WO2015182631A1 - 接着剤組成物、偏光板用接着剤組成物、偏光板用接着剤、およびそれを用いてなる偏光板 - Google Patents
接着剤組成物、偏光板用接着剤組成物、偏光板用接着剤、およびそれを用いてなる偏光板 Download PDFInfo
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- WO2015182631A1 WO2015182631A1 PCT/JP2015/065167 JP2015065167W WO2015182631A1 WO 2015182631 A1 WO2015182631 A1 WO 2015182631A1 JP 2015065167 W JP2015065167 W JP 2015065167W WO 2015182631 A1 WO2015182631 A1 WO 2015182631A1
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- acrylate
- adhesive composition
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
Definitions
- the present invention relates to an adhesive composition, an adhesive composition for a polarizing plate, an adhesive for a polarizing plate, and a polarizing plate using the same, and more specifically, a polarizing plate used for a liquid crystal display device or the like.
- the present invention relates to an adhesive composition used as an active energy ray-curable adhesive suitable for laminating a constituting polarizer and a protective film.
- Liquid crystal display devices are widely used as image display devices for liquid crystal televisions, computer displays, mobile phones and digital cameras.
- Such a liquid crystal display device has a configuration in which polarizing plates are laminated on both sides of a glass substrate in which liquid crystal is encapsulated, and various optical functional films such as a retardation plate are laminated thereon as necessary.
- a polarizing plate has been used as a structure in which a protective film is bonded to at least one surface, preferably both surfaces, of a polarizer made of a polyvinyl alcohol film.
- a polarizer a dichroic substance such as iodine is formed in a PVA film formed by using a polyvinyl alcohol resin having a high saponification degree (hereinafter, polyvinyl alcohol is abbreviated as “PVA”).
- PVA polyvinyl alcohol resin having a high saponification degree
- a uniaxially stretched PVA-based film in which the material is dispersed and adsorbed and preferably further crosslinked with a crosslinking agent such as boric acid is widely used. Since such a polarizer is a uniaxially stretched PVA-based film, it easily contracts under high humidity. Therefore, a protective film is bonded to the polarizer for the purpose of supplementing moisture resistance and strength.
- thermoplastic resins such as cellulose resin, polycarbonate resin, cyclic polyolefin resin, (meth) acrylic resin, and polyester resin are transparent, mechanical strength, thermal stability, moisture barrier property, isotropic property, etc.
- a protective film made of a triacetyl cellulose (TAC) resin has been widely used.
- These protective films are bonded to the polarizer by an adhesive, and as such an adhesive, from the viewpoint of adhesiveness to a polarizer having a hydrophilic surface, it is the same as the PVA resin aqueous solution, particularly the polarizer.
- a PVA resin aqueous solution mainly composed of a high saponification degree PVA resin is preferably used.
- the PVA adhesive is used as a solution or dispersion using water, it is necessary to dry the water when the adhesive is cured, and it takes a long time to dry the water. Accordingly, there has been a demand for improvement in that the drying efficiency is poor and the production efficiency of the polarizing plate is lowered.
- Patent Document 1 proposes an adhesive composed of a composition containing an epoxy resin that does not contain an aromatic ring as a main component and a photocationic polymerization initiator.
- Such an adhesive is cationic polymerization by irradiation with active energy rays. Even if a resin film with low moisture permeability is used as the protective film, the protective film is applied to one or both sides of the polarizer with sufficient adhesive strength and without causing problems such as poor appearance. It is described that a combined polarizing plate can be provided.
- the active energy ray hardening-type adhesive composition containing 3 types of radically polymerizable compounds from which SP value differs as a hardening component is excellent in adhesiveness of a polarizer and a protective film, and durability, It has been proposed as an adhesive with excellent water resistance.
- Patent Document 3 4-butylhydroxyacrylate: 20 to 90% by weight, ⁇ -carboxy-polycaprolactone acrylate: 1 to 70% by weight, other radical polymerizable compound: 0 to 15% by weight, photopolymerization initiator : 0.01-20% by weight, Silane coupling agent: 0-10% by weight, radically polymerizable adhesive for forming a polarizing plate having a glass transition temperature after curing of -80 to 0 ° C
- a composition has been proposed, and by using the adhesive composition, a PVA polarizer and a hard-to-adhere protective film typified by an acrylic film or a cycloolefin film are used as constituent layers, and the adhesive strength It is said that it is a polarizing plate which can form the small polarizing plate piece which is large and is excellent in durability, and is excellent in the punching workability.
- Patent Document 4 contains a (meth) acrylamide compound having no hydroxyl group, boric acid, and a photopolymerization initiator, and 0.5 to 5 parts by mass of the boric acid is used with respect to 100 parts by mass of the acrylamide compound.
- An ultraviolet curable composition has been proposed, and by using the composition, an ultraviolet curable composition having excellent adhesive strength can be obtained not only for various protective films, but particularly for acrylic resin films. ing.
- the adhesive of Patent Document 1 uses a cationic polymerizable UV curable adhesive instead of a water-based adhesive.
- the cationic polymerizable UV curable adhesive has a dark reaction after UV irradiation. Therefore, when a long cured product is formed into a take-up roll, there is a problem that curling tends to occur during storage.
- the cationic polymerizable ultraviolet curable adhesive has a problem that it is easily affected by humidity during curing and the cured state tends to vary.
- the adhesive layer is relatively hard, resulting in a decrease in adhesive strength over time, which is not satisfactory in terms of punching resistance and durability. There wasn't.
- the radical polymerizable adhesive composition of the above-mentioned Patent Document 3 since the shrinkage is accompanied by curing shrinkage when the (meth) acrylic acid monomer is cured, the stability of the initial adhesion is lowered and the adhesive force is not sufficient.
- the ultraviolet curable composition of Patent Document 4 shows an adhesive force to the acrylic resin film, but the adhesive force to the polarizer is not sufficient.
- the active energy ray-curable adhesive does not require a drying step and the production efficiency is higher than the PVA adhesive used as an aqueous solution, it can sufficiently bond various protective films for polarizing plates and polarizers. Was difficult and further improvement was required.
- the adhesive property between the polarizer and the protective film varies depending on the moisture content of the polarizer itself, but it is a polarizing plate that exhibits good adhesion even if the moisture content of the polarizer changes somewhat.
- an adhesive composition In general, it is considered that the adhesiveness decreases when the moisture content of the polarizer is small. However, even when the moisture content of the polarizer is small, it is required to have good adhesiveness.
- an adhesive having excellent adhesive force, and is suitable for bonding various protective films for polarizing plates and polarizers, particularly protective films other than TAC and polarizers.
- an adhesive composition exhibiting good adhesiveness without being influenced by the moisture content of the polarizer itself, excellent in production efficiency, and also excellent in color loss resistance, particularly an adhesive composition for polarizing plates. It is intended to provide.
- the photopolymerizable compound (A) is the main component and the Group 13 metals and metalloids.
- the photopolymerizable compound (A) is the main component and the Group 13 metals and metalloids.
