Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
• • 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 a pressure-sensitive adhesive composition for polarizing films, a pressure-sensitive adhesive layer for polarizing films formed from the pressure-sensitive adhesive composition for polarizing films, and a polarizing film with a pressure-sensitive adhesive layer using the pressure-sensitive adhesive layer for polarizing films. Furthermore, the present invention relates to an image display device such as a liquid crystal display device, an organic EL display device, and a PDP using the polarizing film with an adhesive layer.
• the adhesive is a polarizing film with an adhesive layer provided in advance as an adhesive layer on one side of the polarizing film.
• a film is generally used.
• a release film is usually attached to the pressure-sensitive adhesive layer of the polarizing film with a pressure-sensitive adhesive layer.
• the release film is peeled off from the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer. Static electricity is generated.
• the static electricity generated in this way affects the orientation of the liquid crystal inside the liquid crystal display device, leading to defects. For example, if white unevenness occurs during black display due to static electricity during use of a liquid crystal display device, the phenomenon that the white unevenness does not disappear for several minutes occurs and the display characteristics of the screen deteriorate. Had a point. Even after mounting on a television or the like, similar white unevenness may occur due to static electricity generated when the backlight and the polarizing plate rub.
• the generation of static electricity can be suppressed, for example, by forming an antistatic layer on the outer surface of the polarizing film, but the effect is small and there is a problem that the generation of static electricity cannot be fundamentally prevented. Therefore, in order to suppress the occurrence of static electricity at a fundamental position, it is required to provide an antistatic function to the adhesive layer.
• As means for imparting an antistatic function to the pressure-sensitive adhesive layer for example, mixing an ionic compound with the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer has been proposed (for example, see Patent Document 1 or 2).
• Patent Document 1 describes that the use of an ionic liquid or an alkali metal salt as an antistatic agent for the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is excellent in antistatic properties.
• Patent Document 2 describes that an antistatic function and durability can be maintained even after a humidification test under severe conditions by using an alkali metal salt in combination with an onium-anion salt as an ionic compound. .
• Static electricity which has been regarded as a problem in the past, is relatively small.
• white unevenness disappears in a few seconds.
• the conventional pressure-sensitive adhesive layer having an antistatic function cannot sufficiently neutralize the generated charge, and thus white unevenness may not disappear in a short time. In this case, white unevenness is present on the screen, and so-called “white spots” are generated.
• the pressure-sensitive adhesive composition containing the ionic compound described in Patent Documents 1 and 2 since the addition amount of the ionic compound and the alkali metal salt is not sufficiently controlled, white spots are generated when the generated static electricity is large. In some cases, there is room for further study in terms of the antistatic function.
• the present invention can eliminate the generated white unevenness in a short time even when large static electricity is generated, can satisfy the durability even after a heating and humidification test under severe conditions, and It aims at providing the adhesive composition for polarizing films which can form the adhesive layer which has the outstanding external appearance. Moreover, this invention provides the adhesive layer formed from the said adhesive composition, the polarizing film with an adhesive layer using the said adhesive layer, and the image display apparatus using the said polarizing film with an adhesive layer. Also aimed.
• the present invention contains a (meth) acrylic polymer (A), an onium-anion salt (B1), an alkali metal salt (B2),
• the alkali metal salt (B2) is contained in an amount of 0.4 to 3.5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer (A).
• the present invention relates to a pressure-sensitive adhesive composition for a polarizing film, wherein the weight ratio (B2 / B1) of the alkali metal salt (B2) to the onium-anion salt (B1) is 1.2 to 4.
• the pressure-sensitive adhesive composition for polarizing film of the present invention further contains a thiol-based silane coupling agent (C1).
• the thiol-based silane coupling agent (C1) is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer (A).
• the onium-anion salt (B1) is preferably 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer (A).
• the pressure-sensitive adhesive composition for polarizing film of the present invention further contains a crosslinking agent (D).
• the cross-linking agent (D) is preferably contained in an amount of 0.01 to 20 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer (A).
• the cross-linking agent (D) is preferably at least one cross-linking agent selected from the group consisting of isocyanate compounds and peroxides.
• the pressure-sensitive adhesive composition for polarizing film of the present invention further contains an acetoacetyl group-containing silane coupling agent (C2).
• the present invention also relates to a pressure-sensitive adhesive layer for polarizing film, which is formed from the pressure-sensitive adhesive composition for polarizing film.
• the present invention is a polarizing film and a polarizing film with an adhesive layer having an adhesive layer provided on the polarizing film
• the polarizing film has a transparent protective film only on one side of the polarizer, the pressure-sensitive adhesive layer is provided on the surface of the polarizer that does not have the transparent protective film, and
• the pressure-sensitive adhesive layer is the pressure-sensitive adhesive layer for a polarizing film, and relates to a polarizing film with a pressure-sensitive adhesive layer.
• the thickness of the polarizer is 10 ⁇ m or less.
• the present invention relates to an image display device using at least one polarizing film with an adhesive layer.
• the pressure-sensitive adhesive composition for a polarizing film of the present invention contains a (meth) acrylic polymer (A), an onium-anion salt (B1), and an alkali metal salt (B2), and the onium-anion salt (B1). ) And alkali metal salt (B2) added in a specific range, even when large static electricity is generated, the generated white unevenness can be eliminated in a short time, and heating under severe conditions Even after the humidification test, durability can be satisfied, and a pressure-sensitive adhesive layer having an excellent appearance can be formed.
• the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition for polarizing film of the present invention and the polarizing film with the pressure-sensitive adhesive layer containing the pressure-sensitive adhesive layer satisfy an excellent antistatic function and durability.
