WO2015008384A1 - 光学部材用粘着剤組成物、粘着シートおよび積層体 - Google Patents
光学部材用粘着剤組成物、粘着シートおよび積層体 Download PDFInfo
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- WO2015008384A1 WO2015008384A1 PCT/JP2013/069655 JP2013069655W WO2015008384A1 WO 2015008384 A1 WO2015008384 A1 WO 2015008384A1 JP 2013069655 W JP2013069655 W JP 2013069655W WO 2015008384 A1 WO2015008384 A1 WO 2015008384A1
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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
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
Definitions
- the present invention relates to an adhesive composition for optical members, an adhesive sheet, and a laminate.
- image display devices have been used under various applications and conditions. For example, they are often used not only under room temperature conditions but also under severe conditions such as high temperature and high temperature and humidity. .
- high temperature or high temperature and humidity condition examples include use in a tropical region, use inside a vehicle, and inside an outdoor measuring instrument.
- an optical member for example, a polarizing plate
- a liquid crystal display device which is a kind of image display device
- the thinning of the polarizing plate tends to cause deformation.
- the present invention provides a pressure-sensitive adhesive composition for optical members, a pressure-sensitive adhesive sheet, and a laminate that can suppress deformation of the optical member and have excellent long-term durability.
- the present inventors can suppress the deformation of the optical member by adjusting the amount of the functional group contained in the copolymer and the ratio of the copolymer and the crosslinking agent, and And the adhesive composition for optical members which can acquire long-term durability was discovered.
- the pressure-sensitive adhesive composition for an optical member includes (A) a copolymer, (B) an isocyanate-based crosslinking agent, (C) an epoxy-based crosslinking agent, Including Containing 8 to 50 parts by mass of the (B) isocyanate crosslinking agent with respect to 100 parts by mass of the copolymer (A),
- the copolymer is a copolymer of a monomer mixture containing the carboxyl group-containing monomer in an amount of more than 0% by mass and less than 0.5% by mass.
- the pressure-sensitive adhesive composition for optical members according to any one of 1 to 4 above may further comprise (D) a silane coupling agent.
- the pressure-sensitive adhesive composition for optical members according to 5 above may contain 0.01 to 1 part by mass of the (D) silane coupling agent with respect to 100 parts by mass of the (A) copolymer.
- the (C) epoxy-based crosslinking agent may have an epoxy group and an amino group.
- the pressure-sensitive adhesive composition for optical members according to any one of 1 to 7 above may further comprise (E) a basic compound.
- the pressure-sensitive adhesive sheet according to another aspect of the present invention is obtained by forming the pressure-sensitive adhesive composition for optical members according to any one of 1 to 8 above into a film shape, heating and drying.
- the laminated body which concerns on the other aspect of this invention is the adhesive for optical members in any one of said 1 thru
- a pressure-sensitive adhesive layer obtained by forming the composition into a film, heating and drying.
- the glass substrate may be a glass substrate used for an image display device.
- the pressure-sensitive adhesive composition for an optical member includes (A) a copolymer, (B) an isocyanate-based crosslinking agent, and (C) an epoxy-based crosslinking agent, and (A) 100 parts by mass of the copolymer. On the other hand, it contains 8 to 50 parts by mass of the (B) isocyanate-based crosslinking agent, and the (A) copolymer is a simple substance containing more than 0% by mass and less than 0.5% by mass of the carboxyl group-containing monomer.
- the content of the carboxyl group contained in the copolymer (A) is suppressed by being a copolymer of the monomer mixture, the pressure-sensitive adhesive resulting from the reaction between the carboxyl group and other components The deterioration of the layer over time can be prevented. Therefore, the optical member excellent in long-term durability can be obtained by using the adhesive layer obtained using the said adhesive composition for optical members.
- the said adhesive composition for optical members since the ratio of the said (B) isocyanate type crosslinking agent with respect to the said (A) copolymer is adjusted to the said range, the said adhesive composition for optical members is used.
- the pressure-sensitive adhesive layer had a reduced hardness. For this reason, deformation of the optical member can be suppressed by using the pressure-sensitive adhesive layer.
- the carboxyl group contained in the copolymer (A) reacts with the functional group contained in the other component (or the functional group derived from the other component), thereby the component (A) and the other component. Since the compatibility with the components is enhanced, the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition for optical members is less prone to white turbidity and is excellent in transparency.
- the pressure-sensitive adhesive sheet obtained by forming the pressure-sensitive adhesive composition for optical members into a film, heating and drying can suppress deformation of the optical members and is excellent in long-term durability.
- the laminate includes an adhesive layer provided between a glass substrate and a polarizing film, the adhesive composition for optical members being formed into a film, heated and dried. Therefore, it is possible to obtain a polarizing film that can suppress deformation of the polarizing film and is excellent in long-term durability.
- Drawing 1 is a sectional view showing typically an example of a layered product containing an adhesive layer obtained using an adhesive constituent for optical members concerning one embodiment of the present invention.
- part means “mass%” and “%” means “mass%” unless otherwise specified.
- optical member pressure-sensitive adhesive composition is a (A) copolymer (hereinafter referred to as “pressure-sensitive adhesive composition”). , May be simply described as “component (A)”), (B) an isocyanate-based cross-linking agent (hereinafter sometimes simply referred to as “component (B)”), and (C) an epoxy system.
- component (A) a copolymer
- component (B) an isocyanate-based cross-linking agent
- component (C) an epoxy system.
- component (C) an epoxy system.
- component (C) A cross-linking agent
- the copolymer which is the (A) component is a polymer containing a carboxyl group. More specifically, the component (A) is a copolymer of a monomer mixture containing more than 0% by mass and less than 0.5% by mass of the carboxyl group-containing monomer. Since the component (A) is a copolymer of a monomer mixture containing more than 0% by mass and less than 0.5% by mass of the carboxyl group-containing monomer, the composition contains a small amount of carboxyl groups. The change with time of the pressure-sensitive adhesive layer obtained by using can be reduced.
- the pressure-sensitive adhesive layer obtained by using the agent composition is less likely to be clouded and is not easily whitened even at a high drying temperature.
- the component (A) may further contain a hydroxyl group.
- the component (A) further contains a hydroxyl group, the component (B) and the component (C) react with the hydroxyl group.
- the compatibility of the component (A) with the component (B) and the component (C) is improved. Therefore, whitening of the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition according to this embodiment can be prevented.
- the monomer mixture is a mixture of the following monomers (a1) to (a4) (provided that the monomers (a1) to (a4) are added together at 100% by mass). Is preferred).
- component (a1) Carboxyl group-containing monomer (hereinafter sometimes simply referred to as “component (a1)”): more than 0 mass% and less than 0.5 mass% (a2) (meth) acrylic acid alkyl ester Polymer (hereinafter sometimes simply referred to as “component (a2)”): 90 to 99.9% by mass (A3) Hydroxyl group-containing monomer (hereinafter sometimes simply referred to as “component (a3)”): 0 to 0.3% by mass (A4) Copolymerizable monomer other than the above (a1) to (a3) (hereinafter sometimes simply referred to as “component (a4)”): 0 to 9% by mass
- the component (A) is preferably an acrylic copolymer having a carboxyl group, An acrylic copolymer having both hydroxyl groups is more preferred.
- the “acrylic copolymer” refers to at least one selected from acrylic acid, acrylate, acrylate, methacrylic acid, methacrylate, and methacrylate in the structural unit.
