a base material and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive of the present invention.
- the pressure-sensitive adhesive sheet can be obtained, for example, by forming a pressure-sensitive adhesive layer by applying a pressure-sensitive adhesive to a substrate and drying it. Moreover, an adhesive is applied to the peelable sheet and dried to form an adhesive layer, and the substrate is bonded.
- the adhesive layer should just be provided in the at least one surface of the base material.
- a sheet, a film and a tape are synonymous. Needless to say, the peelable sheet is bonded to the surface of the pressure-sensitive adhesive layer that is not in contact with the base material.
- a suitable liquid medium for example, a hydrocarbon solvent such as toluene, xylene, hexane, heptane; an ester solvent such as ethyl acetate or butyl acetate; a ketone solvent such as acetone or methyl ethyl ketone;
- the viscosity can be adjusted by adding halogenated hydrocarbon solvents such as dichloromethane and chloroform; ether solvents such as diethyl ether, methoxytoluene and dioxane, and other hydrocarbon solvents.
- the pressure-sensitive adhesive can be heated to reduce the viscosity.
- water, alcohol, etc. inhibit the crosslinking reaction of an acrylic copolymer (B) and a polyisocyanate compound, it is preferable to avoid use.
- the substrate examples include cellophane, plastic, rubber, foam, cloth, rubber cloth, resin-impregnated cloth, glass plate, and wood.
- the substrate may be plate-shaped or film-shaped.
- stacked the base material independently or several base materials is also preferable.
- plastic examples include polyolefin resins such as polyvinyl alcohol, triacetyl cellulose, polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymer, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.
- polyolefin resins such as polyvinyl alcohol, triacetyl cellulose, polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymer
- polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.
- Polycarbonate resin polynorbornene resin, polyarylate resin (PAR: copolymer resin of bisphenol A and phthalic acid), polyacrylic resin, polyphenylene sulfide resin, polystyrene resin, polyamide resin, polyimide resin, epoxy resin Examples thereof include resins (resins obtained by reacting epoxy group-containing resins with polyamines or carboxylic anhydrides).
- the pressure-sensitive adhesive can be applied by a known method.
- Mayer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma coater, knife coater, reverse coater, spin coater and the like can be mentioned.
- limiting in particular in a drying method The thing using hot air drying, infrared rays, and the pressure reduction method is mentioned.
- the drying condition may be hot air heating of about 60 to 160 ° C.
- the thickness of the pressure-sensitive adhesive layer is preferably 0.1 to 300 ⁇ m, more preferably 1 to 100 ⁇ m. When the thickness is less than 0.1 ⁇ m, sufficient adhesive strength may not be obtained, and even when the thickness exceeds 300 ⁇ m, the performance such as adhesive strength is often not improved.
- the pressure-sensitive adhesive film of the present invention has an adhesive strength of preferably 2 to 20 N / 25 mm, more preferably 2 to 15 N / 25 mm after 1 day at 23 ° C. after being bonded to alkali-free glass.
- the adhesive strength is 2 N / 25 mm or more, it becomes easy to obtain sufficient adhesive strength that is unlikely to cause floating and peeling.
- the adhesive strength is 20 N / 25 mm or less, peeling from the adherend becomes easier.
- the storage elastic modulus (G ′) at 23 ° C. of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention is preferably 0.1 to 5 MPa.
- the storage elastic modulus (G ′) at 23 ° C. is 0.1 MPa or more, the adhesive physical properties are further improved. Moreover, adhesive force improves more because the storage elastic modulus (G ') in 23 degreeC becomes 5 Mpa or less.
- the storage elastic modulus (G ′) at 23 ° C. is more preferably 0.1 to 2.0 MPa.
- the pressure-sensitive adhesive layer preferably has a storage elastic modulus (G ′) at 80 ° C. of 0.1 to 2 MPa. When the storage elastic modulus (G ′) at 80 ° C.
- the storage elastic modulus (G ′) at 80 ° C. is more preferably 0.1 to 1 MPa. Details of the method for measuring storage elastic modulus (G ′) are described in Examples.
- the adhesive When the adhesive is coated on a substrate to produce an adhesive sheet, it is common to temporarily wind the coated adhesive sheet and then perform processing such as cutting. In some cases, foreign matters such as dust or dust mixed from the outside during the processing adhere to the adhesive sheet, and the foreign matter may leave a trace such as a press mark (referred to as an indentation in the present invention) on the adhesive layer.