• the image display apparatus which has a polarizing film with an adhesive layer of this invention can suppress generation
• the pressure-sensitive adhesive composition for polarizing film of the present invention comprises a (meth) acrylic polymer (A), an onium-anion salt (B1), and an alkali metal salt (B2).
• the alkali metal salt (B2) is contained in an amount of 0.4 to 3.5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer (A).
• the weight ratio (B2 / B1) of the alkali metal salt (B2) to the onium-anion salt (B1) is 1.2 to 4.
• the pressure-sensitive adhesive composition for polarizing film of the present invention contains a (meth) acrylic polymer (A) as a base polymer.
• the (meth) acrylic polymer (A) usually contains an alkyl (meth) acrylate as a main component as a monomer unit.
• (Meth) acrylate refers to acrylate and / or methacrylate, and (meth) of the present invention has the same meaning.
• alkyl (meth) acrylate constituting the main skeleton of the (meth) acrylic polymer (A) include those having a linear or branched alkyl group having 1 to 18 carbon atoms.
• the alkyl group includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, hexyl group, cyclohexyl group, heptyl group, 2-ethylhexyl group, isooctyl group, nonyl group, decyl group.
• isodecyl group isodecyl group, dodecyl group, isomyristyl group, lauryl group, tridecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like. These can be used alone or in combination.
• the alkyl (meth) acrylate is a main component in all monomers constituting the (meth) acrylic polymer (A).
• the main component means that the alkyl (meth) acrylate is about 80 to 100% by weight in all monomers constituting the (meth) acrylic polymer (A), and about 85 to 99.9% by weight. It is preferably about 90 to 99.9% by weight.
• the (meth) acrylic polymer (A) has a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group for the purpose of improving adhesiveness and heat resistance.
• One or more copolymerization monomers can be introduced by copolymerization.
• copolymerizable monomers include, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid 6 Hydroxyl-containing monomers such as hydroxyhexyl, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate and (4-hydroxymethylcyclohexyl) -methyl acrylate Carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid; acid anhydrides such as maleic anhydride and itaconic anhydride Monomer-containing monomer; acrylic Caprolactone adduct of phosphoric acid; styrene
• (N-substituted) amides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, etc.
• Monomer (meth) acrylic acid aminoethyl, (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid t-butylaminoethyl, etc.
• (meth) acrylic alkylaminoalkyl monomers examples include itaconimide monomers such as imide, N-butyl itaconimide, N-octyl it
• Further modifying monomers include vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholine, N Vinyl monomers such as vinylcarboxylic acid amides, styrene, ⁇ -methylstyrene, N-vinylcaprolactam; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; (Meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, (meth) acrylic acid methoxy Glycol acrylic ester monomers such as propylene glycol; acrylic ester monomers such as tetrahydrofurfuryl (me
• examples of copolymerizable monomers other than the above include silane-based monomers containing silicon atoms.
• examples of the silane monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, and 8-vinyloctyltrimethoxysilane.
• copolymer monomers examples include tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate (Meth) acryloyl such as esterified product of (meth) acrylic acid and polyhydric alcohol such as caprolactone-modified dipentaerythritol hexa (meth) acrylate Groups such as polyfunctional
• polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, or the like to which two or more saturated double bonds have been added can also be used.
• the proportion of the copolymerization monomer is not particularly limited, but is about 0 to 20% by weight, preferably about 0.1 to 15% by weight, based on the total monomers constituting the (meth) acrylic polymer (A). About 1 to 10% by weight is more preferable.
• hydroxyl group-containing monomers and carboxyl group-containing monomers are preferably used from the viewpoint of adhesion and durability.
• a hydroxyl group-containing monomer and a carboxyl group-containing monomer can be used in combination.
• These copolymerization monomers serve as reaction points with the crosslinking agent when the pressure-sensitive adhesive composition contains a crosslinking agent. Since a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and the like are rich in reactivity with an intermolecular crosslinking agent, they are preferably used for improving the cohesiveness and heat resistance of the resulting pressure-sensitive adhesive layer.
• the proportion is preferably 0.01 to 15% by weight, more preferably 0.03 to 10% by weight, and further preferably 0.05 to 7% by weight.
• the proportion thereof is preferably 10% by weight or less, more preferably 0.05 to 10% by weight, further preferably 0.1 to 8% by weight, ⁇ 6% by weight is particularly preferred.
• the (meth) acrylic polymer (A) of the present invention usually has a weight average molecular weight in the range of 500,000 to 3,000,000. In view of durability, particularly heat resistance, it is preferable to use those having a weight average molecular weight of 700,000 to 2,700,000. Further, it is preferably 800,000 to 2.5 million. A weight average molecular weight of less than 500,000 is not preferable in terms of heat resistance. On the other hand, if the weight average molecular weight is more than 3 million, a large amount of dilution solvent is required to adjust the viscosity for coating, which is not preferable.
• the weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
• the production of such a (meth) acrylic polymer (A) can be appropriately selected from known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations. Further, the obtained (meth) acrylic polymer (A) may be a random copolymer, a block copolymer, a graft copolymer, or the like.
• solution polymerization for example, ethyl acetate, toluene or the like is used as a polymerization solvent.
• the reaction is carried out in an inert gas stream such as nitrogen and a polymerization initiator is added, and the reaction is usually performed at about 50 to 70 ° C. under reaction conditions for about 5 to 30 hours.
• the polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited and can be appropriately selected and used.
• the weight average molecular weight of the (meth) acrylic polymer (A) can be controlled by the amount of polymerization initiator, the amount of chain transfer agent used, and the reaction conditions, and the amount used is appropriately adjusted according to these types.