- the component (A) is a copolymer of the above monomer mixture
- the component (A) can be a polymer having a carboxyl group and a hydroxyl group, and the content of the carboxyl group in the component (A) Is suppressed, and the hydroxyl group content is adjusted within a predetermined range.
- the carboxyl group-containing monomer contained in the monomer mixture for preparing the component (A) is less than 0.5% by mass.
- functional groups for example, ( The amount of the carboxyl group that reacts with time with the functional group contained in the component (B) and / or the component (C), the functional group derived from the component (B) and / or the component (C)
- the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition according to the present embodiment is excellent in long-term durability (for example, 1 month or more, preferably 3 months or more).
- the component (A) contains a hydroxyl group
- the functional group contained in the other component for example, the functional group contained in the component (B) and / or the component (C), the component (B) and / or Since the reaction between the functional group derived from the component (C) and the hydroxyl group proceeds, the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition according to this embodiment tends to be hard.
- the amount of the hydroxyl group contained in the component (A) is reduced to a predetermined amount or less, or the component (A) does not contain a hydroxyl group.
- (B) and / or (C) the functional groups contained in the component may be reduced (or eliminated). it can). For this reason, it can prevent that the adhesive layer obtained from the adhesive composition which concerns on this embodiment becomes hard.
- the carboxyl group-containing monomer as the component (a1) is a monomer having a carboxyl group in the molecular structure, and the component (a1) is derived from the carboxyl group contained in the component (A). obtain.
- the content of the component (a1) in the monomer mixture is 0% by mass, the reaction with the component (B) and the component (C) does not occur, so that the durability may be inferior.
- the content of the component (a1) in the monomer composition is 0.5% by mass or more, the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition according to this embodiment becomes harder with time, and the durability with time is increased. May fall.
- the content of the component (a1) in the monomer mixture is preferably 0.01 to 0.48% by mass, preferably 0.05 to 0.45. More preferably, it is mass%.
- Examples of the component (a1) include acrylic acid, methacrylic acid, maleic acid, and itaconic acid, and one of these can be used alone or in combination of two or more.
- (A2) component When the monomer mixture contains the (meth) acrylic acid alkyl ester monomer as the component (a2), durability can be imparted to the component (A). When the content of the component (a2) in the monomer mixture is less than 90% by mass, the durability may be inferior. On the other hand, the content of the component (a2) in the monomer composition is 99.9. Even if it exceeds mass%, since the ratio of the component (a1) becomes relatively low, the durability may be inferior. In view of superior durability, the content of the component (a2) in the monomer mixture is preferably 95 to 99.6% by mass, and more preferably 98 to 99.6% by mass.
- Examples of the component (a2) include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, acrylic N-pentyl acid, n-hexyl acrylate, n-hexyl methacrylate, n-heptyl acrylate, n-octyl acrylate, n-octyl methacrylate, n-nonyl acrylate, n-lauryl methacrylate, n-acrylate -Alkyl (meth) acrylic acid alkyl ester having a linear alkyl group at the ester site such as lauryl, n-tetradecyl methacrylate, n-hexadecyl acrylate, n-hexadecyl methacryl
- One species can be used alone, or two or more species can be used in combination.
- the component (a2) is such that the alkyl chain constituting the alkyl ester moiety is straight from the point that the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition according to the present embodiment can obtain more excellent durability. It is preferably a chain or branched alkyl chain, and more preferably a linear alkyl chain. In this case, the number of carbon atoms of the alkyl chain contained in the component (a2) is 1 in that the pressure-sensitive adhesive layer obtained by using the pressure-sensitive adhesive composition according to this embodiment can obtain further excellent durability. More preferably, it is ⁇ 20 (preferably 1-10).
- the hydroxyl group-containing monomer as the component (a3) is a monomer having a hydroxyl group in the molecular structure, and the component (a3) can be derived from the hydroxyl group contained in the component (A).
- the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition according to this embodiment becomes hard, and the optical member includes the pressure-sensitive adhesive layer. May be deformed.
- the optical member is a polarizing plate, light leakage may occur due to deformation of the optical member.
- the content of the component (a3) in the monomer mixture is preferably 0.25% by mass or less, more preferably 0.2% by mass or less, in that the occurrence of deformation of the optical member can be more reliably suppressed. It is more preferable.
- the content of the component (a3) in the monomer mixture is preferably 0.01 to 0.25% by mass, and 0.01 to 0 More preferably, it is 2% by mass.
- Examples of the component (a3) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, and 3-hydroxypropyl methacrylate.
- Acrylic alkylene glycols such as 2-hydroxy-3-phenoxypropyl, ethylene glycol acrylate, polyethylene glycol acrylate, propylene glycol acrylate, polypropylene glycol acrylate, etc.
- Ethylene glycol dimethacrylate polyethylene glycol methacrylate, propylene glycol methacrylate, alkylene glycol such as methacrylic acid polypropylene glycol, hydroxyl group-containing (meth) acrylic acid ester monomers such as phenoxyethyl acrylate.
- the monomer mixture may contain a copolymerizable monomer other than the components (a1) to (a3) as the component (a4).
- Component (a4) is, for example, an amide group-containing (meth) acrylic acid ester monomer such as N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropylacrylamide, N, N′-dimethylacrylamide, N, N′-diethylacrylamide, N, N′-dimethylaminoethylacrylamide, N, N′-dimethylaminopropylacrylamide, N-isopropylacrylamide, etc.
- an amide group-containing (meth) acrylic acid ester monomer such as N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethyla
- Amide group-containing (meth) acrylamide monomers acryloylmorpholine, acrylamide, t-octyl (meth) acrylamide, diacetone acrylamide and other nitrogen atom-containing monomers, carboxyethyl acrylate, acrylonitrile, pentamethyl (Meth) acrylic acid ester monomers having an aromatic ring group at ester sites such as peridine methacrylate, benzyl methacrylate, benzyl acrylate, 2-naphthyl acrylate; dicyclopentenyloxyethyl acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate Styrenic monomers such as (meth) acrylates having an ether group at the ester site, styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene; carboxylic acid vinyl esters such as vinyl acetate;
- Total amount of components (a1) to (a3) in the pressure-sensitive adhesive composition according to this embodiment from the viewpoint of achieving excellent durability and high adhesion to the adherend, may be 90 to 100% by mass.
- the weight average molecular weight (A) component has a weight average molecular weight (Mw) of 500,000 to 2,000,000.
- Mw weight average molecular weight
- the durability may be inferior.
- the weight average molecular weight exceeds 2 million, the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition according to the present embodiment is obtained. It may become too hard to prevent deformation of the optical member.
- the weight average molecular weight of the component (A) is more preferably from 800,000 to 1,500,000.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the component (A) are obtained by using GPC (gel permeation chromatography) and obtaining the weight average molecular weight (Mw) in terms of standard polystyrene under the following conditions. It is a thing.
- the molecular weight distribution (Mw / Mn) of the component (A) is preferably 6.0 to 9.5.