- a polarizing plate is used for the base material, after the pressure-sensitive adhesive sheet is cut into a desired size, a polishing step is performed to smooth the end portion. In the process, since indentation is likely to occur, the yield is remarkably reduced. Since the pressure-sensitive adhesive of the present invention has a storage elastic modulus (G ′) at 23 ° C.
- the pressure-sensitive adhesive sheet of the present invention can be suitably used for laminating optical members. That is, it is preferable to use an optical member for the substrate.
- the optical member include a polarizing plate, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film.
- the pressure-sensitive adhesive sheet of the present invention using an optical member as a base material is attached to a glass member of a liquid crystal cell and used as a liquid crystal cell member.
- the optical member is a polarizing plate, even when left in a high-temperature atmosphere and a high-temperature and high-humidity atmosphere, the pressure-sensitive adhesive layer has good stress relaxation properties, so that light leakage due to warping of the polarizing plate can be suppressed.
- the pressure-sensitive adhesive sheet of the present invention can be preferably used for various electronics-related members such as liquid crystal displays, plasma displays, touch panels, and electrode peripheral members, protective films, building materials, glass members such as vehicle window glass, polyolefin, ABS, acrylic, etc. It can also be used for metals such as plastic, cardboard, wood, plywood, stainless steel and aluminum.
- reaction vessel (hereinafter simply referred to as “reaction vessel”) equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, 99.5 parts of butyl acrylate, 0.5 part of acrylic acid, 100 parts of ethyl acetate and 0.025 part of 2,2′-azobisisobutyronitrile (hereinafter referred to as AIBN) were charged, and the air in the reaction vessel was replaced with nitrogen gas. Then, it heated to 80 degreeC, stirring under nitrogen atmosphere, and reaction was started. Thereafter, the reaction solution was reacted at reflux temperature for 7 hours.
- reaction vessel hereinafter simply referred to as “reaction vessel” equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, 99.5 parts of butyl acrylate, 0.5 part of acrylic acid, 100 parts of ethyl acetate and 0.025 part of 2,2′-azobisiso
- copolymer (A-1) After completion of the reaction, the reaction mixture was cooled, diluted with ethyl acetate and measured for a nonvolatile content of 30% and a viscosity of 3000 m (Mw). The weight average molecular weight was 1,000,000.
- the resulting copolymer is referred to as copolymer (A-1).
- the weight average molecular weight (Mw) was measured using Shimadzu GPC “LC-GPC system”.
- GPC is liquid chromatography in which a substance dissolved in a solvent (THF; tetrahydrofuran) is separated and quantified by the difference in molecular size, and the weight average molecular weight (Mw) is determined in terms of polystyrene.
- Device name LC-GPC system “Prominence” manufactured by Shimadzu Corporation Column: Tosoh Co., Ltd. 4 GMHXL and Tosoh Co., Ltd. HXL-H 1 were connected.
- Mobile phase solvent Tetrahydrofuran Flow rate: 1.0 ml / min Column temperature: 40 ° C
- the pressure-sensitive adhesive was coated on a polyethylene terephthalate peelable sheet having a thickness of 38 ⁇ m so that the thickness after drying was 25 ⁇ m, and dried with hot air at 100 ° C. for 2 minutes to form a pressure-sensitive adhesive layer.
- a polarizing plate having a laminated structure in which both sides of a polyvinyl alcohol (PVA) polarizer are sandwiched between triacetyl cellulose films (hereinafter referred to as “TAC film”) is bonded to the pressure-sensitive adhesive layer.
- An adhesive sheet having a configuration of “/ adhesive layer / TAC film / PVA / TAC film” was obtained.
- the obtained pressure-sensitive adhesive sheet was aged at a temperature of 35 ° C. and a relative humidity of 55% for 1 week to obtain a laminate.
- Examples 2 to 50, Comparative Examples 1 to 20 A pressure-sensitive adhesive was obtained in the same manner as in Example 1 according to the blending ratios in Table 3 and Table 4. Further, a laminate was obtained in the same manner as in Example 1.
- the obtained laminate was evaluated by the following method.
- the obtained laminate was prepared to have a width of 160 mm and a length of 120 mm.
- the peelable sheet was peeled off and attached to an alkali-free glass plate using a laminator.