• polymerization initiator examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2 -Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine), 2,2 Azo initiators such as' -azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (trade name: VA-057, manufactured by Wako Pure Chemical Industries, Ltd.), potassium persulfate, Persulfates such as ammonium sulfate, di (2-ethylhexyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, di-se -Butylperoxydicarbon
• the polymerization initiator may be used singly or as a mixture of two or more, but the total content is 0.005 to 1 part by weight with respect to 100 parts by weight of the monomer. Is preferably about 0.02 to 0.5 parts by weight.
• the amount of the polymerization initiator used Is preferably about 0.06 to 0.2 parts by weight, and more preferably about 0.08 to 0.175 parts by weight with respect to 100 parts by weight of the total amount of monomer components.
• Onium-anion salt (B1) The onium-anion salt (B1) relates to an “ionic compound” and is also called an ionic liquid or an ionic solid.
• the onium-anion salt (B1) relates to a cation-anion salt composed of a cation component and an anion component.
• onium-anion salts in which the cation is onium are used.
• ⁇ Anion component examples include Cl ⁇ , Br ⁇ , I ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , BF 4 ⁇ , PF 6 ⁇ , ClO 4 ⁇ , NO 3 ⁇ , CH 3 COO ⁇ , CF 3 COO.
• fluorine-containing imide anion examples include an imide anion having a perfluoroalkyl group.
• the fluorine-containing imide anion include an imide anion having a perfluoroalkyl group.
• (CF 3 SO 2 ) (CF 3 CO) N ⁇ examples include the general formulas (1), (2), (4), (1): (C n F 2n + 1 SO 2 ) 2 N ⁇ (where n is an integer of 1 to 10), (2): CF 2 (C m F 2m SO 2 ) 2 N ⁇ (where m is an integer of 1 to 10), (4) :( C p F 2p + 1 SO 2) N - (C q F 2q + 1 SO 2), ( where, p, q is an integer of 1 to 10), in represented by those such as are used.
• fluorine-containing imide anions are preferably used because an ionic compound having a good ion dissociation property can be obtained.
• the fluorine-containing imide anion having a fluorinated alkyl group or fluorinated alkylene group having 1 to 4 carbon atoms is preferable in terms of controlling the surface resistance value and suppressing static electricity unevenness.
• the fluorine-containing imide anion is preferably (perfluoroalkylsulfonyl) imide represented by the general formula (1) such as (CF 3 SO 2 ) 2 N ⁇ , (C 2 F 5 SO 2 ) 2 N ⁇ , and the like.
• (trifluoromethanesulfonyl) imide represented by (CF 3 SO 2 ) 2 N ⁇ is preferable.
• the onium constituting the cation moiety in the onium-anion salt (B1) is one in which atoms that become onium ions are protonated.
• the onium of the present invention is preferably one in which an onium salt is not formed by an unsaturated bond such as a double bond or a triple bond. That is, the onium of the present invention is preferably an organic onium having an onium ion formed by substitution with an organic group or the like.
• examples of the organic group in the organic onium include an alkyl group, an alkoxyl group, and an alkenyl group. Among these, those having no unsaturated bond are preferable.
• the number of carbon atoms of the alkyl group can be selected, for example, from 1 to 12, but is preferably 1 to 8, and more preferably 1 to 4.
• all the substituents are preferably alkyl oniums having an alkyl group having 1 to 4 carbon atoms.
• the alkyl group can be linear or branched, but is preferably linear.
• the organic onium has a cyclic structure, the onium preferably has a 5-membered or 6-membered ring, and the other substituent is preferably an alkyl group having 1 to 4 carbon atoms.
• the onium is not particularly limited, and examples thereof include nitrogen-containing onium, sulfur-containing onium, and phosphorus-containing onium. Among these, nitrogen-containing onium and sulfur-containing onium are preferable.
• nitrogen-containing onium ammonium cation, piperidinium cation, pyrrolidinium cation, pyridinium cation, cation having pyrroline skeleton, cation having pyrrole skeleton, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation
• Examples include pyrazolium cation and pyrazolinium cation.
• ammonium cation, piperidinium cation, and pyrrolidinium cation are preferable, and pyrrolidinium is particularly preferable.
• tetraalkylammonium cations, alkylpiperidinium cations, and alkylpyrrolidinium cations are preferable.
• sulfur-containing onium examples include a sulfonium cation.
• phosphorus-containing phosphonium examples include phosphonium cations.
• the onium-anion salt (B1) a compound composed of a combination of the onium component and the anion component is appropriately selected and used.
• an onium-fluorine-containing imide anion salt in which the anion is a fluorine-containing imide anion is preferable.
• the onium-fluorine-containing imide anion salt a compound comprising a combination of the onium component and the fluorine-containing imide anion component is appropriately selected and used. Any one selected from the above is preferably used. Furthermore, at least one selected from ammonium salts, pyrrolidinium salts, piperidinium salts and sulfonium salts is preferably used.
• 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) Imido, 1-ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) imide, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1,2-dimethyl-3-propylimidazolium bis ( Trifluoromethanesulfonyl) imide, tetrahexylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethyl
• CIL-314 manufactured by Nippon Carlit Co., Ltd.
• ILA2-1 manufactured by Guangei Chemical Industry Co., Ltd.