- Measuring device HLC-8120GPC (manufactured by Tosoh Corporation)
- GPC column configuration The following five columns (all manufactured by Tosoh Corporation) (I) TSK-GEL HXL-H (guard column) (Ii) TSK-GEL G7000HXL (Iii) TSK-GEL GMHXL (Iv) TSK-GEL GMHXL (V) TSK-GEL G2500HXL Diluted with tetrahydrofuran so that the sample concentration is 1.0 mg / cm 3
- Mobile phase solvent Tetrahydrofuran Flow rate: 1.0 cm 3 / min Column temperature: 40 ° C
- the content of the component (A) in the pressure-sensitive adhesive composition according to this embodiment can be 60 to 90 parts by mass of the pressure-sensitive adhesive composition, and is 65 to 90 parts by mass. It is preferable.
- the polymerization method of component (A) is not particularly limited and can be polymerized by known methods such as solution polymerization, emulsion polymerization, suspension polymerization, etc. In producing the pressure-sensitive adhesive composition of the present invention using a mixture of coalesces, it is preferable to perform polymerization by solution polymerization from the viewpoint that the treatment process is relatively simple and can be performed in a short time.
- solution polymerization generally, a predetermined organic solvent, each monomer, a polymerization initiator, and a chain transfer agent used as necessary are charged in a polymerization tank, under a nitrogen stream or a reflux temperature of the organic solvent, The reaction is carried out by heating for several hours with stirring.
- the organic solvent include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-propylbenzene, t-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, aromatic naphtha;
- aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-propylbenzene, t-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, aromatic naphtha
- aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, i-octane, n-decane, dipentene, petroleum spirit, petroleum naphtha, turpentine oil
- Esters such as
- Ketones for example, ethylene glycol monomer And the like; ethers, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, glycol ethers such as diethylene glycol monobutyl ether.
- organic solvents can be used alone or in admixture of two or more.
- component (A) in the polymerization of component (A), it is preferable to use, for example, esters and ketones.
- esters and ketones In particular, from the viewpoints of solubility of component (A), ease of polymerization reaction, etc.
- Use of ethyl acetate, methyl ethyl ketone, acetone or the like is preferable.
- organic peroxides and azo compounds that can be used in ordinary solution polymerization.
- organic peroxides include t-butyl hydroperoxide, cumene hydroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, and di-i-propyl peroxydicarbonate.
- azo compound examples include 2,2′-azobis-i-butyronitrile, 2,2 ′. -Azobis-2,4-dimethylvaleronitrile, 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and the like.
- polymerization initiators that do not cause a graft reaction during the polymerization reaction of component (A) are preferable, and azo-based compounds are particularly preferable.
- the amount used is usually 0.01 to 2 parts by weight, preferably 0.1 to 1.0 part by weight, based on 100 parts by weight of the total monomer mixture.
- the component (A) contained in the pressure-sensitive adhesive composition according to this embodiment it is normal not to use a chain transfer agent, but as long as the purpose and effect of the present invention are not impaired. It is possible to use it accordingly.
- chain transfer agents examples include cyanoacetic acid; alkyl esters having 1 to 8 carbon atoms of cyanoacetic acid; bromoacetic acid; alkyl esters having 1 to 8 carbon atoms of bromoacetic acid; anthracene, phenanthrene, fluorene, 9
- Aromatic compounds such as phenylfluorene; aromatic nitro compounds such as p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol, p-nitrotoluene; benzoquinone, 2, 3, 5, Benzoquinone derivatives such as 6-tetramethyl-p-benzoquinone; borane derivatives such as tributylborane; carbon tetrabromide, carbon tetrachloride, 1,1,2,2-tetrabromoethane, tribromoethylene, trichloroethylene, bromotrichloro Methane, tribromomethane
- the polymerization temperature of the component (A) is generally about 30 to 180 ° C, preferably 40 to 150 ° C, more preferably 50 to 90 ° C.
- an unreacted monomer is contained in a polymer obtained by a solution polymerization method or the like, it can be purified by a reprecipitation method using methanol or the like in order to remove the monomer.
- the isocyanate-based crosslinking agent as component (B) is a crosslinking agent having an isocyanate group (—N ⁇ C ⁇ O) and capable of crosslinking with component (A) at room temperature or under heating.
- Preferred are, for example, xylylene diisocyanate, tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate and the like, and trimethylolpropane and the like.
- Illustrative examples include isocyanate compounds and isocyanurates obtained by addition reaction with bivalent or higher alcohol compounds.
- urethane prepolymer type isocyanates obtained by addition reaction of isocyanate compounds with known polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, and the like can be mentioned. Of these, xylylene diisocyanate and its derivatives are preferably used.
- the content of the component (B) in the pressure-sensitive adhesive composition according to this embodiment is preferably 8 to 50 parts by mass, more preferably 9 to 48 parts by mass with respect to 100 parts by mass of the component (A). preferable.
- the content of the component (B) in the pressure-sensitive adhesive composition according to this embodiment is less than 8 parts by mass with respect to 100 parts by mass of the component (A)
- the pressure-sensitive adhesive composition according to this embodiment is used.
- the pressure-sensitive adhesive layer is not sufficiently adhesive, and on the other hand, when it exceeds 50 parts by mass, the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition according to the present embodiment becomes too hard, and the optical system including the pressure-sensitive adhesive layer Unexpected deformation may occur in the member.
- the component (B) is blended in a relatively large amount of 8 to 50 parts by mass with respect to the component (A), so that the isocyanate groups are condensed with each other in the system. So-called isocyanate polymers can be produced.
- active isocyanate groups in the isocyanate polymer react with water in the system, amino groups are generated in the polymer chain via decarboxylation. Since the amino group can react with the epoxy group of the component (C) described later, when the crosslinking point (for example, the component (A)) included in the component (A) is an acrylic polymer, the amino group is included in the acrylic polymer. It is possible to build a new polymer network in the system, which is different from the polymer network formed by the reaction between the crosslinking point) and the crosslinking agent. Thereby, the adhesive layer obtained using the adhesive composition which concerns on this embodiment is excellent in durability.
- the epoxy crosslinking agent as component (C) has an epoxy group (see the following formula (1)) and can be crosslinked with component (A) at room temperature or under heating. Good.
- the content of the component (C) in the pressure-sensitive adhesive composition according to this embodiment is preferably 0.05 to 4 parts by mass, and 0.08 to 3 parts by mass with respect to 100 parts by mass of the component (A). More preferably.
- the content of the component (C) in the pressure-sensitive adhesive composition according to this embodiment is less than 0.05 parts by mass with respect to 100 parts by mass of the component (A), the adhesive force is not sufficient, while 4 masses. If it exceeds the area, the pressure-sensitive adhesive layer becomes too hard, and unexpected deformation may occur in the optical member including the pressure-sensitive adhesive layer.
- the component (C) can be an epoxy crosslinking agent having an epoxy group and an amino group (amine type epoxy crosslinking agent).
- the component (C) is an amine type epoxy group, so that the epoxy group can enhance nucleophilicity with respect to other components (for example, the component (A) and / or the component (B)) and promote crosslinking. I can do it.
- the pressure-sensitive adhesive composition according to this embodiment may further contain (E) a basic compound (hereinafter, sometimes simply referred to as “component (E)”). Good.
- a commercially available epoxy-based crosslinking agent can be used as the component (C).
- the amine type epoxy crosslinking agent include 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (trade name: Tetrad C, Mitsubishi Gas Chemical Co., Inc.), 1,3-bis (N, N -Diglycidylaminomethyl) benzene (trade name: Tetrad X, Mitsubishi Gas Chemical Co., Ltd.).