- the measurement sample was obtained by hold
- the measurement sample was evaluated for heat resistance as resistance evaluation in a high temperature atmosphere. That is, the measurement sample was allowed to stand at 85 ° C. for 500 hours and then visually observed for foaming, floating and peeling.
- the heat resistance of the measurement sample was evaluated as an evaluation of resistance in a high-temperature and high-humidity atmosphere. That is, the measurement sample was allowed to stand at 60 ° C. and a relative humidity of 95% for 500 hours and then visually observed for foaming, floating and peeling. Heat resistance and moist heat resistance were evaluated based on the following criteria. A: “Foaming, floating and peeling are not recognized at all, and it is good” ⁇ : “Bubbling, floating or peeling of 0.5 mm or less is recognized, but there is no practical problem” X: “There is foaming, floating and peeling all over and cannot be used”
- the obtained laminate was prepared in a width of 25 mm and a length of 150 mm.
- the peelable sheet was peeled off and attached to a non-alkali glass plate using a laminator.
- the measurement sample was obtained by making it hold
- a peeling test was performed in which the sample was pulled at a speed of 300 mm / min in the 180 ° direction using a tensile tester in an environment of 23 ° C. and 50% relative humidity. .
- the pressure-sensitive adhesive of the present invention is excellent in durability in high temperature atmosphere and high temperature and high humidity atmosphere, stress relaxation property, and removability.
- Comparative Examples 1 to 20 could not satisfy all the above characteristics.
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Abstract
Description
そして、液晶ディスプレイには、様々な光学的機能を有する偏光板や位相差板等が用いられており、これらは粘着剤を介してガラスや透明なプラスチックを使用した液晶セル等の被着体に貼付される。
カルボキシル基を含有する単量体は、例えば(メタ)アクリル酸、フタル酸モノヒドロキシエチルアクリル酸エステル、p-カルボキシベンジルアクリル酸エステル、エチレンオキサイド変性(付加モル数:2~18)フタル酸アクリル酸エステル、フタル酸モノヒドロキシプロピルアクリル酸エステル、コハク酸モノヒドロキシエチルアクリル酸エステル、アクリル酸β-カルボキシエチル、アクリル酸2-(4-ベンゾイル-3-ヒドロキシフェノキシ)エチル、マレイン酸、モノエチルマレイン酸、イタコン酸、シトラコン酸、及びフマル酸などが挙げられる。これらは単独または2種以上を併用できる。