• tetramethylammonium bis (trifluoromethanesulfonyl) imide trimethylethylammonium bis (trifluoromethanesulfonyl) imide, trimethylbutylammonium bis (trifluoromethanesulfonyl) imide, trimethylpentylammonium bis (trifluoromethanesulfonyl) imide, trimethylheptyl Ammonium bis (trifluoromethanesulfonyl) imide, trimethyloctylammonium bis (trifluoromethanesulfonyl) imide, tetraethylammonium bis (trifluoromethanesulfonyl) imide, triethylbutylammonium bis (trifluoromethanesulfonyl) imide, tetrabutylammonium bis (trifluoromethanesulfonyl) Imide, te
• 1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethane) Sulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium Bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl
• bis (trifluoromethanesulfonyl) imide bis (pentafluorosulfonyl) imide, bis (heptafluoropropanesulfonyl) imide, bis (nonafluorobutanesulfonyl) imide, trifluoromethanesulfonyl nonafluorobutanesulfonylimide, And compounds using heptafluoropropanesulfonyl trifluoromethanesulfonylimide, pentafluoroethanesulfonylnonafluorobutanesulfonylimide, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide anion, and the like.
• onium-anion salt (B1) other than the onium-fluorine-containing imide anion salt a compound comprising a combination of the above onium component and an anion component other than the fluorine-containing imide anion salt is appropriately selected and used.
• the onium-anion salt (B1) may be used alone or in combination of two or more.
• 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide is preferred.
• the ratio of the onium-anion salt (B1) in the pressure-sensitive adhesive composition of the present invention is preferably 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer (A). If the onium-anion salt (B1) is less than 0.1 part by weight, the effect of improving the antistatic performance may not be sufficient.
• the onium-anion salt (B1) is preferably 0.2 parts by weight or more, and more preferably 0.5 parts by weight or more. On the other hand, if the amount of the onium-anion salt (B1) is more than 1.5 parts by weight, durability and appearance may not be sufficient.
• the onium-anion salt (B1) is preferably 1.3 parts by weight or less, more preferably 1.0 part by weight or less, and still more preferably less than 1.0 part by weight.
• the ratio of the onium-anion salt (B1) can be set within a preferable range by adopting the upper limit value or the lower limit value.
• those which are solid and have a large molecule such as 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide have an addition amount of more than 1.5 parts by weight. Then, crystallization occurs in the pressure-sensitive adhesive, and appearance defects may occur, which is not particularly preferable.
• Alkali metal salt (B2) As the alkali metal salt (B2), alkali metal organic salts and inorganic salts can be used.
• alkali metal ions constituting the cation part of the alkali metal salt (B2) include lithium, sodium and potassium ions. Of these alkali metal ions, lithium ions are preferred.
• the anion part of the alkali metal salt may be composed of an organic material or an inorganic material.
• Examples of the anion part constituting the organic salt include CH 3 COO ⁇ , CF 3 COO ⁇ , CH 3 SO 3 ⁇ , CF 3 SO 3 ⁇ , (CF 3 SO 2 ) 3 C ⁇ , and C 4 F 9 SO 3.
• an anion moiety containing a fluorine atom is preferably used because an ionic compound having good ion dissociation properties can be obtained.
• the anion part constituting the inorganic salt includes Cl ⁇ , Br ⁇ , I ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , BF 4 ⁇ , PF 6 ⁇ , ClO 4 ⁇ , NO 3 ⁇ , AsF 6 ⁇ , SbF. 6 ⁇ , NbF 6 ⁇ , TaF 6 ⁇ , (CN) 2 N ⁇ , and the like are used.
• (perfluoroalkylsulfonyl) imide represented by the general formula (1) such as (CF 3 SO 2 ) 2 N ⁇ , (C 2 F 5 SO 2 ) 2 N ⁇ , etc. is preferable, (Trifluoromethanesulfonyl) imide represented by CF 3 SO 2 ) 2 N ⁇ is preferable.
• alkali metal organic salt examples include sodium acetate, sodium alginate, sodium lignin sulfonate, sodium toluene sulfonate, LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, Li (C 2 F 5 SO 2) 2 N, Li ( C 4 F 9 SO 2) 2 N, Li (CF 3 SO 2) 3 C, KO 3 S (CF 2) 3 SO 3 K, LiO 3 S (CF 2) 3 SO 3 K and the like.
• LiCF 3 SO 3 Li (CF 3 SO 2 ) 2 N, Li (C 2 F 5 SO 2 ) 2 N, Li (C 4 F 9 SO 2 ) 2 N, Li ( CF 3 SO 2) 3 C and the like are preferable, Li (CF 3 SO 2) 2 N, Li (C 2 F 5 SO 2) 2 N, Li (C 4 F 9 SO 2) fluorine-containing lithium imide such as 2 N It is more preferable, especially (perfluoroalkyl sulfonyl) imide lithium salts are preferred.
• examples of the alkali metal inorganic salt include lithium perchlorate and lithium iodide.
• the alkali metal salt (B2) can be used singly or in combination of two or more.
• the proportion of the alkali metal salt (B2) in the pressure-sensitive adhesive composition of the present invention is 0.4 to 3.5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer (A).
• the alkali metal salt (B2) is less than 0.4 part by weight, the surface resistance value of the pressure-sensitive adhesive layer surface formed from the pressure-sensitive adhesive composition of the present invention increases, and as a result, white unevenness may occur. there were.
• the said alkali metal salt (B2) 0.5 weight part or more is more preferable.
• the amount of the alkali metal salt (B2) is more than 3.5 parts by weight, the effect of improving the antistatic performance after a humid test under severe conditions is not sufficient.
• the alkali metal salt (B2) is preferably 3.0 parts by weight or less, and more preferably 2.0 parts by weight or less.
• the ratio of the said alkali metal salt (B2) can employ
• the weight ratio (B2 / B1) of the alkali metal salt (B2) to the onium-anion salt (B1) is 1.2 to 4, preferably 1.2 to 3.5. More preferably, it is 2 to 3.0.