- non-amine type epoxy-based crosslinking agents examples include 2,2 ′-[[2,2-bis (Oxirane-2-ylmethoxymethyl) -1,3-propanediyl] bis (oxymethylene)] bisoxirane (trade name: Denacol EX-411, manufactured by Nagase ChemteX Corporation).
- the component (E) has the nucleophilicity of the hydroxyl group contained in the other component (and / or derived from the other component). Can be increased.
- the content of the component (E) in the pressure-sensitive adhesive composition according to this embodiment is preferably 0 to 0.1 parts by mass, and 0 to 0.08 parts by mass with respect to 100 parts by mass of the component (A). More preferably.
- the component (E) is preferably a basic nitrogen atom-containing compound in that it has an excellent electron donating property. 1 (trade name, Kao Corporation).
- the pressure-sensitive adhesive composition according to the present embodiment may further contain (D) a silane coupling agent (hereinafter sometimes simply referred to as “(D) component”).
- (D) component a silane coupling agent
- the pressure-sensitive adhesive composition according to the present embodiment is used to form a pressure-sensitive adhesive layer on the surface of the optical member. Good adhesion to the body can be maintained.
- an isocyanate group (or a group derived from the isocyanate group) and a component (D) contained in the component (A) and / or the component (B).
- the adhesiveness between the pressure-sensitive adhesive composition according to this embodiment and the adherend for example, glass
- Component (C) is, for example, a polymerizable unsaturated group-containing silicon compound such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Silicon compounds having an epoxy structure such as methyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane And amino group-containing silicon compounds such as N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; and 3-chloropropyltrimethoxysilane; oligomer-type silane coupling agents, etc. Points that are superior , (A) component, (B
- 0.01 to 1 part by mass of the component (D) can be contained with respect to 100 parts by mass of the component (A) from the viewpoint of further increasing the adhesiveness of the composition. .
- the pressure-sensitive adhesive composition according to this embodiment further includes components other than the components (A), (B), (C), (D), and (E) as necessary. Can do.
- the pressure-sensitive adhesive composition according to the present embodiment may contain a surfactant, an antioxidant, an ultraviolet absorber, a tackifier, a plasticizer, and the like as long as the effects of the present invention are not impaired. .
- the pressure-sensitive adhesive composition for an optical member according to another embodiment of the present invention includes (A) a copolymer having a carboxyl group, (B) an isocyanate-based crosslinking agent, and (C) an epoxy-based crosslinking agent. Containing 8 to 50 parts by mass of the (B) isocyanate-based crosslinking agent with respect to 100 parts by mass of the (A) copolymer, and (100) with respect to 100 parts by mass of the copolymer (A) C) 0.05 to 4 parts by mass of an epoxy-based crosslinking agent is contained.
- the (A) copolymer can be a copolymer of a monomer mixture containing the carboxyl group-containing monomer in an amount of more than 0% by mass and less than 0.5% by mass. According to the pressure-sensitive adhesive composition for optical members according to the other embodiments, the same effect as the pressure-sensitive adhesive composition for optical members according to the present embodiment is obtained.
- the pressure-sensitive adhesive composition according to the present embodiment is usually prepared by mixing the components (A) to (E) and optional components as needed, simultaneously or in any order.
- the component (A) when mixing the component (A) with the component (B) and the component (C), when the component (A) is prepared by solution polymerization, the solution containing the component (A) after completion of the polymerization is added to the component (B). The component and the component (C) may be added.
- the component (A) is prepared by bulk polymerization, uniform mixing becomes difficult after completion of the polymerization. Therefore, during the polymerization, the component (B) and the component (C) It is preferable to add and mix the components.
- the pressure-sensitive adhesive composition according to this embodiment can be used for bonding an optical member and an adherend, and in particular, durability for a long period (for example, 1 month or more, preferably 3 months or more). Can be suitably used for bonding optical members that are required.
- Examples of the optical member to be bonded using the pressure-sensitive adhesive composition according to this embodiment include a polarizing film (polarizing plate), a retardation film, an elliptically polarizing film, an antireflection film, a brightness enhancement film, and light diffusion.
- Examples thereof include an optical film selected from the group consisting of a film and a hard coat film.
- examples of the adherend include a metal layer such as an ITO layer, and a base material made of glass or plastic. Among them, in terms of adhesion, the optical member and glass are bonded together. It can be used suitably.
- the optical member is a polarizing plate
- the polarizing plate and another adherend for example, a glass substrate
- the pressure-sensitive adhesive layer has an appropriate hardness, deformation of the polarizing plate can be prevented, and the change of the pressure-sensitive adhesive layer with time can be suppressed. Thereby, this adhesive layer is excellent in long-term durability.
- Pressure-sensitive adhesive sheet A pressure-sensitive adhesive sheet according to another embodiment of the present invention is obtained by forming the pressure-sensitive adhesive composition according to the present embodiment into a film shape, and appropriately heating and drying.
- the pressure-sensitive adhesive sheet according to this embodiment can be obtained by, for example, forming a film by coating the pressure-sensitive adhesive composition according to this embodiment on a separator (release film), and then heating and drying. .
- the pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer) according to this embodiment between the optical member and another adherend, the adherend and the optical member can be bonded to each other.
- the thickness of the pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer) according to this embodiment is usually 1 to 50 ⁇ m, preferably about 5 to 30 ⁇ m.
- the pressure-sensitive adhesive composition according to this embodiment includes the component (A), the component (B), and the component (C), and the component (B) with respect to 100 parts by mass of the component (A).
- the component (A) is a copolymer of a monomer mixture containing more than 0% by mass and less than 0.5% by mass of the carboxyl group-containing monomer, Since the content of the carboxyl group contained in the component (A) is suppressed and the ratio of the component (B) to the component (A) is adjusted to the above range, the deformation of the optical member can be suppressed. It has excellent durability for a long time.
- the carboxyl group is in the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition according to this embodiment. It can suppress that the hardness of this adhesive layer changes with time by reacting with the functional group.
- the carboxyl group is included in the component (A), so that the group included in the component (B). And / or the group contained in the component (C) (further, the group derived from the component (B) and / or the group derived from the component (C)) reacts with the carboxyl group contained in the component (A). Due to the improved compatibility between the component (A), the component (B) and the component (C), white turbidity is unlikely to occur, and even if the drying temperature of the pressure-sensitive adhesive layer is high or long, Whitening hardly occurs.
- the pressure-sensitive adhesive layer when the optical member is a polarizing plate, by using the pressure-sensitive adhesive layer obtained by using the pressure-sensitive adhesive composition according to the present embodiment, the pressure-sensitive adhesive layer has an appropriate hardness and is excellent. Therefore, the optical member can be prevented from being deformed, so that light leakage can be prevented.
- the pressure-sensitive adhesive layer is easy to adjust to the surface of the glass, and can improve the adhesion between the glass substrate and the optical member.
- the pressure-sensitive adhesive layer can exhibit excellent durability under high temperature and high humidity conditions, and can reduce light leakage.
- the laminated body which concerns on one Embodiment of this invention is the adhesive composition for optical members which concerns on the said embodiment provided between the glass substrate, the polarizing plate, and the said glass substrate and the said polarizing plate. And a pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) obtained by molding into a film and heating.
- FIG. 1 is a cross-sectional view schematically showing an example (laminated body 100) of a laminated body according to an embodiment of the present invention.
- the laminated body 100 contains the glass substrate 10, the polarizing film 30, and the adhesive layer 20 provided between the glass substrate 10 and the polarizing film 30, as FIG. 1 shows.