- the photopolymerizable compound (B) and water (C) selected from the group of compounds it is excellent in the adhesion between the polarizer and the protective film, regardless of the moisture content of the polarizer itself.
- the present invention was completed by finding out that the color fading resistance of the polarizing plate was also excellent.
- the gist of the present invention includes a photopolymerizable compound (A), at least one oxo acid (B) selected from the group consisting of group 13 metals and metalloid compounds, and water (C). It is related with the adhesive composition which becomes.
- the present invention also provides an adhesive composition for a polarizing plate using the adhesive composition, an adhesive for a polarizing plate obtained by curing the adhesive composition, and a polarizing plate.
- the present invention it is important to contain at least one oxoacid (B) and water (C) selected from the group 13 metal and metalloid group, It focuses on moisture in the polarizer, which has not been noticed so far, and by using water, the water can migrate to the surface of the polarizer and make the polarizer surface layer hydrophilic. Is trying to improve.
- the present inventors have found an unexpected effect that the water content of the polarizer is adjusted by the presence of water and the adhesive property between the polarizer and the protective film is excellent.
- boric acid is preferred for the oxo acid (B) consisting of at least one selected from the group 13 metal and metalloid compounds, and the photopolymerizable compound (A) is a photopolymerization containing a proton-accepting group.
- Compound (A1) is preferred. This is because, for example, the hydroxyl group in the polarizer and boric acid are cross-linked, and tetrahydroboric acid generated by water chemically bonds with a photopolymerizable compound containing a proton-accepting group. It is also an attempt to improve the sex.
- the amount of water used in the present invention is not an amount that hinders the performance of the polarizing plate and does not need to be dried.
- the adhesive composition of the present invention especially the adhesive composition for polarizing plates, has high production efficiency of polarizing plates, and various protective films for polarizing plates and polarizers, particularly acrylic films and cyclic polyolefin resin films.
- a protective film other than TAC and a polarizer can be sufficiently adhered to each other, and the adhesive film exhibits good adhesiveness regardless of the moisture content of the polarizer. Even in the state immersed in the polarizing plate, it is possible to obtain a polarizing plate excellent in color loss resistance in which color loss is suppressed.
- (meth) acryl means acryl or methacryl
- (meth) acryloyl means acryloyl or methacryloyl
- (meth) acrylate means acrylate or methacrylate.
- the acrylic monomer is a monomer having at least one of an acryloyl group and a methacryloyl group
- the acrylic resin is a resin obtained by polymerizing a polymerization component containing at least one acrylic monomer.
- the adhesive composition of the present invention contains a photopolymerizable compound (A), at least one oxo acid (B) selected from the group consisting of group 13 metals and metalloid compounds, and water (C). It will be.
- the photopolymerizable compound (A) used in the present invention is used for coating properties, curability, adhesiveness, and the like.
- an ethylenically unsaturated compound having one ethylenically unsaturated group ( Hereinafter, it may be described as a monofunctional monomer.)
- at least one selected from the group of ethylenically unsaturated compounds having two or more ethylenically unsaturated groups (hereinafter, sometimes referred to as polyfunctional monomers).
- it is a seed.
- a monofunctional monomer is preferable in terms of coatability.
- monofunctional monomers examples include styrene, vinyl toluene, chlorostyrene, ⁇ -methyl styrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, vinyl acetate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3- Chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobol (Meth) acrylate, tricyclodecanyl (meth)
- a Michael adduct of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester can be used in combination.
- the Michael adduct of acrylic acid acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid A trimer, an acrylic acid tetramer, a methacrylic acid tetramer, etc. are mentioned.
- the 2-acryloyloxyethyl dicarboxylic acid monoester is a carboxylic acid having a specific substituent, such as 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxy Examples include ethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid monoester, and the like. Furthermore, other oligoester acrylates can also be mentioned.
- examples of the polyfunctional monomer include a bifunctional monomer and a trifunctional or higher monomer.
- bifunctional monomer examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene.
- tri- or higher functional monomer examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth).
- the photopolymerizable compound (A) preferably contains a photopolymerizable compound (A1) containing a proton-accepting group in terms of adhesive strength.
- the photopolymerizable compound (A1) containing a proton-accepting group is preferably a photopolymerizable compound containing a nitrogen atom in terms of compatibility, and in particular, a photopolymerizable compound containing an amide group. It is preferable that it is a compound represented by the following general formula (1).
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent
- R 3 represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, or R 2 and R 3 may be bonded to each other to contain an oxygen atom, or a 5-membered ring or 6 A member ring may be formed, provided that R 2 and R 3 are not hydrogen atoms at the same time.
- Examples of the compound represented by the general formula (1) include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N-isopropyl (meth).
- the content (weight ratio) of the photopolymerizable compound (A1) containing a proton-accepting group in the photopolymerizable compound (A) is preferably 20 to 100% by weight, particularly 25 to It is preferably 98% by weight, more preferably 30 to 95% by weight.
- the content ratio of the photopolymerizable compound (A1) containing such a proton-accepting group is too low, the adhesive force with the polarizer and the protective film tends to be low.
- the oxo acid (B) used in the present invention may be at least one selected from the group consisting of Group 13 metals and metalloid compounds, and is included for imparting an adhesive function. is there.
- the Group 13 metal and metalloid compound include boron, aluminum, gallium, indium, thallium, and the like. Among these, boron is preferable in terms of solubility in the photopolymerizable compound (A).
- boric acid is particularly preferable from the viewpoint of solubility in the photopolymerizable compound (A).
- the water (C) used in the present invention makes the surface layer of the polarizer hydrophilic, as an oxo acid (B) composed of at least one selected from the group 13 metal and metalloid compounds.
- oxo acid (B) composed of at least one selected from the group 13 metal and metalloid compounds.
- tetrahydroboric acid produced from boric acid and water (C) is chemically bonded to the photopolymerizable compound (A1) containing a proton-accepting group to improve adhesion. In order to give the function to make it contain.
- water (C) it is preferable to use water close to pure water from which impurities have been removed.
- ion-exchanged water or the like is used.
- so-called industrial water can be used as long as it does not depart from the spirit of the present invention.
- industrial water, soft water, ion-exchanged water, or the like can be used in combination. preferable.
- an adhesive comprising the photopolymerizable compound (A), at least one oxo acid (B) selected from the group of group 13 metals and metalloid compounds, and water (C).
- An agent composition in particular, an adhesive composition for polarizing plates can be obtained.
- the content of at least one oxoacid (B) selected from the group 13 metal and metalloid compound group is 0.1 to 100 parts by weight of the photopolymerizable compound (A).
- the amount is preferably ⁇ 20 parts by weight, particularly 1 to 18 parts by weight, more preferably 1.5 to 15 parts by weight, and particularly preferably 2 to 10 parts by weight. If the content of the oxo acid (B) is too small, the adhesive force between the polarizer and the protective film tends to be low, and if it is too large, the solubility in the photopolymerizable compound (A) tends to decrease. .