前記(メタ)アクリル酸アルキルエステルは、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸デシル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸テトラデシル、(メタ)アクリル酸ヘキサデシル、(メタ)アクリル酸オクタデシルなどが挙げられる。これらの中でも(メタ)アクリル酸ブチルが、良好な粘着性能を得やすいという点から好ましい。これらは単独または2種以上を併用できる。
またアクリル系重合体(B)の重量平均分子量は、10万~100万が好ましい。10万~100万の範囲にあることで凝集力などがより向上するため、浮きおよび剥がれがより抑制でき、応力緩和性もより向上する。
また、アクリル系重合体(A)および(B)を混合したときの分子量分布(重量平均分子量(Mw)と数平均分子量(Mn)の比率を表す分子量分布(Mw/Mn))は、2~20が好ましい。前記範囲にあることで、浮きおよび剥がれが生じにくく、粘着力が寄り向上する。なお、上記重量平均分子量及び数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)法により測定したポリスチレン換算の値である。GPCの測定法の詳細は、実施例に記載する。
前記過酸化物は、例えばジ-t-ブチルパーオキサイド、ジクミルパーオキサイド、t-ブチルクミルパーオキサイド、α,α'-ビス(t-ブチルパーオキシ-m-イソプロピル)ベンゼン、2,5-ジ(t-ブチルパーオキシ)ヘキシン-3などのジアルキルパーオキサイド類;
t-ブチルパーオキシベンゾエート、t-ブチルパーオキシアセテート、2,5-ジメチル-2,5-ジ(ベンゾイルパーオキシ)ヘキサンなどのパーオキシエステル類;
シクロヘキサノンパーオキサイド、3,3,5-トリメチルシクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイドなどのケトンパーオキサイド類;
2,2-ビス(4,4-ジ-t-ブチルパーオキシシクロヘキシル)プロパン、1,1-ビス(t-ブチルパーオキシ)3,3,5-トリメチルシクロヘキサン、1,1-ビス(t-ブチルパーオキシ)シクロヘキサン、n-ブチル-4,4-ビス(t-ブチルパーオキシ)バレート、などのパーオキシケタール類;
クメンヒドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、2,5-ジメチルシクロヘキサン-2,5-ジハイドロパーオキサイドなどのハイドロパーオキサイド類;
ベンゾイルパーオキサイド、デカノイルパーオキサイド、ラウロイルパーオキサイド、2,4-ジクロロベンゾイルパーオキサイドなどのジアシルパーオキサイド類;
ビス(t-ブチルシクロヘキシル)パーオキシジカーボネートなどのパーオキシジカーボネート類などの有機過酸化物、又はこれらの混合物があげられる。
2,2'-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)、2,2'-アゾビス(2,4-ジメチルバレロニトリル)などの2,2'-アゾビスバレロニトリル類;
2,2'-アゾビス(2-ヒドロキシメチルプロピオニトリル)などの2,2'-アゾビスプロピオニトリル類;
1,1'-アゾビス(シクロヘキサン-1-カルボニトリル)などの1,1'-アゾビス-1-アルカンニトリル類などが使用できる。
ラジカル重合開始剤は、単独または2種以上を併用できる。
ここでカルボキシル基を有するアクリル系重合体(A)と反応する硬化剤は、エポキシ化合物、金属キレート化合物、アジリジン化合物、酸無水物基含有化合物、カルボジイミド化合物、およびN-メチロール基含有化合物等が好ましい。また水酸基を有するアクリル系重合体(B)と反応する硬化剤は、ポリイソシアネート系化合物が好ましい。なおアクリル系重合体(A)の硬化剤は凝集力及び応力緩和性がより向上することから、エポキシ化合物、金属キレート化合物、およびアジリジン化合物のいずれかが好ましい。
1,3-ビス(2-ヒドロキシエトキシ)ベンゼン、1,2-ビス(2-ヒドロキシエトキシ)ベンゼン、1,4-ビス(2-ヒドロキシエトキシ)ベンゼン、4,4'-メチレンジフェノール、4,4'-(2-ノルボルニリデン)ジフェノール、4,4'-ジヒドロキシビフェノール、o-,m-,及びp-ジヒドロキシベンゼン、4,4'-イソプロピリデンフェノール、あるいはビスフェノールAやビスフェノールF等のビスフェノール類にエチレンオキサイド、プロピレンオキサイド等のアルキレンオキサイドを付加させてなるビスフェノール類等の芳香族ジオール類;