- the laminate 100 includes a glass substrate 10, a pressure-sensitive adhesive layer 20 provided on the glass substrate 10, and a polarizing film 30 provided on the glass substrate 10 via the pressure-sensitive adhesive layer 20. Including. The glass substrate 10 and the polarizing film 30 are bonded via the pressure-sensitive adhesive layer 20.
- the pressure-sensitive adhesive layer 20 is formed on the surface of an adherend (glass substrate 10).
- an adherend glass substrate 10
- the transfer method which transfers the said coating film to the surface of a specific resin film can be mentioned.
- the laminate according to this embodiment is included in, for example, an image display device (particularly a liquid crystal display device).
- the glass substrate included in the laminate according to the present embodiment is a glass substrate for a liquid crystal display device.
- the glass substrate which comprises the laminated body which concerns on this embodiment can be a glass substrate used for image display apparatuses.
- the image display device can be, for example, a TFT (thin film transistor) liquid crystal display device used for liquid crystal televisions, computer monitors, mobile phones, tablets, and the like.
- the laminated body according to the present embodiment is a glass substrate, a polarizing film, and a pressure-sensitive adhesive composition for an optical member according to the embodiment, which is provided between the glass substrate and the polarizing film.
- the content of carboxyl groups in the component (A) is suppressed by including a pressure-sensitive adhesive layer obtained by molding, heating and drying appropriately. Therefore, the reaction between the carboxyl group and the functional group contained in the pressure-sensitive adhesive composition can be suppressed. Thereby, it is excellent in long-term durability.
- the carboxyl group in (A) component with which content is suppressed reacts with the functional group contained in (B) component and (C) component.
- the pressure-sensitive adhesive layer can exhibit appropriate hardness and excellent adhesive strength. Thereby, a deformation
- Example 1 (Production of copolymer) In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, a dropping funnel and a stirring device, 0.1 part by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator and 130 weight of ethyl acetate as a solvent Parts, 99.6 parts by weight of butyl acrylate and 0.4 parts by weight of acrylic acid were added as monomer components, and after refluxing nitrogen at room temperature for 1 hour, the temperature of the monomer composition solution in the reaction vessel was changed to 67 The temperature was raised to 0 ° C., and polymerization was carried out in a nitrogen stream for 5 hours to obtain a solution of a copolymer (component (A) in Example 1).
- the weight average molecular weight of the obtained copolymer measured by gel permeation chromatography (GPC) was 1,000,000, and the molecular weight distribution (Mw / Mn) was 8.0.
- Examples 2 to 14 and Comparative Examples 1 to 10 (Production of Copolymer) Except for using monomer mixtures having the compositions shown in Table 1 and Table 2, respectively, the solutions of the copolymers of Examples 2 to 14 and Comparative Examples 1 to 10 were prepared by the method described in Example 1 above. Obtained. The results of measuring the weight average molecular weight of the obtained copolymer by the method described in Example 1 are shown in Tables 1 and 2.
- Test method 3.3.1. Wet heat durability Each polarizing plate with pressure-sensitive adhesive obtained in “3.2. Preparation of polarizing plate with pressure-sensitive adhesive” is cut into 250 mm ⁇ 350 mm, peeled off the PET film, and pasted on a glass substrate. The sample piece was left to stand at 60 ° C./95% RH for 500 hours, and a wet heat durability test was conducted. After the test, the state of foaming, floating and peeling generated on the sample piece was visually observed, and the durability was evaluated according to the following criteria.
- the adhesive type polarizing plate obtained in “3.2. Preparation of polarizing plate with adhesive” was pasted on a 19-inch size liquid crystal panel so as to be in a crossed Nicol state, and 240 ° C./95% RH atmosphere 240 After being allowed to stand for an hour, it was left for 2 hours in an atmosphere of 23 ° C./50% RH. Thereafter, light leakage was visually observed and evaluated according to the following criteria.
- Coronate L Tolylene diisocyanate crosslinking agent (manufactured by Nippon Polyurethane Industry Co., Ltd.)
- Coronate 342 Tolylene diisocyanate crosslinking agent (manufactured by Nippon Polyurethane Industry Co., Ltd.) Tetrad X: Amine-type epoxy crosslinking agent (Mitsubishi Gas Chemical Co., Ltd.) Tetrad C: Amine-type epoxy crosslinking agent (Mitsubishi Gas Chemical Co., Ltd.)
- Denacol EX-411 Non-amine type epoxy crosslinking agent (manufactured by Nagase ChemteX Corporation)
- KBM-403 Silane coupling agent (3-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) Kaulizer No. 1: Amine-based crosslinking accelerator (Kao Corporation)
- the pressure-sensitive adhesive layers of Examples 1 to 14 are excellent in wet heat durability, resistance to whitening after drying, sheet aging properties, peel strength after wet heat, and light leakage prevention properties.
- the pressure-sensitive adhesive compositions of Examples 1 to 14 include (A) a copolymer, (B) an isocyanate-based crosslinking agent, and (C) an epoxy-based crosslinking agent.
- A) 8 to 50 parts by mass of the (B) isocyanate-based crosslinking agent is contained with respect to 100 parts by mass of the copolymer, and the (A) copolymer contains more than 0% by mass of the carboxyl group-containing monomer. Since it is a copolymer of a monomer mixture containing less than 0.5% by mass, the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition of Examples 1 to 14 is excellent in resistance to whitening after drying. Yes.
- Whitening resistance after drying is an indicator of the transparency of the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition, and that the whitening resistance after drying is excellent is a pressure-sensitive adhesive obtained using the pressure-sensitive adhesive composition. It means that the transparency of the layer is excellent.
- the copolymer (A) contains 0% by mass of the carboxyl group-containing monomer. By being a monomer mixture containing more than 0.5% by mass, the carboxyl group contained in the copolymer (A) is converted into the (B) isocyanate-based crosslinking agent and / or the (C) epoxy-based compound.
- the copolymer (A) By reacting with the functional group contained in the crosslinking agent (or the functional group derived from the (B) isocyanate-based crosslinking agent and / or the (C) epoxy-based crosslinking agent), the copolymer (A) and the It is presumed that (B) the compatibility with the isocyanate-based crosslinking agent and the (C) epoxy-based crosslinking agent is enhanced.
- the pressure-sensitive adhesive compositions of Examples 1 to 14 contain 8 to 50 parts by mass of the (B) isocyanate-based crosslinking agent with respect to 100 parts by mass of the (A) copolymer.
- the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition of 1 to 14 is excellent in wet heat durability, sheet aging property, and post-wet heat peeling evaluation.
- the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition should have an appropriate hardness when the content of the isocyanate-based crosslinking agent (B) is 8 to 50 parts by mass with respect to parts by mass. Therefore, the deformation (polarizing plate) of the optical member is small, and as described above, the copolymer (A) contains the carboxyl group-containing monomer in an amount of more than 0% by mass and less than 0.5% by mass. It is presumed that this is because of the excellent long-term reliability because the content of the carboxyl group contained in the copolymer (A) is suppressed by being a copolymer of monomer mixture .
- the pressure-sensitive adhesive layers of Comparative Examples 1 to 5 contain (a1) a carboxyl group-containing monomer of 0.5% by mass or more as the (A) copolymer. Since the copolymer of the monomer mixture to be used is used, it can be understood that the peel strength after wet heat is inferior.