- the content of the oxo acid (B) is preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the photopolymerizable compound (A1) containing a proton-accepting group, particularly 1
- the amount is preferably 50 parts by weight, more preferably 1.5 to 20 parts by weight, and particularly preferably 2 to 15 parts by weight. If the content of the oxo acid (B) is too small, the adhesive force between the polarizer and the protective film tends to be low. If the content is too large, the photopolymerizability containing the photopolymerizable compound (A) and a proton-accepting group. There exists a tendency not to melt
- the content of water (C) is preferably 0.01 to 30 parts by weight, particularly 0.5 to 25 parts by weight, more preferably 100 parts by weight of the photopolymerizable compound (A).
- the amount is preferably 1 to 20 parts by weight, particularly 1.5 to 15 parts by weight.
- the content of water (C) is preferably 0.01 to 150 parts by weight with respect to 100 parts by weight of the photopolymerizable compound (A1) containing a proton-accepting group, and is particularly preferably 0.00.
- the amount is preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, and particularly preferably 1.5 to 20 parts by weight. If the water (C) content is too small, the adhesive force between the polarizer and the protective film tends to be low, and if it is too large, the photopolymerizable compound (A) and a photopolymerizable compound containing a proton-accepting group are present. There is a tendency not to dissolve in (A1).
- the content ratio (weight ratio) (B / C) of at least one oxo acid (B) and water (C) selected from the group 13 metal and metalloid group is 2/8 to It is preferably 8/2, particularly preferably 2.5 / 7.5 to 7.5 / 2.5, more preferably 3/7 to 7/3. If the content ratio (B / C) is too small or too large, the adhesive force between the polarizer and the protective film tends to be low.
- the urethane (meth) acrylate type compound (D) (however, except a photopolymerizable compound (A)) is contained by the point which can make hardening shrinkage of the hardened
- Such a urethane (meth) acrylate compound (D) is obtained by reacting a hydroxyl group-containing (meth) acrylate compound (d1) and a polyvalent isocyanate compound (d2), or a hydroxyl group-containing (meth) acrylate compound ( Examples include those obtained by reacting d1), a polyvalent isocyanate compound (d2), and a polyol compound (d3).
- a urethane (meth) acrylate compound obtained by reacting a hydroxyl group-containing (meth) acrylate compound (d1), a polyvalent isocyanate compound (d2), and a polyol compound (d3) is particularly preferable.
- Examples of the hydroxyl group-containing (meth) acrylate compound (d1) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) ) Acrylate, hydroxyalkyl (meth) acrylate such as 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethyl acryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone modified 2-hydroxyethyl ( (Meth) acrylate, dipropylene glycol (meth) acrylate, fatty acid modified-glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (Meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerin
- a hydroxyl group (meth) acrylate compound having 1 to 3 ethylenically unsaturated groups is preferable from the viewpoint of ensuring the flexibility of the cured product and excellent curability, and having one ethylenically unsaturated group.
- Compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyalkyl (meth) acrylates such as 6-hydroxyhexyl (meth) acrylate,
- hydroxyalkyl (meth) acrylates such as 6-hydroxyhexyl (meth) acrylate
- pentaerythritol tri (meth) acrylate is preferable in terms of excellent reactivity and versatility.
- compounds having one ethylenically unsaturated group are preferable from the viewpoint that the curing shrinkage of the cured product when cured can be reduced, and in particular, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meta) ) Acrylate is preferred.
- These hydroxyl group-containing (meth) acrylate compounds (d1) can be used alone or in combination of two or more.
- polyvalent isocyanate compound (d2) examples include aromatics such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate.
- Aliphatic polyisocyanates such as polyisocyanates, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, Alicyclic polyisocyanates such as 1,3-bis (isocyanatomethyl) cyclohexane, trimer compounds or multimeric compounds of these polyisocyanates, allophanate polyisocyanates, burette polyisocyanates, water-dispersed polyisocyanates, etc. Can be mentioned.
- diisocyanate compounds are preferred from the viewpoint of stability during the urethanization reaction, and in particular, aliphatic diisocyanates such as pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and hydrogenated diphenylmethane diisocyanate.
- An alicyclic diisocyanate such as hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane is preferably used, and more preferably isophorone diisocyanate, water in view of low curing shrinkage.
- Hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate are used, and particularly preferred Hydrogenated diphenylmethane diisocyanate in view of excellent reactivity and versatility, hydrogenated xylylene diisocyanate, isophorone diisocyanate is used.
- the polyvalent isocyanate compound (d2) can be used alone or in combination of two or more.
- polyol compound (d3) examples include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, (meth) acrylic polyols, polysiloxane polyols, and the like.
- polyether polyols examples include polyether polyols containing alkylene structures such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol, and random or block copolymers of these polyalkylene glycols. Is mentioned.
- polyester polyol examples include three kinds of components such as a condensation polymer of polyhydric alcohol and polycarboxylic acid, a ring-opening polymer of cyclic ester (lactone), polyhydric alcohol, polycarboxylic acid and cyclic ester. And reactants.
- polyhydric alcohol examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethyl.
- Methylene diol 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin , Trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), sugar alcohols (such as xylitol and sorbitol)
- polyvalent carboxylic acid examples include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid, 1,4 -Arocyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, trimellitic acid, etc.
- aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid
- 1,4 -Arocyclic dicarboxylic acids
- cyclic ester examples include propiolactone, ⁇ -methyl- ⁇ -valerolactone, and ⁇ -caprolactone.
- polycarbonate polyol examples include a reaction product of a polyhydric alcohol and phosgene, a ring-opening polymer of a cyclic carbonate (alkylene carbonate, etc.), and the like.
- polyhydric alcohol examples include polyhydric alcohols exemplified in the description of the polyester-based polyol, and examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like. It is done.
- the polycarbonate-based polyol may be a compound having a carbonate bond in the molecule and having a hydroxyl group at the end, and may have an ester bond together with the carbonate bond.
- polyolefin-based polyol examples include those having a homopolymer or copolymer such as ethylene, propylene, and butene as a saturated hydrocarbon skeleton, and having a hydroxyl group at the molecular end.
- polybutadiene-based polyol examples include those having a butadiene copolymer as a hydrocarbon skeleton and having a hydroxyl group at the molecular end.
- the polybutadiene-based polyol may be a hydrogenated polybutadiene polyol in which all or part of the ethylenically unsaturated groups contained in the structure thereof are hydrogenated.
- Examples of the (meth) acrylic polyol include those having at least two hydroxyl groups in the polymer or copolymer molecule of the (meth) acrylic acid ester. , For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic acid And (meth) acrylic acid alkyl esters such as 2-ethylhexyl, decyl (meth) acrylate, dodecyl (meth) acrylate, and octadecyl (meth) acrylate.
- polysiloxane polyol examples include dimethyl polysiloxane polyol and methylphenyl polysiloxane polyol.
- polyester-based polyols and polyether-based polyols are preferable, and polyether-based polyols are particularly preferable in terms of flexibility of the cured product and compatibility with the photopolymerizable compound (A) and water (C).
- Polytetramethylene glycol is most preferred.