• the weight ratio (B2 / B1) is less than 1.2, a high level of conductive performance cannot be obtained.
• the weight ratio (B2 / B1) exceeds 4 the appearance deteriorates due to the precipitation of the alkali metal salt and the moisture resistance. Deterioration of performance during testing tends to occur.
• the pressure-sensitive adhesive composition for polarizing film of the present invention preferably contains a thiol-based silane coupling agent (C1). Since the thiol-based silane coupling agent (C1) hardly affects the conductive performance, the durability of adhesion to the adherend can be improved without impairing the conductive performance of the pressure-sensitive adhesive layer. Therefore, white unevenness can be suppressed even when a large amount of static electricity that cannot be eliminated by the conventional antistatic pressure-sensitive adhesive composition is generated.
• the thiol-based silane coupling agent (C1) may be any one having a siloxane skeleton and a mercapto group, for example, X-41-1810 (trade name, mercapto equivalent: 450 g / mol), X-41- 1805 (trade name, mercapto equivalent: 800 g / mol), X-41-1818 (trade name, mercapto equivalent: 850 g / mol) (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. These can be used alone or in admixture of two or more. Among these, X-41-1810 is preferable from the viewpoint that it is possible to rework from the adherend while suppressing an abrupt increase in the adhesive strength of the pressure-sensitive adhesive layer.
• the thiol group content of the thiol-based silane coupling agent (C1) is preferably 1000 g / mol or less, more preferably 850 g / mol or less, and rapid adhesion. It is more preferably 650 g / mol or less from the viewpoint that it is possible to suppress the increase in force and rework from the adherend.
• the lower limit value of the mercapto equivalent is not particularly limited, but for example, it is preferably 100 g / mol or more.
• the ratio of the thiol-based silane coupling agent (C1) in the pressure-sensitive adhesive composition of the present invention is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer (A).
• the thiol-based silane coupling agent (C1) is less than 0.001 part by weight, it may be difficult to improve the reliability of the surface of the transparent conductive layer such as glass and ITO.
• the thiol-based silane coupling agent (C1) is preferably 0.01 parts by weight or more, and more preferably 0.1 parts by weight or more.
• the thiol-based silane coupling agent (C1) is preferably 4 parts by weight or less, preferably 3 parts by weight or less, preferably 2.5 parts by weight or less, and more preferably 2 parts by weight or less.
• the ratio of the thiol-based silane coupling agent (C1) can be set within a preferable range by adopting the upper limit value or the lower limit value.
• the pressure-sensitive adhesive composition of the present invention can contain a crosslinking agent (D).
• a crosslinking agent (D) an organic crosslinking agent or a polyfunctional metal chelate can be used.
• the organic crosslinking agent include an isocyanate crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent, and an imine crosslinking agent.
• a polyfunctional metal chelate is one in which a polyvalent metal is covalently or coordinately bonded to an organic compound.
• Examples of polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. Can be mentioned.
• Examples of the atom in the organic compound to be covalently bonded or coordinated include an oxygen atom, and examples of the organic compound include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, and ketone compounds.
• crosslinking agent (D) one or more kinds of crosslinking agents selected from the group consisting of isocyanate crosslinking agents and peroxide crosslinking agents are preferred, and an isocyanate crosslinking agent and a peroxide crosslinking agent are used in combination. More preferably, it is used.
• the compound related to the isocyanate-based crosslinking agent include isocyanate monomers such as tolylene diisocyanate, chlorophenylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and these isocyanate monomers.
• Examples include isocyanate compounds added with trimethylolpropane, isocyanurates, burette compounds, and urethane prepolymer type isocyanates such as polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, etc. be able to.
• a polyisocyanate compound which is one or a polyisocyanate compound derived from one selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate.
• examples include hexamethylene diisocyanate, polyol-modified hydrogenated xylylene diisocyanate, trimer-type hydrogenated xylylene diisocyanate, and polyol-modified isophorone diisocyanate.
• the exemplified polyisocyanate compound is particularly preferable because the reaction with a hydroxyl group proceeds rapidly, particularly using an acid or base contained in the polymer as a catalyst, thus contributing to the speed of crosslinking.
• any radical active species can be used as long as it generates radical active species by heating or light irradiation to advance the crosslinking of the base polymer of the pressure-sensitive adhesive composition, but in consideration of workability and stability. It is preferable to use a peroxide having a one-minute half-life temperature of 80 ° C. to 160 ° C., more preferably a peroxide having a 90 ° C. to 140 ° C.
• peroxides examples include di (2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6 ° C.), di (4-t-butylcyclohexyl) peroxydicarbonate (1 Minute half-life temperature: 92.1 ° C.), di-sec-butyl peroxydicarbonate (1 minute half-life temperature: 92.4 ° C.), t-butyl peroxyneodecanoate (1 minute half-life temperature: 103 0.5 ° C.), t-hexyl peroxypivalate (1 minute half-life temperature: 109.1 ° C.), t-butyl peroxypivalate (1 minute half-life temperature: 110.3 ° C.), dilauroyl peroxide ( 1 minute half-life temperature: 116.4 ° C.), di-n-octanoyl peroxide (1 minute half-life temperature: 117.4 ° C.), 1,1,3,3-tetramethylbutyl
• di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 ° C.)
• dilauroyl peroxide (1 minute half-life temperature: 116. 4 ° C.
• dibenzoyl peroxide (1 minute half-life temperature: 130.0 ° C.) and the like are preferably used.
• the peroxide half-life is an index representing the decomposition rate of the peroxide, and means the time until the remaining amount of peroxide is reduced to half.