- the pressure-sensitive adhesive layer of Comparative Example 2 is inferior in durability and cracks because the pressure-sensitive adhesive composition used for the production of the pressure-sensitive adhesive layer contains neither the component (C) nor the component (D). It can be understood that light leakage has occurred as a result of the peeling that occurs.
- the pressure-sensitive adhesive layer of Comparative Example 3 was whitened under wet heat conditions because the pressure-sensitive adhesive composition used for the production of the pressure-sensitive adhesive layer did not contain the component (C). It can be understood that since the transmittance was lowered, the light leakage evaluation was improved as a result.
- the copolymer does not contain a carboxyl group, the carboxyl group and the functional group contained in the (B) isocyanate crosslinking agent and / or the (C) epoxy crosslinking agent (or the (B) isocyanate crosslinking) Reaction with the agent and / or the group derived from the (C) epoxy crosslinking agent), the (A) copolymer, the (B) isocyanate crosslinking agent, and the (C) epoxy crosslinking agent. This is presumably because of the low compatibility.
- the pressure-sensitive adhesive layer of Comparative Example 7 is inferior in wet heat durability and sheet aging.
- the copolymer (A3) is a copolymer of a monomer mixture containing (a3) a hydroxyl group-containing monomer in an amount exceeding 0.3 mass%. Since the polymer was used, the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition became too hard as a result of the reaction between the hydroxyl group in the (a3) hydroxyl group-containing monomer and the functional group contained in the other component. This is presumed to be due to this.
- the pressure-sensitive adhesive layer of Comparative Example 8 is inferior in whitening resistance after drying.
- the (B) isocyanate crosslinking agent was not used, so the carboxyl group contained in the (A) copolymer and the (B) isocyanate crosslinking agent. Reaction with the functional group contained in (or the group derived from the (B) isocyanate-based crosslinking agent) hardly occurs, and the compatibility between the (A) copolymer and the (B) isocyanate-based crosslinking agent is low. Therefore, it is estimated that the transparency of the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition was lowered.
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Abstract
Description
を含み、
前記(A)共重合体100質量部に対して前記(B)イソシアネート系架橋剤を8~50質量部含有し、
前記共重合体は、前記カルボキシル基含有単量体を0質量%超かつ0.5質量%未満含有する単量体混合物の共重合体である。
(a1)カルボキシル基含有単量体:0質量部%超かつ0.5質量%未満
(a2)(メタ)アクリル酸アルキルエステル単量体:90~99.9質量%
(a3)水酸基含有単量体:0~0.3質量%
(a4)前記(a1)~(a3)以外の共重合性単量体:0~9質量%
本発明の一実施形態に係る光学部材用粘着剤組成物(以下、単に「粘着剤組成物」と記載することもある。)は、(A)共重合体(以下、単に「(A)成分」と記載することもある。)と、(B)イソシアネート系架橋剤(以下、単に「(B)成分」と記載することもある。)と、(C)エポキシ系架橋剤(以下、単に「(C)成分」と記載することもある。)と、を含む。
(A)成分である共重合体は、カルボキシル基を含有するポリマーである。(A)成分はより具体的には、前記カルボキシル基含有単量体を0質量%超かつ0.5質量%未満含有する単量体混合物の共重合体である。(A)成分が、前記カルボキシル基含有単量体を0質量%超かつ0.5質量%未満含有する単量体混合物の共重合体であることにより、少量のカルボキシル基を含むため、組成物を用いて得られた粘着剤層の経時変化を低減することができる。また、(B)成分および(C)成分と該カルボキシル基とが反応することにより、(A)成分と(B)成分および(C)成分との相溶性が高まるため、本実施形態に係る粘着剤組成物を用いて得られた粘着剤層は白濁が生じにくく、また、乾燥温度が高くても白化しにくい。
(a2)(メタ)アクリル酸アルキルエステル単量体(以下、単に「(a2)成分」と記載することもある。):90~99.9質量%
(a3)水酸基含有単量体(以下、単に「(a3)成分」と記載することもある。):0~0.3質量%
(a4)前記(a1)~(a3)以外の共重合性単量体(以下、単に「(a4)成分」と記載することもある。):0~9質量%
(a1)成分であるカルボキシル基含有単量体は、分子構造中にカルボキシル基を有する単量体であり、(a1)成分は、(A)成分に含まれるカルボキシル基の由来となり得る。
前記単量体混合物が、(a2)成分である(メタ)アクリル酸アルキルエステル単量体を含むことにより、耐久性を(A)成分に付与することができる。前記単量体混合物における(a2)成分の含有量が90質量%未満であると、耐久性に劣る場合があり、一方、前記単量体組成物における(a2)成分の含有量が99.9質量%を超えても、(a1)成分の割合が相対的に低くなるため、耐久性に劣る場合がある。耐久性により優れている点で、前記単量体混合物における(a2)成分の含有量は95~99.6質量%であることが好ましく、98~99.6質量%であることがより好ましい。