- the polyol compound (d3) can be used alone or in combination of two or more.
- the polyol compound (d3) preferably has a number average molecular weight of 250 to 3,000, particularly 250 to 2,000, and more preferably 250 to 1,000. If the number average molecular weight is too large, the crystallinity tends to be high and the viscosity tends to be high.
- said number average molecular weight is a number average molecular weight by standard polystyrene molecular weight conversion, a column is put into a high performance liquid chromatography (Nippon Waters, "Waters 2695 (main body)” and “Waters 2414 (detector)”).
- Shodex GPC KF-806L exclusion limit molecular weight: 2 ⁇ 10 7 , separation range: 100 to 2 ⁇ 10 7 , theoretical plate number: 10,000 plates / piece
- filler material styrene-divinylbenzene copolymer, filler It is measured by using three series of particle diameters: 10 ⁇ m).
- the urethane (meth) acrylate compound (D) can be produced as follows. The following explanation is about the reaction of the hydroxyl group-containing (meth) acrylate compound (d1), the polyvalent isocyanate compound (d2) and the polyol compound (d3), but according to this method. By performing, the thing formed by making a hydroxyl-containing (meth) acrylate type compound (d1) and a polyvalent isocyanate type compound (d2) react can also be manufactured.
- (1) A method in which the above hydroxyl group-containing (meth) acrylate compound (d1), polyvalent isocyanate compound (d2), and polyol compound (d3) are charged into a reactor or separately and reacted (2) ) A method of reacting a hydroxyl group-containing (meth) acrylate compound (d1) with a reaction product obtained by reacting a polyol compound (d3) with a polyvalent isocyanate compound (d2) in advance; The reaction product obtained by reacting the isocyanate compound (d2) with the hydroxyl group-containing (meth) acrylate compound (d1) in advance may be reacted with the polyol compound (d3).
- the method (2) is preferred from the standpoint of properties and reduction of byproducts.
- the reaction between the polyol compound (d3) and the polyvalent isocyanate compound (d2) known reaction means can be used.
- the molar ratio of the isocyanate group in the polyvalent isocyanate compound (d2) to the hydroxyl group in the polyol compound (d3) is usually about 2n: (2n-2) (n is an integer of 2 or more).
- the addition reaction of the reaction product obtained by reacting the polyol compound (d3) and the polyvalent isocyanate compound (d2) in advance with the hydroxyl group-containing (meth) acrylate compound (d1) is also a known reaction. Means can be used.
- the reaction molar ratio between the reaction product and the hydroxyl group-containing (meth) acrylate compound (d1) is, for example, that the polyisocyanate compound (d2) has two isocyanate groups and the hydroxyl group-containing (meth) acrylate compound (d1).
- ) Has one hydroxyl group
- the reaction product: hydroxyl group-containing (meth) acrylate compound (d1) is about 1: 2
- the polyisocyanate compound (d2) has three isocyanate groups.
- the reaction product: hydroxyl group-containing (meth) acrylate compound (d1) is about 1: 3.
- a catalyst is used for the purpose of promoting the reaction. It is also preferable to use, for example, organometallic compounds such as dibutyltin dilaurate, trimethyltin hydroxide, tetra-n-butyltin, zinc octenoate, tin octenoate, cobalt naphthenate, stannous chloride.
- Metal salts such as stannic chloride, triethylamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene, N, N, N ′,
- Amine catalysts such as N'-tetramethyl-1,3-butanediamine and N-ethylmorpholine, bismuth nitrate, bromide Organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, lauryl Organic acid bismuth such as bismuth acid salt, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth a
- an organic solvent having no functional group for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatic solvents such as toluene and xylene can be used.
- the reaction temperature is usually 30 to 90 ° C., preferably 40 to 80 ° C.
- the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.
- the urethane (meth) acrylate compound (D) is obtained.
- the weight average molecular weight of the urethane (meth) acrylate compound (D) is preferably 1,000 to 60,000, particularly 1,500 to 50,000, more preferably 2,000 to 30,000. It is preferable. If the weight average molecular weight is too small, the cured shrinkage of the cured product tends to be large when cured, and if too large, the viscosity tends to be high and handling tends to be difficult.
- the above-mentioned weight average molecular weight is a weight average molecular weight in terms of standard polystyrene molecular weight, and the column: Shodex GPC KF-806L (excluded) was subjected to high performance liquid chromatography (manufactured by Showa Denko Co., Ltd., “Shodex GPC system-11 type”).
- Shodex GPC KF-806L excludeded
- high performance liquid chromatography manufactured by Showa Denko Co., Ltd., “Shodex GPC system-11 type”.
- the viscosity of the urethane (meth) acrylate compound (D) is preferably 500 to 100,000 mPa ⁇ s, particularly 800 to 50,000 mPa ⁇ s, more preferably 1, at 60 ° C. 000 to 35,000 mPa ⁇ s is preferable. If the viscosity is too high, a large amount of diluent must be used, and workability tends to be reduced. If the viscosity is too low, adhesion tends to be reduced. The viscosity is measured with an E-type viscometer.
- the content of the urethane (meth) acrylate compound (D) is preferably 3 to 70 parts by weight, particularly 5 to 65 parts by weight, based on 100 parts by weight of the photopolymerizable compound (A). Further, it is preferably 8 to 60 parts by weight. If the content is too small, the adhesiveness tends to decrease, and if it is too large, the viscosity is too high and the workability tends to decrease.
- a polymerization initiator (E) it is preferable to further contain a polymerization initiator (E) to form an adhesive composition.
- a polymerization initiator (E) for example, various polymerization initiators such as a photopolymerization initiator (e1) and a thermal polymerization initiator (e2) can be used, and in particular, a photopolymerization initiator ( It is preferable to use e1) in that it can be cured by irradiation with active energy rays such as ultraviolet rays for a very short time.
- the adhesive composition is cured by irradiation with active energy rays
- the thermal polymerization initiator (e2) is used, the adhesive composition is cured by heating.
- Examples of the photopolymerization initiator (e1) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4- Acetophenones such as morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomers; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl Ether etc.
- auxiliary agents include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid.
- Ethyl, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Etc. can be used in combination.
- photopolymerization initiators (e1) benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-hydroxy It is preferable to use -2-methyl-1-phenylpropan-1-one.
- thermal polymerization initiator (e2) examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetate peroxide, 1,1-bis (t-hexyl peroxide).
- the content of the polymerization initiator (E) is preferably 0.5 to 20 parts by weight, particularly 0.8 to 15 parts by weight with respect to 100 parts by weight of the photopolymerizable compound (A). Further, it is preferably 1 to 10 parts by weight. If the content of the polymerization initiator (E) is too small, the curability tends to be poor and the physical properties tend to be unstable. If the content is too large, the low molecular weight component increases, the crosslinking density decreases, and the water resistance and heat resistance decrease. Tend to.
- the polymerization initiator (E) can be mixed at once, or any two to four components can be mixed, and then the remaining components can be mixed.