• the decomposition temperature for obtaining a half-life at an arbitrary time and the half-life time at an arbitrary temperature are described in the manufacturer catalog, for example, “Nippon Yushi Co., Ltd.“ Organic Peroxide Catalog 9th Edition ” ( May 2003) ".
• the amount of the crosslinking agent (D) used is preferably 0.01 to 20 parts by weight, more preferably 0.03 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer (A). If the crosslinking agent (D) is less than 0.01 parts by weight, the cohesive force of the pressure-sensitive adhesive tends to be insufficient, and foaming may occur during heating. On the other hand, if it exceeds 20 parts by weight, the moisture resistance is sufficient. Instead, peeling easily occurs in a reliability test or the like.
• the isocyanate-based crosslinking agent may be used singly or as a mixture of two or more, but the total content thereof is the (meth) acrylic polymer (A) 100
• the isocyanate-based crosslinking agent is contained in an amount of 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, and 0.05 to 1.5 parts by weight with respect to parts by weight. It is more preferable to contain a part. It can be appropriately contained in consideration of cohesive force, prevention of peeling in a durability test, and the like.
• the peroxide may be used alone or as a mixture of two or more, but the total content is 100 weight of the (meth) acrylic polymer (A).
• the peroxide is 0.01 to 2 parts by weight, preferably 0.04 to 1.5 parts by weight, and more preferably 0.05 to 1 part by weight. . In order to adjust processability, reworkability, cross-linking stability, peelability, etc., it is appropriately selected within this range.
• the peroxide decomposition amount remaining after the reaction treatment for example, it can be measured by HPLC (High Performance Liquid Chromatography).
• the pressure-sensitive adhesive composition after the reaction treatment is taken out, immersed in 10 ml of ethyl acetate, extracted by shaking at 25 ° C. and 120 rpm for 3 hours with a shaker, and then at room temperature. Leave for 3 days. Next, 10 ml of acetonitrile was added, shaken at 120 rpm at 25 ° C. for 30 minutes, and about 10 ⁇ l of the extract obtained by filtration through a membrane filter (0.45 ⁇ m) was injected into the HPLC for analysis. The amount of peroxide can be set.
• the pressure-sensitive adhesive composition of the present invention preferably contains an acetoacetyl group-containing silane coupling agent (C2) from the viewpoint of improving durability.
• the acetoacetyl group-containing silane coupling agent (C2) include A-100 (trade name) manufactured by Soken Chemical Co., Ltd.
• the silane coupling agent (C2) may be used alone or as a mixture of two or more, but the total content is the (meth) acrylic polymer (A) 100.
• the amount of the silane coupling agent (C2) is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight, still more preferably 0.02 to 1 part by weight, based on parts by weight. 0.05 to 0.6 parts by weight are preferred. It is an amount that improves the durability and appropriately maintains the adhesive force to the polarizing film.
• the ratio of the silane coupling agent (C2) to the thiol-based silane coupling agent (C1) is not particularly limited, but the weight ratio of (C2) / (C1) is about 0.1 to 2 It is preferably about 0.1 to 1, more preferably about 0.2 to 0.6.
• the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention is adhered to the adherend when the mixing ratio of the silane coupling agent (C2) and the thiol-based silane coupling agent (C1) is in the above range. It is preferable that the adhesive layer can be reworked from the adherend at the initial stage of application, and further, the adhesive strength durability over time can be imparted.
• the pressure-sensitive adhesive composition of the present invention can also contain a silane coupling agent other than the thiol-based silane coupling agent (C1) and the acetoacetyl group-containing silane coupling agent (C2).
• Epoxy group-containing silane cups such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Ring agent, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N- Amino group-containing sila such as phenyl- ⁇ -aminopropyltrimethoxysilane Co
• addition amounts are not particularly limited, and can be added within a range not impairing the effects of the present invention.
• the amount is preferably less than part, and in the present invention, it is preferably not added.
• the pressure-sensitive adhesive composition of the present invention may contain other known additives such as a polyether compound of polyalkylene glycol such as polypropylene glycol, a colorant, a powder such as a pigment, a dye, Surfactant, plasticizer, tackifier, surface lubricant, leveling agent, softener, antioxidant, anti-aging agent, light stabilizer, UV absorber, polymerization inhibitor, inorganic or organic filler, metal It can be added as appropriate according to the intended use of powder, particles, foils and the like. Moreover, you may employ
• the pressure-sensitive adhesive layer for polarizing film is formed from the pressure-sensitive adhesive composition for polarizing film.
• Examples of the method for forming the pressure-sensitive adhesive layer include a method in which the pressure-sensitive adhesive composition is applied to a release-treated separator and the like, and the polymerization solvent is dried and removed to form the pressure-sensitive adhesive layer. Moreover, it can also produce by the method etc. which apply
• a silicone release liner is preferably used as the release-treated separator.
• an appropriate method can be adopted as a method for drying the pressure-sensitive adhesive depending on the purpose.
• a method of heating and drying the coating film is used.
• the heating and drying temperature is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 180 ° C, and particularly preferably 70 ° C to 170 ° C. By setting the heating temperature within the above range, an adhesive having excellent adhesive properties can be obtained.
• the drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.
• Various methods are used as a method for applying the pressure-sensitive adhesive composition. Specifically, for example, by roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.
• the thickness of the pressure-sensitive adhesive layer is not particularly limited, and is, for example, about 1 to 100 ⁇ m.
• the thickness is preferably 2 to 50 ⁇ m, more preferably 2 to 40 ⁇ m, and still more preferably 5 to 35 ⁇ m.