1,1,1-トリメチロールプロパン、1,1,1-トリメチロールブタン、1,1,1-トリメチロールペンタン、1,1,1-トリメチロールヘキサン、1,1,1-トリメチロールヘプタン、1,1,1-トリメチロールオクタン、1,1,1-トリメチロールノナン、1,1,1-トリメチロールデカン、1,1,1-トリメチロールウンデカン、1,1,1-トリメチロールドデカン、1,1,1-トリメチロールトリデカン、1,1,1-トリメチロールテトラデカン、1,1,1-トリメチロールペンタデカン、1,1,1-トリメチロールヘキサデカン、1,1,1-トリメチロールヘプタデカン、1,1,1-トリメチロールオクタデカン、1,1,1-トリメチロールナノデカン、1,1,1-トリメチロール-sec-ブタン、1,1,1-トリメチロール-tert-ペンタン、1,1,1-トリメチロール-tert-ノナン、1,1,1-トリメチロール-tert-トリデカン、1,1,1-トリメチロール-tert-ヘプタデカン、1,1,1-トリメチロール-2-メチル-ヘキサン、1,1,1-トリメチロール-3-メチル-ヘキサン、1,1,1-トリメチロール-2-エチル-ヘキサン、1,1,1-トリメチロール-3-エチル-ヘキサン、1,1,1-トリメチロールイソヘプタデカンなどのトリメチロール分岐アルカン類、トリメチロールブテン、トリメチロールヘプテン、トリメチロールペンテン、トリメチロールヘキセン、トリメチロールヘプテン、トリメチロールオクテン、トリメチロールデセン、トリメチロールドデセン、トリメチロールトリデセン、トリメチロールペンタデセン、トリメチロールヘキサデセン、トリメトロールヘプタデセン、トリメチロールオクタデセン、1,2,6-ブタントリオール、1,2,4-ブタントリオール、グリセリン等の3官能ポリオール類;
ペンタエリスリトール、ジペンタエリスリトール、ソルビトール、キシリトール等の4官能以上のポリオール類;
エチレンジアミン、プロピレンジアミン、ブチレンジアミン、ペンチレンジアミン、ヘキシレンジアミン、ヘプチレンジアミン、オクチレンジアミン、ノニレンジアミン、ジアミノジシクロヘキシルメタン、3-アミノメチル-3,5,5-トリメチルシクロヘキシルアミン、1,3-ビス(アミノメチル)シクロヘキサン、トリエチレンテトラミン、ジエチレントリアミン、トリアミノプロパン等の脂肪族ポリアミン類;
フェニレンジアミン、トリレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルエーテル等の芳香族ポリアミン類;
エチレンジチオール、プロピレンジチオール、ブチレンジチオール、ペンチレンジチオール、ヘキシレンジチオール、ヘプチレンジチオール、オクチレンジチオール、ノニレンジチオール、ジメルカプトジシクロヘキシルメタン、3-メルカプトメチル-3,5,5-トリメチルシクロヘキシルチオール、1,3-ビス(メルカプトメチル)シクロヘキサン、1,4-ビス(3-メルカプトブチリルオキシ)ブタン、ペンタエリスリトール テトラキス(3-メルカプトブチレート)等のポリチオール類を挙げることができる。
これら多官能低分子活性水素含有化合物は、単独または2種以上を併用できる。
ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリイソプロポキシシラン、ビニルトリブトキシシラン、ビニルメチルジメトキシシラン、ビニルメチルジエトキシシランなどのビニル基を有するアルコキシシラン化合物;
3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-アミノプロピルトリプロポキシシラン、3-アミノプロピルメチルジメトキシシラン、3-アミノプロピルメチルジエトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリエトキシシラン、N-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルメチルジエトキシシラン、N-フェニル-3-アミノプロピルトリメトキシシランなどのアミノ基を有するアルコキシシラン化合物;
3-メルカプトプロピルトリメトキシシラン、3-メルカプトプロピルトリエトキシシラン、3-メルカプトプロピルトリプロポキシシラン、3-メルカプトプロピルメチルジメトキシシラン、3-メルカプトプロピルメチルジエトキシシランなどのメルカプト基を有するアルコキシシラン化合物;
3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルトリプロポキシシラン、3-グリシドキシプロピルトリブトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランなどのエポキシ基を有するアルコキシシラン化合物;
テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシランなどのテトラアルコキシシラン化合物;
3-クロロプロピルトリメトキシシラン、n-ヘキシルトリメトキシシラン、n-ヘキシルトリエトキシシラン、n-デシルトリメトキシシラン、n-デシルトリエトキシシラン、スチリルトリメトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、3-トリエトキシシリル-N-(1,3-ジメチルブチリデン)プロピルアミン、1,3,5-トリス(3-トリメトキシシリルプロピル)イソシアヌレート、3-イソシアネートプロピルトリメトキシシラン、3-イソシアネートプロピルトリエトキシシラン、ヘキサメチルジシラザン、分子内にアルコキシシリル基を有するシリコーンレジンなどが挙げられる。