- the photopolymerizable compound (A ) And oxo acid (B) are mixed, heated to 30 to 90 ° C., preferably 40 to 80 ° C., more preferably 50 to 70 ° C., and dissolved by stirring, then water (C), urethane (meta ) It is preferable in terms of solubility to mix the acrylate compound (D) and the polymerization initiator (E). More preferably, among the photopolymerizable compounds (A), the photopolymerizable compound (A1) containing a proton-accepting group and the oxo acid (B) are first mixed, dissolved as described above, and then subjected to other photopolymerization. A method of mixing the functional compound (A), water (C), urethane (meth) acrylate compound (D), and polymerization initiator (E) is more preferable from the viewpoint of solubility.
- an antistatic agent in addition to the above components, an antistatic agent, other acrylic adhesives, other adhesives, urethane resin, rosin, rosin ester, as long as the effects of the present invention are not impaired.
- Conventionally known additives such as agents, anti-aging agents, ultraviolet absorbers, functional dyes and the like, and compounds that cause coloration or discoloration upon irradiation with ultraviolet rays or radiation can be blended. Is preferably 30% by weight or less, particularly preferably 20% by weight or less, based on the total composition.
- a small amount of impurities contained in the raw materials for producing the constituent components of the adhesive composition may be contained.
- the adhesive composition of the present invention preferably functions as an adhesive by being cured by irradiation with active energy rays, and is preferably used as an adhesive for a polarizing plate for bonding a polarizer and a protective film. It is something that can be done.
- the adhesive composition of the present invention may contain a solvent or may be used as a solvent-free composition, but the solvent-free type that can omit the step of drying the solvent in the adhesive. It is preferable to use it as a composition.
- a dichroic material such as iodine or a dichroic dye is adsorbed on a vinyl alcohol resin film such as a PVA film, a partially formalized PVA film, or an ethylene-vinyl alcohol resin film.
- a birefringent material having liquid crystallinity together with a dichroic material in the above is a vinyl alcohol resin
- a uniaxially stretched thermoplastic norbornene resin film containing a dichroic material for example, Japanese Patent Application Laid-Open No. 2001-356213
- PVA resin or ethylene-vinyl alcohol resin is dehydrated or deaceticated. Introducing a polyene structure continue, polyene-based film obtained by stretching them (e.g., see JP Patent 2007-17845.), And the like.
- a uniaxially stretched film in which iodine is adsorbed on a PVA-based film is preferable because of excellent polarization characteristics.
- the thickness of such a polarizer is usually 0.1 to 100 ⁇ m, particularly 0.5 to 80 ⁇ m, more preferably 1 to 60 ⁇ m.
- the water content of the polarizer is usually 15% by weight or less, preferably 14% by weight or less, and particularly preferably 0.2 to 13% by weight.
- the protective film used in the present invention can make up for the lack of durability under high humidity, which is a problem of polarizers, by bonding to at least one surface, preferably both surfaces, of the polarizer. Furthermore, the properties required for the protective film used in the present invention include transparency, mechanical strength, thermal stability, moisture shielding properties, optical isotropy, and the like.
- a cellulose ester resin, a cyclic olefin resin, and a (meth) acrylic resin are preferably used from the viewpoints of optical properties and durability.
- Other materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polystyrene resins such as polystyrene and acrylonitrile / styrene copolymers, polyolefin resins such as polyethylene and polypropylene, polyarylate resins, and polycarbonate resins.
- Vinyl chloride resins such as nylon and aromatic polyamide, (fluorine-containing) polyimide resins, polyether ether ketone resins, polyphenylene sulfide resins, vinylidene chloride resins, polyvinyl acetal resins such as polyvinyl butyral And polyoxymethylene resins and epoxy resins. These may be used alone or in combination of two or more.
- Typical examples of the cellulose ester resin used in the cellulose ester resin film include triacetyl cellulose and diacetyl cellulose, but other lower fatty acid esters of cellulose, cellulose acetate propionate, cellulose acetate butyrate, and the like.
- the mixed fatty acid ester can be used.
- Examples of the cyclic olefin resin used in the cyclic olefin resin film include norbornene resins.
- Such norbornene resins include, for example, ring-opening (co) polymers of norbornene monomers, resins obtained by addition polymerization of norbornene monomers, and addition copolymers of norbornene monomers and olefin monomers such as ethylene and ⁇ -olefins. Resin etc. are included.
- norbornene-based monomers include dimers such as norbornene and norbornadiene; tricyclics such as dicyclopentadiene and dihydroxypentadiene; heptacyclics such as tetracyclopentadiene; these methyl, ethyl, propyl and butyl Substituents such as alkyl, alkenyl such as vinyl, alkylidene such as ethylidene, aryl such as phenyl, tolyl and naphthyl; and further ester groups, ether groups, cyano groups, halogens, alkoxycarbonyl groups, pyridyl groups, hydroxyl groups, carvone Examples include substituents having groups containing elements other than carbon and hydrogen, such as acid groups, amino groups, hydroxyl-free groups, silyl groups, epoxy groups, acryloyl groups, and methacryloyl groups.
- cyclic olefin-based resin films examples include “ARTON” manufactured by JSR, “ZEONOR”, “ZEONEX” manufactured by Nippon Zeon, “OPTOREZ” manufactured by Hitachi Chemical, and “APEL” manufactured by Mitsui Chemicals. it can.
- Examples of the (meth) acrylic resin used in the (meth) acrylic resin film include poly (meth) acrylic acid esters such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, and methyl methacrylate.
- acrylic resin films examples include “Acrypet VRL20A”, “Acrypet IRD-70” manufactured by Mitsubishi Rayon Co., Ltd., and “MUX-60” manufactured by UMGABS.
- the protective film is subjected to surface hydrophilization treatment such as saponification treatment with an alkali solution for a film made of a cellulose ester resin or corona discharge treatment or plasma treatment for a film made of a cyclic olefin resin, as necessary. It may be what you did.
- the thickness of such a protective film is not particularly limited, but is usually thicker than that of a polarizer, and has a function of imparting strength as a base material of the polarizer, and is usually 10 to 100 ⁇ m, preferably 20 to 80 ⁇ m. is there.
- such a protective film can be provided with a hard coat layer on a surface not laminated with a polarizer, or can be subjected to various treatments such as anti-sticking, anti-reflection, and anti-glare.
- various optical functional films such as a retardation plate and a viewing angle widening film can be laminated.
- the polarizing plate of the present invention is formed by laminating the above polarizer and a protective film via an adhesive for polarizing plates.
- the polarizing plate adhesive composition is usually a liquid polarizing plate, which is formed by laminating a protective film on at least one surface, preferably both surfaces of the polarizer, using the polarizing plate adhesive of the present invention. Is uniformly applied to a polarizer and / or a protective film, and then both are bonded together, pressure-bonded, and irradiated with active energy rays to form a polarizing plate.
- a polarizer or a protective film for example, reverse coater, gravure coater (direct, reverse or offset), bar reverse coater, roll coater, die coater, bar coater, rod coater, etc. Or can be applied by dipping.