• Polarizing film with pressure-sensitive adhesive layer has a polarizing film and a pressure-sensitive adhesive layer provided on the polarizing film,
• the polarizing film has a transparent protective film only on one side of the polarizer, the pressure-sensitive adhesive layer is provided on the surface of the polarizer that does not have the transparent protective film, and
• the pressure-sensitive adhesive layer is the pressure-sensitive adhesive layer for polarizing film of the present invention.
• the method for forming the pressure-sensitive adhesive layer is as described above.
• the pressure-sensitive adhesive layer on the separator is transferred to a surface of the polarizing film that does not have a transparent protective film. Can be formed. Moreover, it is produced also by the method of apply
• an anchor layer was formed on the surface of the polarizing film on which the pressure-sensitive adhesive composition was applied (the surface having no transparent protective film of the polarizing film), and various easy adhesion treatments such as corona treatment and plasma treatment were performed.
• a pressure-sensitive adhesive layer can be formed later. Moreover, you may perform an easily bonding process on the surface of an adhesive layer.
• the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer When the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a sheet (separator) that has been subjected to a release treatment until practical use.
• constituent material of the separator examples include, for example, plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof.
• plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films
• porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof.
• a plastic film is used suitably from the point which is excellent in surface smoothness.
• the plastic film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer.
• a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, and a vinyl chloride co-polymer are used.
• examples thereof include a polymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
• the thickness of the separator is usually about 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
• silicone type, fluorine type, long chain alkyl type or fatty acid amide type release agent, release by a silica powder and antifouling treatment, coating type, kneading type, vapor deposition type, if necessary It is also possible to perform antistatic treatment such as.
• the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, and fluorine treatment on the surface of the separator.
• seat which carried out the peeling process used in preparation of said polarizing film with an adhesive layer can be used as a separator of the polarizing film with an adhesive layer as it is, and can simplify in the surface of a process.
• a polarizing film having a transparent protective film only on one side of the polarizer is used.
• the polarizer is not particularly limited, and various types can be used.
• polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
• hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
• polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products.
• a polarizer composed of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable, and an iodine polarizer containing iodine and / or iodine ions is more preferable.
• the thickness of these polarizers is not particularly limited, but is generally about 5 to 80 ⁇ m.
• a polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing.
• Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching.
• the film can be stretched even in an aqueous solution such as boric acid or potassium iodide or in a water bath.
• a thin polarizer having a thickness of 10 ⁇ m or less can also be used.
• the thickness is preferably 1 to 7 ⁇ m.
• Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing film can be reduced.
• the thin polarizer typically, JP-A-51-069644, JP-A-2000-338329, WO2010 / 100917, WO2010 / 100917, or a patent.
• the thin polarizing film described in the specification of 4751481 and Unexamined-Japanese-Patent No. 2012-0753563 can be mentioned.
• These thin polarizing films can be obtained by a production method including a step of stretching and dyeing a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin substrate in the state of a laminate. With this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.
• PVA-based resin polyvinyl alcohol-based resin
• International Publication No. 2010/100917 pamphlet in that it can be stretched at a high magnification and the polarization performance can be improved among the production methods including the step of stretching in the state of a laminate and the step of dyeing.
• those obtained by a production method including a step of stretching in a boric acid aqueous solution as described in International Publication No. 2010/100917 pamphlet, or Japanese Patent No. 47514881 and Japanese Patent Application Laid-Open No. 2012-0753563 are preferable.
• Those obtained by a production method including a step of stretching in the air before stretching in a boric acid aqueous solution described in the specification of 4751481 and Japanese Patent Application Laid-Open No. 2012-0753563 are preferable.
• thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is used.
• thermoplastic resins include cellulose resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, cyclic Examples thereof include polyolefin resins (norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof.
• One or more kinds of arbitrary appropriate additives may be contained in the transparent protective film.
• the additive examples include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, a coloring inhibitor, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent.
• the content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. .
• content of the said thermoplastic resin in a transparent protective film is 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.
• a transparent protective film is bonded to one side of the polarizer by an adhesive layer.
• An adhesive is used for the adhesion treatment between the polarizer and the transparent protective film.
• the adhesive include isocyanate adhesives, polyvinyl alcohol adhesives, gelatin adhesives, vinyl latexes, and water-based polyesters.
• the adhesive is usually used as an adhesive made of an aqueous solution, and usually contains 0.5 to 60% by weight of a solid content.
• examples of the adhesive between the polarizer and the transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive.
• the electron beam curable polarizing film adhesive exhibits suitable adhesiveness to the various transparent protective films.
• the adhesive used in the present invention can contain a metal compound filler.
• the present invention relates to an image display device using at least one polarizing film with an adhesive layer.
• the polarizing film with an adhesive layer of the present invention can be preferably used for forming various image display devices such as a liquid crystal display device.
• the liquid crystal display device can be formed according to the conventional method.
• a liquid crystal display device is generally formed by appropriately assembling components such as a display panel such as a liquid crystal cell, a polarizing film with an adhesive layer, and an illumination system as necessary, and incorporating a drive circuit.
• a display panel such as a liquid crystal cell
• a polarizing film with an adhesive layer such as a liquid crystal cell
• an illumination system as necessary
• an arbitrary type such as an arbitrary type such as a TN type, STN type, ⁇ type, VA type, or IPS type can be used.
• liquid crystal display devices such as a liquid crystal display device in which a polarizing film with an adhesive layer is disposed on one or both sides of a display panel such as a liquid crystal cell, or a lighting system using a backlight or a reflecting plate can be formed.
• the polarizing film with an adhesive layer by this invention can be installed in the one side or both sides of display panels, such as a liquid crystal cell.
• optical films are provided on both sides, they may be the same or different.