アクリル酸i-プロピル、アクリル酸i-ブチル、アクリル酸t-ブチル、メタクリル酸i-プロピル、メタクリル酸i-ブチル、メタクリル酸t-ブチル、アクリル酸i-オクチル、メタクリル酸i-オクチル、アクリル酸2-エチルヘキシル、メタクリル酸2-エチルヘキシル等のエステル部位に分岐状アルキル基を有する(メタ)アクリル酸アルキルエステル単量体;
アクリル酸シクロヘキシル、メタクリル酸シクロヘキシル、アクリル酸イソボルニル、メタクリル酸イソボルニル、アクリル酸ジシクロペンタニル等のエステル部位に脂環アルキル基を有する(メタ)アクリル酸アルキルエステル単量体が挙げられ、このうち1種を単独でまたは2種以上を組み合わせて使用することもできる。
(a3)成分である水酸基含有単量体は、分子構造中に水酸基を有する単量体であり、(a3)成分は、(A)成分に含まれる水酸基の由来となり得る。
前記単量体混合物は、(a4)成分である前記(a1)~(a3)成分以外の共重合性単量体を含むことができる。
本実施形態に係る粘着剤組成物では、優れた耐久性、ならびに被着体との高い密着性を達成できる観点から、(A)成分である共重合体の原料である前記単量体混合物中における前記(a1)成分、(a2)成分、および(a3)成分の合計量が90~100質量%であることができる。
(A)成分は、重量平均分子量(Mw)が50万~200万である。(A)成分の重量平均分子量が50万未満であると、耐久性に劣ることがあり、一方、200万を超えると、本実施形態に係る粘着剤組成物を用いて得られる粘着剤層が硬くなりすぎ、光学部材の変形を防止できないことがある。光学部材の変形を防止することができ、かつ耐久性を高めることができる観点から、(A)成分の重量平均分子量は、80万~150万であることがより好ましい。ここで、(A)成分の重量平均分子量(Mw)および数平均分子量(Mn)は、GPC(ゲルパーミエーションクロマトグラフィー)を用い、下記の条件で標準ポリスチレン換算による重量平均分子量(Mw)を求めたものである。また、(A)成分の分子量分布(Mw/Mn)は6.0~9.5であることが好ましい。
測定装置:HLC-8120GPC(東ソー社製)
GPCカラム構成:以下の5連カラム(すべて東ソー社製)
(i)TSK-GEL HXL-H (ガードカラム)
(ii)TSK-GEL G7000HXL
(iii)TSK-GEL GMHXL
(iv)TSK-GEL GMHXL
(v)TSK-GEL G2500HXL
サンプル濃度:1.0mg/cm3となるように、テトラヒドロフランで希釈
移動相溶媒:テトラヒドロフラン
流量:1.0cm3/min
カラム温度:40℃
本実施形態に係る粘着剤組成物における(A)成分の含有量は、該粘着剤組成物の60~90質量部であることができ、65~90質量部であることが好ましい。
(A)成分の重合方法は、特に制限されるものではなく、溶液重合、乳化重合、懸濁重合などの公知の方法により重合できるが、重合により得られた共重合体の混合物を用いて、本発明の粘着剤組成物を製造するにあたり、処理工程が比較的簡単でかつ短時間で行える観点から、溶液重合により重合することが好ましい。
(B)成分であるイソシアネート系架橋剤は、イソシアネート基(-N=C=O)を有し、かつ、常温又は加熱下で(A)成分と架橋し得る架橋剤であるのが好ましく、例えば、キシリレンジイソシアネート、トリレンジイソシアネート、クロルフェニレンジイソシアネート、ヘキサメチレンジイソシアネート、テトラメチレンジイソシアネート、イソホロンジイソシアネート、ジフェニルメタンジイソシアネート、水添されたジフェニルメタンジイソシアネートなどのイソシアネートモノマーや、それらをトリメチロールプロパンなどの2価以上のアルコール化合物等に付加反応させたイソシアネート化合物やイソシアヌレート化物等が例示される。
(C)成分であるエポキシ系架橋剤は、エポキシ基(下記式(1)参照)を有し、かつ、常温又は加熱下で(A)成分と架橋し得る架橋剤であればよい。
本実施形態に係る粘着剤組成物は(D)シランカップリング剤(以下、単に「(D)成分」と記載することもある。)をさらに含むことができる。本実施形態に係る粘着剤組成物が(D)成分をさらに含むことにより、本実施形態に係る粘着剤組成物を用いて光学部材の表面に粘着剤層を形成した場合、光学部材と被着体との粘着を良好に保つことができる。
本実施形態に係る粘着剤組成物は、必要に応じて、(A)成分、(B)成分、(C)成分、(D)成分、(E)成分以外の成分をさらに含むことができる。例えば、本実施形態に係る粘着剤組成物には、本発明の効果を損なわない範囲で、界面活性剤、酸化防止剤、紫外線吸収剤、粘着付与剤、可塑剤等が配合されていても良い。
本発明の他の実施形態に係る光学部材用粘着剤組成物は、(A)カルボキシル基を有する共重合体と、(B)イソシアネート系架橋剤と、(C)エポキシ系架橋剤と、を含み、前記(A)共重合体100質量部に対して前記(B)イソシアネート系架橋剤を8~50質量部含有し、前記(A)共重合体100質量部に対して前記(C)エポキシ系架橋剤を0.05~4質量部含有する。この場合、前記(A)共重合体は、前記カルボキシル基含有単量体を0質量%超かつ0.5質量%未満含有する単量体混合物の共重合体であることができる。上記他の実施形態に係る光学部材用粘着剤組成物によれば、上記本実施形態に係る光学部材用粘着剤組成物と同様の作用効果を有する。
本実施形態に係る粘着剤組成物は、通常、前記(A)~(E)成分および必要に応じて任意成分を、同時にあるいは任意の順番で混合して調製される。また、(A)成分と(B)成分および(C)成分とを混合するにあたり、(A)成分を溶液重合により調製した場合は、重合完了後の(A)成分を含む溶液に(B)成分および(C)成分を添加してもよく、(A)成分を塊状重合により調製する場合は、重合完了後では均一混合が困難になるため、この重合の途中で(B)成分および(C)成分を添加して混合することが好ましい。
本実施形態に係る粘着剤組成物は、光学部材と被着体との貼り合わせに使用することができ、なかでも、長期(例えば1か月以上、好ましくは3か月以上)の耐久性が要求される光学部材の貼り合わせに好適に使用することができる。
本発明の他の実施形態に係る粘着シートは、本実施形態に係る粘着剤組成物を膜状に成形し、適宜加熱、乾燥して得られる。本実施形態に係る粘着シートは、例えば、本実施形態に係る粘着剤組成物をセパレーター(剥離フィルム)上に塗工することにより膜状に形成した後、加熱、乾燥することにより得ることができる。本実施形態に係る粘着シート(粘着剤層)を光学部材と他の被着体との間に設けることにより、該被着体と該光学部材との貼り合わせを行うことができる。
本実施形態に係る粘着剤組成物では、(A)成分と、(B)成分と、(C)成分と、を含み、前記(A)成分100質量部に対して前記(B)成分を8~50質量部含有し、前記(A)成分は、前記カルボキシル基含有単量体を0質量%超かつ0.5質量%未満含有する単量体混合物の共重合体であることにより、前記(A)成分に含まれるカルボキシル基の含有量が抑えられ、かつ、該(A)成分に対する前記(B)成分の割合が上記範囲に調整されているため、光学部材の変形を抑えることができ、かつ、長期の耐久性に優れている。
本発明の一実施形態に係る積層体は、ガラス基板と、偏光板と、前記ガラス基板と前記偏光板との間に設けられた、上記実施形態に係る光学部材用粘着剤組成物を膜状に成形し、加熱して得られる粘着剤層(粘着シート)と、を含む。
図1は、本発明の一実施形態に係る積層体の一例(積層体100)を模式的に示す断面図である。積層体100は、図1に示されるように、ガラス基板10と、偏光フィルム30と、ガラス基板10と偏光フィルム30との間に設けられた粘着剤層20と、を含む。
本実施形態に係る積層体を構成するガラス基板は、画像表示装置用に用いられるガラス基板であることができる。画像表示装置としては、例えば、液晶テレビ、コンピュータのモニタ、携帯電話、タブレットなどに用いられるTFT(薄膜トランジスタ)液晶表示装置であることができる。