- a roll laminator or the like can be used, and the pressure is selected from the range of 0.1 to 10 MPa.
- rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and ⁇ rays, electron beams, proton rays, neutron rays, etc.
- Curing by ultraviolet irradiation is advantageous from the standpoint of availability of the device and price.
- electron beam irradiation it can harden
- a high pressure mercury lamp, an electrodeless lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, a black light, an LED lamp or the like is used as a light source for such ultraviolet irradiation.
- Such ultraviolet irradiation 2 ⁇ 3000mJ / cm 2, preferably carried out at a 10 ⁇ 2000mJ / cm 2 conditions.
- the high-pressure mercury lamp for example, 5 ⁇ 3000mJ / cm 2, preferably at a 50 ⁇ 2000mJ / cm 2 conditions.
- the electrodeless lamp for example, it is performed under the conditions of 2 to 2000 mJ / cm 2 , preferably 10 to 1000 mJ / cm 2 .
- the irradiation time varies depending on the type of light source, the distance between the light source and the coating surface, the coating thickness, and other conditions, but it is usually several seconds to several tens of seconds, and in some cases may be a fraction of a second.
- the electron beam irradiation for example, an electron beam having an energy in the range of 50 to 1000 keV is used, and the irradiation amount is preferably 2 to 50 Mrad.
- the irradiation direction of such active energy rays can be irradiated from any appropriate direction, but it is preferable to irradiate from the transparent protective film side in terms of preventing the polarizer from being deteriorated.
- the thickness of the adhesive layer in the polarizing plate of the present invention obtained as described above is usually 0.01 to 10 ⁇ m, preferably 0.01 to 5 ⁇ m, particularly preferably 0.01 to 2 ⁇ m, more preferably 0.01 to 1 ⁇ m. It is. If the thickness is too thin, the cohesive force of the adhesive force itself cannot be obtained and the adhesive strength tends not to be obtained. If the thickness is too thick, the workability of the polarizing plate tends to be reduced due to cracks during punching.
- the adhesive composition of the present invention is an adhesive having excellent adhesive strength at the initial stage and over time, and can be used for various applications.
- various protective films for polarizing plates and polarizers particularly those other than TAC. It is suitable for laminating a protective film and a polarizer, and exhibits good adhesion without being influenced by the moisture content of the polarizer itself, and further eliminates the need for a drying step, and also improves the production efficiency of the polarizing plate. It also has excellent resistance to color loss of the polarizing plate.
- a bifunctional polyether urethane acrylate (D-1) was obtained.
- the obtained bifunctional polyether urethane acrylate (D-1) had a weight average molecular weight of 3,000 and a viscosity of 12,000 mPa ⁇ s / 60 ° C.
- Example 1 ⁇ Preparation of adhesive composition for polarizing plate> Prepare 85 parts of dimethylacrylamide (A-1) and 7 parts of boric acid (B-1) at the same time in the preparation flask, and heat them until the liquid temperature reaches 60 ° C while stirring. Mixing was continued for 1 hour until the acid (B-1) was dissolved. After cooling to room temperature, 15 parts of ethylene glycol diacrylate (A-3), 7 parts of ion-exchanged water (C-1), 30 parts of urethane acrylate (D-1), 2 parts of Irgacure 184 (E-1) Then, 2 parts of lucillin TPO (E-2) was charged simultaneously and mixed to obtain an adhesive composition for polarizing plate.
- Examples 2 to 7, Comparative Examples 1 to 3 A polarizing plate adhesive composition was prepared in the same manner as in Example 1 except that the blending components prepared above were blended in the proportions shown in Table 1 below.
- ⁇ Production of Polarizer [F]> a 60 ⁇ PVA film was stretched 1.7 times while immersed in a 25 ° C. water bath. Next, the film was stretched 1.6 times while immersed in a 28 ° C. aqueous solution of iodine 0.5 g / L and potassium iodide 30 g / L, and then boric acid 40 g / L and potassium iodide 30 g / L. While being immersed in an aqueous solution (55 ° C.), boric acid treatment was performed while uniaxially stretching 2.1 times. Thereafter, it was washed with an aqueous potassium iodide solution and dried at 70 ° C.
- a polarizer [F-1] having a total draw ratio of 6 times.
- the moisture content of the polarizer [F-1] was 4%.
- a polarizer [F-2] was obtained in the same manner as the polarizer [F-1] except that the drying temperature was 90 ° C.
- the moisture content of the polarizer [F-2] was 1%.
- UV irradiation is performed with an ultraviolet irradiation device equipped with a high-pressure mercury lamp at a peak illuminance of 130 mW / cm 2 and an integrated exposure amount of 900 mJ / cm 2 (365 nm) to adhere.
- the agent composition was cured to obtain a polarizing plate test piece. Performance evaluation was performed as follows using the polarizing plate test piece obtained above.
- Examples 1 to 4 and 6 comprising a photopolymerizable compound (A), at least one oxo acid (B) selected from the group 13 metal and metalloid compounds, and water (C)
- the polarizing plate adhesive composition of Nos. 7 and 7 can sufficiently bond a polarizer and a protective film, and has an excellent effect on water resistance and color loss resistance.
- the adhesive compositions of Comparative Examples 1 to 3 that do not contain oxo acid (B) or water (C) have excellent effects on adhesion and color loss resistance. It is inferior in resistance to color loss and cannot be put to practical use as an adhesive composition for polarizing plates. It can be seen that the adhesive composition of the present invention is very excellent.
- the adhesive composition for polarizing plates comprising the adhesive composition of the present invention and such an adhesive composition is excellent in adhesion between the polarizer and the protective film, and various protective films and polarizers for the polarizing plate.
- it is suitable for laminating a protective film other than TAC and a polarizer, and exhibits good adhesiveness without being influenced by the moisture content of the polarizer itself. It is also excellent in slipping.
- it does not require a drying step and has excellent production efficiency.
- it is useful not only for a TAC film but also for bonding a protective film such as an acrylic film or a cyclic polyolefin resin film to a polarizer.
- the adhesive composition of the present invention can be used for, for example, bonding of various optical films or sheets, bonding of electronic parts, precision equipment, packaging materials, display materials, etc. It can also be used.