• a liquid crystal display device for example, a single layer or a suitable layer of suitable components such as a diffusion layer, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusion sheet, and a backlight, Two or more layers can be arranged.
• suitable components such as a diffusion layer, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusion sheet, and a backlight.
• Production Example 1 (Preparation of acrylic polymer (A-1)) A monomer mixture containing 99 parts of butyl acrylate and 1 part of 4-hydroxybutyl acrylate was charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser. Furthermore, 0.1 part of 2,2′-azobisisobutyronitrile as a polymerization initiator was charged with ethyl acetate to 100 parts of the monomer mixture (solid content), and nitrogen gas was introduced while gently stirring. Then, the temperature of the liquid in the flask was kept at around 60 ° C., and a polymerization reaction was carried out for 7 hours. Thereafter, ethyl acetate was added to the obtained reaction solution to prepare a solution of an acrylic polymer (A-1) having a weight average molecular weight of 1,400,000 adjusted to a solid content concentration of 30%.
• the weight average molecular weight of the obtained (meth) acrylic polymer (A) was measured by the following method. ⁇ Measurement of weight average molecular weight of (meth) acrylic polymer (A)> The weight average molecular weight of the (meth) acrylic polymer (A) was measured by GPC (gel permeation chromatography).
• Production Example 2 (Production of thin polarizing film)
• a laminated body in which a 9 ⁇ m-thick PVA layer is formed on an amorphous PET base material is produced by air-assisted stretching at a stretching temperature of 130 ° C., and then stretched.
• a colored laminate is produced by dyeing the laminate, and the colored laminate is further stretched integrally with an amorphous PET substrate so that the total draw ratio is 5.94 times by stretching in boric acid water at a stretching temperature of 65 ° C.
• An optical film laminate including a 4 ⁇ m thick PVA layer was produced.
• the PVA molecules in the PVA layer formed on the amorphous PET substrate by such two-stage stretching are oriented in the higher order, and the iodine adsorbed by the dyeing is oriented in the one direction as the polyiodine ion complex. It was possible to produce an optical film laminate including a PVA layer having a thickness of 4 ⁇ m, which constitutes a highly functional polarizing layer. Furthermore, after applying a saponified 40 ⁇ m thick triacetyl cellulose film while applying a polyvinyl alcohol-based adhesive on the surface of the polarizing layer of the optical film laminate, the amorphous PET substrate was peeled off, A thin polarizing film using a thin polarizing layer was produced.
• Example 1 Preparation of adhesive composition
• the onium-anion salt (B1) ethylmethylpyrrolidinium-bis (trifluoromethanesulfonyl) imide (Tokyo Kasei) 0.7 parts of Kogyo Co., Ltd., 1 part of lithium bis (trifluoromethanesulfonyl) imide (Mitsubishi Materials Electronics Chemical Co., Ltd.) as an alkali metal salt (B2), and further a crosslinking agent (D) 0.095 part of trimethylolpropane xylylene diisocyanate (trade name: Takenate D110N, manufactured by Mitsui Chemicals, Inc.) and 0.3 part of dibenzoyl peroxide (trade name: Niper BMT40SV, manufactured by Nippon Oil & Fats Co., Ltd.) , Methyl group and mercapto group-containing alk
• the acrylic pressure-sensitive adhesive solution is uniformly applied to the surface of a polyethylene terephthalate film (separator film) treated with a silicone-based release agent with a fountain coater and dried in an air circulation type thermostatic oven at 155 ° C. for 2 minutes. Then, an adhesive layer having a thickness of 20 ⁇ m was formed on the surface of the separator film. Next, the pressure-sensitive adhesive layer formed on the separator film was transferred to the polarizing layer side of the polarizer of the thin polarizing film produced in Production Example 2 to produce a pressure-sensitive adhesive layer-attached polarizing film.
• Example 2 in preparing the pressure-sensitive adhesive composition, the addition amount of the onium-anion salt (B1) and the alkali metal salt (B2), and the type and addition amount of the silane coupling agent were changed as shown in Table 1.
• a polarizing film with an adhesive layer was produced in the same manner as in Example 1 except that.
• the surface resistance value ( ⁇ / ⁇ ) of the pressure-sensitive adhesive surface was measured using MCP-HT450 manufactured by Mitsubishi Chemical Analytech Co., Ltd. Measured.
• the surface resistance value is preferably less than 1.0 ⁇ 10 11 ⁇ / ⁇ , preferably 9.0 ⁇ 10 10 ⁇ / ⁇ or less, and 5.0 ⁇ 10 10 ⁇ / ⁇ or less. Is more preferable.
• the polarizing film with an adhesive layer obtained in Examples and Comparative Examples was cut into a size of 100 mm ⁇ 100 mm and attached to a liquid crystal panel. This panel was placed on a backlight having a luminance of 10000 cd, and the static electricity generation device ESD (ESD-8012A, manufactured by SANKI) was used to generate 5 kV and 15 kV static electricity, thereby causing alignment disorder of the liquid crystal. .
• ESD static electricity generation device
• the display failure recovery time (seconds) due to the orientation failure was measured using an instantaneous multiphotometric detector (MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.).
• the display failure recovery time is preferably 10 seconds or less, and more preferably 5 seconds or less in both cases of 5 kV and 15 kV.
• (C2) is an acetoacetyl group-containing silane coupling agent (trade name: A-100, manufactured by Soken Chemical Co., Ltd.)
• (C3) is ⁇ -glycidoxypropylmethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
• (C4) represents an epoxy group-containing silane coupling agent (trade name: X-41-1056, manufactured by Shin-Etsu Chemical Co., Ltd.).

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