本実施形態に係る積層体は、ガラス基板と、偏光フィルムと、前記ガラス基板と前記偏光フィルムとの間に設けられた、上記実施形態に係る光学部材用粘着剤組成物を膜状に成形し、適宜加熱、乾燥して得られる粘着剤層と、を含むことにより、上記実施形態に係る光学部材用粘着剤組成物において、(A)成分におけるカルボキシル基の含有量が抑えられているため、該カルボキシル基と、該粘着剤組成物に含まれる官能基との反応を抑制することができる。これにより、長期の耐久性に優れている。
以下、本発明を下記実施例に基づいて説明するが、本発明は実施例に限定されない。
3.1.1.実施例1(共重合体の製造)
冷却管、窒素導入管、温度計、滴下ロート及び撹拝装置を備えた反応容器に、重合開始剤として2,2’-アゾビスイソブチロニトリル0.1重量部、溶媒として酢酸エチル130重量部、単量体成分としてアクリル酸ブチル99.6重量部、アクリル酸0.4重量部を入れ、窒素還流を室温にて1時間行った後、反応容器内のモノマー組成物溶液の温度を67℃に昇温し、窒素気流中で5時間重合を行い、共重合体(実施例1の(A)成分)の溶液を得た。
表1および表2に示される組成の単量体混合物をそれぞれ用いた他は、上記実施例1に記載の方法によって、実施例2ないし14および比較例1ないし10の共重合体の溶液をそれぞれ得た。得られた共重合体の重量平均分子量を上記実施例1に記載の方法にて測定した結果を表1および表2にあわせて示す。
粘着剤溶液の(固形分)100部に対して、(B)イソシアネート系架橋剤としてトリレンジイソシアネートであるコロネートL 20部、(C)エポキシ系架橋剤としてテトラッドX 0.1部、(D)シランカップリング剤としてKBM-403 0.2部を添加し、これらを充分混合して、実施例1の粘着剤組成物を得た。
3.3.1.湿熱耐久性
上記「3.2.粘着剤付偏光板の作製」で得られた各粘着剤付き偏光板をそれぞれ250mm×350mmに裁断し、PETフィルムを剥離後、ガラス基板上に貼り付けて作製した試料片を、60℃/95%RHで500時間放置し、湿熱耐久性試験を行った。当該試験後、試料片に発生する発泡、浮き、剥がれの状態を目視で観察し、下記基準で耐久性を評価した。
◎:剥がれなし
〇:4辺において、外周端部から0.5mm以上の位置に剥がれがないもの
△:4辺において、外周端部から0.5mm以上の位置に剥がれがあり、1.5mm以上の位置に剥がれがないもの
×:4辺において、外周端部から1.5mm以上の位置に剥がれがあるもの
上記「3.2.粘着剤付偏光板の作製」で得られた各粘着剤付偏光板を120℃で10分間乾燥させた後、ヘイズメーターHM-150(村上色彩技研研究所)を用いて測定されたヘイズ測定値を以下の基準により評価した。
◎:0.5%未満
○:0.5%以上~1%未満
△:1%以上~5%未満
×:5%以上
上記「3.2.粘着剤付偏光板の作製」で得られた各粘着剤付偏光板を50℃の恒温器に10日間入れ、取り出してから23℃の雰囲気下で1日間静置した。次いで、この粘着剤付偏光板を310mm×385mmの大きさに裁断し、ガラス板の片面にラミネーターロールを用いて貼着し、次いで、50℃、5気圧に調整されたオートクレーブに20分間保持して、試験板を作成した。同様の試験板を2枚作成し、それぞれ温度60℃、湿度95%RHの条件下(耐湿)および温度80℃の条件下(耐熱)で500時間放置し、試験板における剥がれの発生等を目視で観察し、以下の基準にて評価した。
◎:剥がれ等の外観不良は全く観察されなかった。
○:剥がれ等の外観不良がごく僅かに観察されたが問題ない範囲である。
△:剥がれ等の外観不良が僅かに観察された。
×:剥がれ等の外観不良が明らかに観察された。
上記「3.2.粘着剤付偏光板の作製」で得られた各粘着剤付偏光板を幅25mm、長さ100mmに裁断し、ガラス板の片面にラミネーターロールを用いて貼着し、50℃、5気圧に調整されたオートクレーブに20分間保持した。取り出し23℃/50%の条件化で1時間静置後、ガラス板から180°の角度で剥離した時の力を測定したものを初期剥離力(P0)とした。ガラス板に貼着し、50℃、5気圧に調整されたオートクレーブに20分間保持した後、60℃/90%の恒温恒湿器に24時間入れ、取り出し後、23℃/50%の条件化で1時間静置し、ガラス板から180°の角度で剥離した時の力を測定したものを湿熱後剥離力(Pp)とした。湿熱処理後の剥離力(Pp)と、初期剥離力(P0)との比(Pp/P0)を湿熱後剥離力評価とした。湿熱後に剥離力が上昇、すなわち(Pp/P0)の値が高いほど、湿熱耐久試験での剥がれが起きにくく、耐久性が良好である。
19インチサイズ液晶パネルに、上記「3.2.粘着剤付偏光板の作製」で得られた粘着型偏光板をクロスニコルになるように張り合わせて、60℃/95%RH雰囲気下240時間時間放置した後、23℃/50%RH雰囲気下で2時間放置した。その後、光漏れを目視で観察し、以下の基準で評価した。
◎:光漏れが発生しない。
○:使用上問題ないレベルの範囲で光漏れが発生する。
△:使用上問題あるレベルの範囲で光漏れが発生する。
×:全面に広い範囲で光漏れが発生する。
コロネートL:トリレンジイソシアネート系架橋剤(日本ポリウレタン工業社製)
コロネート342:トリレンジイソシアネート系架橋剤(日本ポリウレタン工業社製)
テトラッドX:アミン型エポキシ系架橋剤(三菱瓦斯化学株式会社)
テトラッドC:アミン型エポキシ系架橋剤(三菱瓦斯化学株式会社)
デナコールEX-411:非アミン型エポキシ系架橋剤(ナガセケムテックス株式会社製)
KBM-403:シランカップリング剤(3-グリシドキシプロピルトリメトキシシラン、信越化学株式会社)
カオライザーNo.1:アミン系架橋促進剤(花王株式会社)
Claims (11)
- (A)共重合体と、
(B)イソシアネート系架橋剤と、
(C)エポキシ系架橋剤と、
を含み、
前記(A)共重合体100質量部に対して前記(B)イソシアネート系架橋剤を8~50質量部含有し、
前記(A)共重合体は、前記カルボキシル基含有単量体を0質量%超かつ0.5質量%未満含有する単量体混合物の共重合体である、光学部材用粘着剤組成物。 - 前記(A)共重合体100質量部に対して前記(C)エポキシ系架橋剤を0.05~4質量部含有する、請求項1に記載の光学部材用粘着剤組成物。
- 前記(B)イソシアネート系架橋剤の含有量に対する前記(C)エポキシ系架橋剤の配合量の関係が、(B):(C)=(10~40質量部):(0.1~2質量部)である、請求項1または2に記載の光学部材用粘着剤組成物。
- 前記単量体混合物は、下記単量体(a1)~(a4)の混合物である(ただし、前記単量体(a1)~(a4)を足し合わせて100質量%である。)、請求項1ないし3のいずれか1項に記載の光学部材用粘着剤組成物。
(a1)カルボキシル基含有単量体:0質量%超かつ0.5質量%未満
(a2)(メタ)アクリル酸アルキルエステル単量体:90~99.9質量%
(a3)水酸基含有単量体:0~0.3質量%
(a4)前記(a1)~(a3)以外の共重合性単量体:0~9質量% - (D)シランカップリング剤をさらに含む、請求項1ないし4のいずれか1項に記載の光学部材用粘着剤組成物。
- 前記(A)共重合体100質量部に対して前記(D)シランカップリング剤を0.01~1質量部含有する、請求項5に記載の光学部材用粘着剤組成物。
- 前記(C)エポキシ系架橋剤は、エポキシ基およびアミノ基を有する、請求項1ないし6のいずれか1項に記載の光学部材用粘着剤組成物。
- (E)塩基性化合物をさらに含む、請求項1ないし7のいずれか1項に記載の光学部材用粘着剤組成物。
- 請求項1ないし8のいずれか1項に記載の光学部材用粘着剤組成物を膜状に成形し、加熱、乾燥して得られる、粘着シート。
- ガラス基板と、
偏光フィルムと、
前記ガラス基板と前記偏光フィルムとの間に設けられた、請求項1ないし8のいずれか1項に記載の光学部材用粘着剤組成物を膜状に成形し、加熱、乾燥して得られる粘着剤層と、
を含む、積層体。 - 前記ガラス基板は、画像表示装置に用いられるガラス基板である、請求項10に記載の積層体。
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