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Abstract
Description
上記特許文献3のラジカル重合性接着剤組成物では、(メタ)アクリル酸モノマーの硬化時に硬化収縮を伴うために、初期接着の安定性が低くなり接着力が充分でないものであった。
上記特許文献4の紫外線硬化型組成物では、アクリル樹脂フィルムに対しては接着力を示すが、偏光子への接着力が充分でないものであった。
なお、本発明において、(メタ)アクリルとはアクリルあるいはメタクリルを、(メタ)アクリロイルとはアクリロイルあるいはメタクリロイルを、(メタ)アクリレートとはアクリレートあるいはメタクリレートをそれぞれ意味するものである。
また、アクリル系モノマーとは、アクリロイル基、メタクリロイル基の少なくとも一方を有するモノマーであり、アクリル系樹脂とは、少なくとも1種のアクリル系モノマーを含む重合成分を重合して得られる樹脂である。
本発明の接着剤組成物は、光重合性化合物(A)、第13族の金属および半金属化合物の群から選ばれる少なくとも1種からなるオキソ酸(B)、および水(C)を含有してなるものである。
光重合性化合物(A)は上記の中から1種を用いてもよいし2種以上併用してもよい。
CH2=C(R1)-CONR2(R3)・・・(1)
(式(1)において、R1は、水素原子またはメチル基を示し、R2は、水素原子または置換基を有してもよい炭素数1~4の直鎖もしくは分岐鎖のアルキル基を示し、R3は、水素原子または炭素数1~4の直鎖または分岐鎖のアルキル基を示し、または、R2とR3は、互いに結合して、酸素原子を含んでもよく5員環または6員環を形成してもよい。ただし、R2とR3は、同時に水素原子である場合を除くものである。)
第13族の金属および半金属化合物としては、ホウ素、アルミニウム、ガリウム、インジウム、タリウム等が挙げられるが、中でも光重合性化合物(A)への溶解性の点でホウ素が好ましい。
かかるオキソ酸(B)としては、光重合性化合物(A)への溶解性の点で、特にホウ酸が好ましい。
また、これら水酸基含有(メタ)アクリレート系化合物(d1)は1種または2種以上組み合わせて使用することができる。
また、多価イソシアネート系化合物(d2)は1種または2種以上組み合わせて使用することができる。
ポリブタジエン系ポリオールは、その構造中に含まれるエチレン性不飽和基の全部または一部が水素化された水添化ポリブタジエンポリオールであってもよい。
ウレタン(メタ)アクリレート系化合物(D)の重量平均分子量は、1,000~60,000であることが好ましく、特には1,500~50,000、更には2,000~30,000であることが好ましい。かかる重量平均分子量が小さすぎると硬化した時の硬化物の硬化収縮が大きくなる傾向にあり、大きすぎると粘度が高くなり取り扱いが困難になる傾向がある。
なお、粘度の測定法はE型粘度計による。
かかる重合開始剤(E)としては、例えば、光重合開始剤(e1)、熱重合開始剤(e2)等の種々の重合開始剤を用いることが可能であるが、特には光重合開始剤(e1)を使用することが、ごく短時間の紫外線等の活性エネルギー線照射により硬化させることが可能となる点で好ましい。
また、上記添加剤の他にも、接着剤組成物の構成成分の製造原料等に含まれる不純物等が少量含有されたものであっても良い。
本発明で用いられる偏光子としては、特に制限はなく、公知のものを使用することができる。
例えば、(i)PVA系フィルム、部分ホルマール化PVA系フィルム、エチレン-ビニルアルコール系樹脂フィルム、等のビニルアルコール系樹脂フィルムに、ヨウ素や二色性色素などの二色性材料を吸着させて一軸延伸したもの(例えば、特開2001-296427号公報、特開平7-333426号公報参照。)、(ii)上記(i)において二色性材料とともに液晶性を有する複屈折材料をビニルアルコール系樹脂フィルム中に有するもの(例えば、特開2007-72203号公報参照。)、(iii)二色性材料を含有する熱可塑性ノルボルネン系樹脂フィルムを一軸延伸したもの(例えば、特開2001-356213号公報参照。)、(iv)PVA系樹脂やエチレン-ビニルアルコール系樹脂を脱水あるいは脱酢酸して連続するポリエン構造を導入し、これを延伸して得られるポリエン系フィルム(例えば、特開2007-17845号公報参照。)、などを挙げることができる。
中でも、偏光特性が優れる点から、PVA系フィルムにヨウ素が吸着された一軸延伸フィルムが好適である。
また、偏光子の水分率については、通常15重量%以下であり、好ましくは14重量%以下、特に好ましくは0.2~13重量%である。
本発明で用いられる保護フィルムは、偏光子の少なくとも一方の面、好ましくは両面に貼り合わせることで、偏光子の問題点である高湿度下での耐久性不足を補うことができるものである。
更に、本発明で用いられる保護フィルムに求められる特性としては、透明性、機械強度、熱安定性、水分遮蔽性、光学的等方性などを挙げることができる。
また、その他の材料として、ポリエチレンテレフタレートやポリエチレンナフタレート等のポリエステル系樹脂、ポリスチレンやアクリロニトリル・スチレン共重合体等のポリスチレン系樹脂、ポリエチレン、ポリプロピレン等のポリオレフィン系樹脂、ポリアリレート系樹脂、ポリカーボネート系樹脂、塩化ビニル系樹脂、ナイロンや芳香族ポリアミド等のアミド系樹脂、(含フッ素)ポリイミド系樹脂、ポリエーテルエーテルケトン系樹脂、ポリフェニレンスルフィド系樹脂、塩化ビニリデン系樹脂、ポリビニルブチラールなどのポリビニルアセタール系樹脂、ポリオキシメチレン系樹脂、エポキシ樹脂などを挙げることができる。これらは単独でもしくは2種以上併せて用いられる。
また、帯電防止剤を保護フィルム表面に塗布あるいはフィルム中に含有させたものも好ましく用いられる。
本発明の偏光板は、偏光板用接着剤を介して上記の偏光子と保護フィルムが貼り合わされてなるものである。詳しくは、偏光子の少なくとも一方の面、好ましくは両面に、本発明の偏光板用接着剤を用いて保護フィルムを貼り合わせてなるものであり、通常は、液状とした偏光板接着剤組成物を偏光子あるいは保護フィルム、あるいはその両方に均一に塗布した後、両者を貼り合わせ、圧着し、活性エネルギー線照射を行なうことで偏光板が形成される。
かかる紫外線照射は、2~3000mJ/cm2、好ましくは10~2000mJ/cm2の条件で行われる。
また、上記無電極ランプの場合は、例えば、2~2000mJ/cm2、好ましくは10~1000mJ/cm2の条件で行われる。
〔光重合性化合物(A)〕
・(A-1)ジメチルアクリルアミド(KJケミカルズ社製「DMAA」)
・(A-2)アクリロイルモルホリン(KJケミカルズ社製「ACMO」)
・(A-3)エチレングリコールジアクリレート(日立化成社製「FA-222A」)
・(B-1)ホウ酸(和光純薬工業社製)
・(C-1)イオン交換水
・(D-1)下記の合成例により得られる2官能ポリエーテル系ウレタンアクリレート
撹拌機を備えた500ml反応容器に、ジブチル錫ジラウレートを0.3g、重合禁止剤として4-メトキシフェノールを0.2g、ポリテトラメチレングリコール(分子量650)166gを仕込み、これらを撹拌しながら液温が40℃になるまで加温した。