前記粘着剤層の80℃における貯蔵弾性率(G')は、0.1~2MPaが好ましい。80℃における貯蔵弾性率(G')が0.1MPa以上になることで高温雰囲気および高温高湿雰囲気での浮きおよび剥がれをより抑制できる。また、80℃における貯蔵弾性率(G')が、2MPa以下になることで高温雰囲気および高温高湿雰囲気での粘着力をより向上できる。なお80℃の貯蔵弾性率(G')は0.1~1MPaがより好ましい。貯蔵弾性率(G')の測定法の詳細は、実施例に記載する。
撹拌機、温度計、還流冷却管、滴下装置、窒素導入管を備えた反応容器(以下、単に「反応容器」と記述する。)にアクリル酸ブチル99.5部、アクリル酸0.5部、酢酸エチル100部、2,2'-アゾビスイソブチロニトリル(以下、AIBNという)0.025部を仕込み、この反応容器内の空気を窒素ガスで置換した。その後、窒素雰囲気下で撹拌しながら、80℃まで加熱し反応を開始した。その後、反応溶液を還流温度で7時間反応させた。反応終了後、冷却し、酢酸エチルで希釈して不揮発分30%、粘度3000m(Mw)を測定したところ、重量平均分子量は100万であった。得られた共重合体を共重合体(A-1)とする。
表1の重量比率に従って各種原料を仕込み、合成例1と同様の方法でアクリル共重合体(A)を合成した。得られたアクリル共重合体の重量平均分子量を表1に示す。
反応容器にアクリル酸ブチル99・8部、アクリル酸2-ヒドロキシエチル0.2部、酢酸エチル100部、AIBN0.025部を仕込み、この反応容器内の空気を窒素ガスで置換した。その後、窒素雰囲気下で撹拌しながら、80℃まで加熱し反応を開始した。その後、反応溶液を還流温度で7時間反応させた。反応終了後、冷却し、酢酸エチルで希釈して不揮発分30%、粘度3000mPa・sの共重合体溶液を得た。また、GPCを用いてアクリル共重合体の重量平均分子(Mw)を測定したところ、重量平均分子量は100万であった。得られた共重合体を共重合体(B-1)とする。
表2の重量比率に従って各種原料を仕込み、合成例21と同様の方法でアクリル共重合体(B)を合成した。得られたアクリル共重合体の重量平均分子量を表2に示す。
重量平均分子量(Mw)の測定は島津製作所製GPC「LC-GPCシステム」を用いた。GPCは溶媒(THF;テトラヒドロフラン)に溶解した物質をその分子サイズの差によって分離定量する液体クロマトグラフィーであり、重量平均分子量(Mw)の決定はポリスチレン換算で行った。
装置名 : 島津製作所製、LC-GPCシステム「Prominence」
カラム : 東ソー(株)製GMHXL 4本、東ソー(株)製HXL-H 1本を連結した。
移動相溶媒 : テトラヒドロフラン
流量 : 1.0ml/min
カラム温度 : 40℃
合成例1で得られた共重合体溶液中のアクリル系共重合体(A-1)と、アクリル系共重合体(B-1)を(A-1)/(B-1)=80/20の重量比(不揮発分換算)で混合し、エポキシ化合物としてエチレングリコールジグリシジルエーテル0.5部、ポリイソシアネート化合物としてトリレンジイソシアネートのトリメチロールプロパンのアダクト体10部を配合し、更に酢酸エチルを加えて不揮発分を20%に調整して粘着剤を得た。
表3及び表4の配合比率に従って、実施例1と同様にして粘着剤を得た。更に実施例1と同様に行うことで積層体を得た。
得られた積層体を幅160mm、縦120mmの大きさに準備した。次いで剥離性シートを剥がして無アルカリガラス板に、ラミネータを用いて貼着した。続いて、この積層体が貼り付けられた前記ガラス板を50℃、5気圧の条件のオートクレーブ内に20分保持して各部材を密着させることで測定試料を得た。前記測定試料を、高温雰囲気での耐性評価として耐熱性を評価した。すなわち測定試料を85℃で500時間放置した後に発泡、浮き、剥がれの有無を目視で観察した。また、前記測定試料を、高温高湿雰囲気での耐性評価として耐湿熱性を評価した。すなわち測定試料を60℃、相対湿度95%で500時間放置した後に発泡、浮き、剥がれの有無を目視で観察した。耐熱性、および耐湿熱性は、以下の基準に基づいて評価した。
◎:「発泡、浮き、剥がれが全く認められず、良好である」
○:「0.5mm以下の発泡、浮き、剥がれのいずれかが認められるが、実用上問題がない」
×:「全面的に発泡、浮き、剥がれがあり、使用できない」
得られた積層体を幅160mm、縦120mmの大きさに2枚準備した。次いで剥離性シートを剥がして無アルカリガラス板の両面に2枚の積層体をその偏光板の吸収軸が直交するようにラミネータを用いて貼着した。続いて、前記圧着物を50℃、5気圧の条件のオートクレーブ内に20分保持させて各部材を密着させることで測定試料を得た。前記測定試料を、85℃で500時間放置した後、偏光板に光を透過させたときの光漏れを目視で観察した。光漏れ性は、以下の基準に基づいて評価した。