反応溶液に水添ジフェニルメタンジイソシアネート200gを徐々に添加し、1時間かけて60℃まで昇温した。60℃で反応を続けながら遊離NCO%が8.6%になるまで反応を継続した後に、2-ヒドロキシエチルアクリレート134gを添加し、遊離NCO%が0.5%以下になるまで反応を継続し、2官能ポリエーテル系ウレタンアクリレート(D-1)を得た。
得られた2官能ポリエーテル系ウレタンアクリレート(D-1)の重量平均分子量は3,000、粘度12,000mPa・s/60℃であった。
・(E-1)1-ヒドロキシシクロヘキシルフェニルケトン(BASF社製「イルガキュア184」)
・(E-2)2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド(BASF社製「ルシリンTPO」)
<偏光板用接着剤組成物の作製>
調製用フラスコに、予めジメチルアクリルアミド(A-1)85部、ホウ酸(B-1)7部を同時に仕込み、これらを撹拌しながら液温が60℃になるまで加温して、完全にホウ酸(B-1)が溶解するまで1時間混合を続けた。その後、室温まで冷却した後、エチレングリコールジアクリレート(A-3)15部、イオン交換水(C-1)7部、ウレタンアクリレート(D-1)30部、イルガキュア184(E-1)2部、ルシリンTPO(E-2)2部を同時に仕込み、混合することで偏光板用接着剤組成物を得た。
上記で用意した各配合成分を、下記の表1示す割合で配合すること以外は実施例1と同様にして偏光板用接着剤組成物を調製した。
まず、60μのPVAフィルムを、25℃の水槽に浸漬しつつ、1.7倍に延伸した。次にヨウ素0.5g/L、ヨウ化カリウム30g/Lよりなる28℃の水溶液中に浸漬しつつ1.6倍に延伸し、ついでホウ酸40g/L、ヨウ化カリウム30g/Lの組成の水溶液(55℃)に浸漬するとともに、同時に2.1倍に一軸延伸しつつホウ酸処理を行なった。その後、ヨウ化カリウム水溶液で洗浄行い、70℃で乾燥して総延伸倍率6倍の偏光子[F-1]を得た。なお、偏光子[F-1]の水分率は4%であった。また、乾燥温度を90℃にする以外は偏光子[F-1]と同様にして、偏光子[F-2]を得た。なお、偏光子[F-2]の水分率は1%であった。
大きさ200mm×100mm、厚み75μmアクリルフィルム(三菱レイヨン社製、商品名「アクリプレン」)に、上記で得られた偏光板用接着剤組成物をバーコーター(No.10)で膜厚5μmとなるように塗工した接着剤組成物層付きアクリルフィルムを2枚作製した後、大きさ180mm×80mmの上記偏光子[F]の両面に重ね合わせ、ロール機を用いてニップ圧0.3MPaで貼り合わせ、積層フィルムを得た。
次いで、積層フィルムのアクリルフィルム側の両側から、高圧水銀ランプの取り付けられた紫外線照射装置にてピーク照度:130mW/cm2、積算露光量:900mJ/cm2(365nm)で紫外線照射を行ない、接着剤組成物を硬化させて偏光板試験片とした。
上記で得られた偏光板試験片を用いて、下記の通り性能評価を行った。
偏光板試験片を120mm×25mmにカットし、2枚のアクリルフィルムに90°方向の応力をかけた際のアクリルフィルムと偏光子の接着具合を下記基準で評価した。
(評価基準)
◎…強固に接着している
○…接着している
△…弱く接着している
×…接着していない
偏光板試験片を5cm×5cmにカットし、60℃の温水に浸漬させ、48時間後の偏光板試験片の密着性を観察し、下記基準で評価した。
○…試験片端部からの剥がれなし
△…試験片端部から5mm未満の範囲において剥がれあり
×…試験片端部から5mm以上の範囲に剥がれあり
偏光板試験片を5cm×5cmにカットし、60℃の温水に浸漬させ、48時間後の偏光板試験片の色調を観察し、下記基準で評価した。
○…試験前の状況と色調変化なし
△…僅かに色抜け(退色)した
×…完全に色抜け(退色)した
Claims (13)
- 光重合性化合物(A)、第13族の金属および半金属化合物の群から選ばれる少なくとも1種からなるオキソ酸(B)、および水(C)を含有してなることを特徴とする接着剤組成物。
- 光重合性化合物(A)が、プロトン受容性基を含有する光重合性化合物(A1)を含むことを特徴とする請求項1記載の接着剤組成物。
- プロトン受容性基を含有する光重合性化合物(A1)が、下記一般式(1)で表される化合物であることを特徴とする請求項2記載の接着剤組成物。
CH2=C(R1)-CONR2(R3)・・・(1)
(式(1)において、R1は、水素原子またはメチル基を示し、R2は、水素原子または置換基を有してもよい炭素数1~4の直鎖もしくは分岐鎖のアルキル基を示し、R3は、水素原子または炭素数1~4の直鎖または分岐鎖のアルキル基を示し、または、R2とR3は、互いに結合して、酸素原子を含んでもよい5員環または6員環を形成してもよい。ただし、R2とR3は、同時に水素原子である場合を除くものである。) - 第13族の金属および半金属化合物の群から選ばれる少なくとも1種からなるオキソ酸(B)が、ホウ酸であることを特徴とする請求項1~3いずれか一項に記載の接着剤組成物。
- 第13族の金属および半金属化合物の群から選ばれる少なくとも1種からなるオキソ酸(B)の含有量が、光重合性化合物(A)100重量部に対して、0.1~20重量部であることを特徴とする請求項1~4いずれか一項に記載の接着剤組成物。
- 水(C)の含有量が、光重合性化合物(A)100重量部に対して、0.01~30重量部であることを特徴とする請求項1~5いずれか一項に記載の接着剤組成物。
- 第13族の金属および半金属化合物の群から選ばれる少なくとも1種からなるオキソ酸(B)と水(C)の含有割合(B/C)(重量比)が2/8~8/2であることを特徴とする請求項1~6いずれか一項に記載の接着剤組成物。
- ウレタン(メタ)アクリレート系化合物(D)(但し、光重合性化合物(A)を除く。)を含有してなることを特徴とする請求項1~7いずれか一項に記載の接着剤組成物。
- 重合開始剤(E)を含有してなることを特徴とする請求項1~8いずれか一項に記載の接着剤組成物。
- 請求項1~9いずれか一項に記載の接着剤組成物を用いてなることを特徴とする偏光板用接着剤組成物。
- 請求項10記載の偏光板用接着剤組成物を硬化してなることを特徴とする偏光板用接着剤。
- 請求項10記載の偏光板用接着剤組成物を活性エネルギー線照射により硬化してなることを特徴とする偏光板用接着剤。
- 請求項11または12記載の偏光板用接着剤を介して偏光子と保護フィルムが貼り合わされてなることを特徴とする偏光板。
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WO2017090637A1 (ja) * | 2015-11-24 | 2017-06-01 | 日本合成化学工業株式会社 | 接着剤組成物、偏光板用接着剤組成物、及びそれを用いる偏光板 |
JP2018199805A (ja) * | 2017-05-25 | 2018-12-20 | 三洋化成工業株式会社 | 硬化性組成物及び硬化物 |
CN109638169A (zh) * | 2018-10-29 | 2019-04-16 | 纳晶科技股份有限公司 | 有机阻隔膜、有机阻隔膜的制备方法以及量子点器件 |
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