◎:「白抜けが無く、良好である」
○:「わずかに白抜けが有るが、実用上問題がない」
×:「全面的に白抜けがあり、使用できない」
得られた積層体を幅25mm、縦150mmの大きさに準備した。次いで剥離性シートを剥がして無アルカリガラス板にラミネータを用いて貼り付けた。続いて、50℃、5気圧の条件のオートクレーブ内に20分保持させて各部材を密着させることで測定試料を得た。前記測定試料を、85℃で3時間放置した後に、23℃、相対湿度50%の環境下で、引張試験機を用いて、180°方向に300mm/分の速度で引っ張る、剥離試験を行った。次いで、剥離後のガラス表面の曇りを目視で観察し、以下の基準に基づいて評価した。
○:「糊残り、曇りが認められず、良好である」
×:「糊残り、曇りが認められ、実用不可である」
得られた積層体を幅50mm、縦50mmの大きさに準備した。次いで剥離性シートを上にしガラス板の上に静置し、前記積層体の中央部に重さ500gのステンレス球を静置し、30分間放置した。直ぐにステンレス球を取り除き、前記積層体に付いた押し跡(圧痕)を目視で観察した。またステンレス球を1分間放置した評価を行い前記同様に押し跡を目視で観察した。以下の基準に基づいて評価した。なお圧痕が残り難いことは、応力緩和性が特に優れているといえる。
◎:「ステンレス球を1分間保持した後の押し跡が、24時間後に完全に消失する」
○:「ステンレス球を1分間保持した後の押し跡は、24時間後に完全に消失しないが、30秒間保持した後の押し跡は、24時間後に完全に消失する」
×:「ステンレス球を30秒間保持した後の押し跡が、24時間後に完全に消失しない」
(5)貯蔵弾性率(G')
得られた粘着剤を乾燥後の厚さが30μmになるように剥離性シートに塗工し、乾燥することで粘着剤層を形成した。得られた粘着剤層を厚みが約30mmになるように複数枚積層した後、オートクレーブで気泡を除去した後、直径8mmに打ち抜いて円柱状の試験片を得た。前記試験片の貯蔵弾性率(G')をねじり剪断法により、下記の条件で測定した。
測定装置:ティー・エイ・インスツルメント・ジャパン社製動的粘弾性測定装置「DYNAMIC ANALYZER RDA III」
周波数:1Hz
温度 :23℃、80℃
Claims (9)
- 水酸基を有さずカルボキシル基を有するアクリル系重合体(A)と、カルボキシル基を有さず水酸基を有するアクリル系重合体(B)と、エポキシ化合物、金属キレート化合物、およびアジリジン化合物から選ばれる少なくとも1つの化合物と、ポリイソシアネート化合物とを含む粘着剤。
- 前記アクリル系重合体(A)と前記アクリル系重合体(B)との割合が、重量比で(A)/(B)=95/5~5/95である、請求項1記載の粘着剤。
- 前記アクリル系重合体(A)は、重量平均分子量が50万~200万で、アクリル系重合体(B)は、重量平均分子量が10万~100万である、請求項1または2記載の粘着剤。
- 基材と、請求項1~3いずれか記載の粘着剤から形成されてなる粘着剤層とを備えた、粘着シート。
- 基材が、光学部材である請求項4記載の粘着シート。
- 23℃における、粘着剤層の貯蔵弾性率(G')が0.1~5.0MPaであり、かつ、80℃における貯蔵弾性率(G')が0.1~2.0MPaであることを特徴とする請求項4または5記載の粘着シート。
- 偏光板と、請求項1~3いずれか記載の粘着剤から形成されてなる粘着剤層とを含む、偏光板粘着シート。
- ガラス層と、請求項1~3いずれか記載の粘着剤から形成されてなる粘着剤層と、光学部材とが順次積層されてなることを特徴とする液晶セル用部材。
- 光学部材が、偏光板であることを特徴とする請求項8記載の液晶セル用部材。
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JP7300850B2 (ja) | 2019-03-07 | 2023-06-30 | アズビル株式会社 | 検出装置及びクランプ装置 |
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CN105102569A (zh) | 2015-11-25 |
KR102153375B1 (ko) | 2020-09-08 |
CN105102569B (zh) | 2018-04-03 |
JP6232723B2 (ja) | 2017-11-22 |
JP2014196376A (ja) | 2014-10-16 |
TW201444933A (zh) | 2014-12-01 |
KR20150140706A (ko) | 2015-12-16 |
TWI648364B (zh) | 2019-01-21 |
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