CN101418198A - Pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive layer for optical film, production method thereof, pressure-sensitive adhesive optical film and image display - Google Patents

Abstract

A pressure-sensitive adhesive composition can form an pressure-sensitive adhesive layer that has satisfactory reworkability such that optical films can be easily peeled from liquid crystal panels with no adhesive residue and also has satisfactory processability such that it can be worked without pressure-sensitive adhesive fouling or dropout. The pressure-sensitive adhesive composition for an optical film of the present invention comprises 100 parts by weight of a (meth)acrylic polymer comprising 45 to 99.99% by weight of an alkyl (meth)acrylate monomer unit and 0.01 to 2% by weight of a tertiary amino group-containing monomer unit; and 0.01 to 2 parts by weight of a peroxide as a crosslinking agent.

Description

Optical thin film binder composition, optical thin film binder layer, its manufacture method and adhesive optical film and image display device

Technical field

The present invention relates to a kind of need using binder composition and pass through optical thin film binder layer and the manufacture method thereof that this binder composition forms by transparent optical thin film.And then the one side at least that the invention still further relates at optical thin film is formed with the adhesive optical film of above-mentioned optical thin film with binder layer.And then, the invention still further relates to image display devices such as the liquid crystal indicator that used above-mentioned adhesive optical film, organic EL display.As above-mentioned optical thin film, can use polarization plates, polarizer, optical compensating film, brightness improving film, and then can also use their member stacked.

Background technology

With regard to liquid-crystal display etc., from its image forming mode, be necessary and indispensable at the both sides of liquid crystal cells configuration polarizer, normally be pasted with polarization plates.In addition, except using polarization plates,, can also use various optical elements on the liquid crystal panel in order to improve the display quality of indicating meter.For example, can use the visual angle that is used to prevent painted polarizer, is used to improve the visual angle of liquid-crystal display to amplify film, and then can also use the brightness improving film etc. of the contrast gradient that is used to improve indicating meter.These films are generically and collectively referred to as optical thin film.

When being attached at above-mentioned optical thin film on the liquid crystal cells, use tackiness agent usually.In addition, with regard to bonding between optical thin film and liquid crystal cells or the optical thin film, usually in order to reduce the loss of light, material separately uses tackiness agent to connect airtight.Under these circumstances, has advantages such as when making optical thin film fastening, not needing drying process, so use tackiness agent to be set at the one-sided adhesive optical film of optical thin film in advance as binder layer usually.In addition, on binder layer, be fitted with distance piece (mould release film) usually.

Necessary characteristic as above-mentioned tackiness agent requirement, be when fitting in optical thin film on the liquid crystal cells, even if under mistaken applying position or the engaging-in situation such of foreign matter, also can peel off optical thin film and liquid crystal cells is utilized again from liquid crystal panel to binding face.In this stripping process, requirement can be at the releasable (re-workability) that does not have easily to peel off from liquid crystal panel under the situation of residual paste optical thin film.Especially in recent years,, the use of the slim liquid crystal panel that used the glass of handling through chemical milling has been increased, from re-workability, the workability of the optical thin film of this slim liquid crystal panel difficulty that becomes except in the past panel makes the operation.

, with regard to tackiness agent, on optical thin film, formed after the binder layer usually with regard to above-mentioned optics, be rolled into drum, it has been carried out stamping-out processing.In addition, for tackiness agent, use linking agent for optics with acrylic acid polymer as base polymer.As this linking agent, for example can enumerate isocyanate compound, but isocyanate compound is needing spended time aspect the formation (wearing out) of binder layer, need long-time until dispatching from the factory.If do not carrying out implementing processing treatment under the above-mentioned aged situation, then because the pollution of tackiness agent or come off to wait and cause the workability reduction.In addition, unfavorable condition such as trace also can take place to beat in aging.Thus, optics is required to have the workability that can process with tackiness agent under pollution that tackiness agent does not take place or situation about coming off etc.

In addition, as the linking agent that uses in tackiness agent at optics, propose to have superoxide.By superoxide crosslinked since finish at dried curing process crosslinked, so have the advantage that does not need digestion time.But if use superoxide, then the peeling force at distance piece significantly rises, and for the panel producer, when peeling off distance piece (mould release film), peels off and becomes heavy, has operation problems such as manufacturing line stagnation.In addition, compared with the past along with the continuous progress of the slimming of optical thin film in recent years, requiring with respect to distance piece is that light separability, operation are good.

And then, for above-mentioned tackiness agent, require the unfavorable condition that is caused by tackiness agent not to take place with respect to the long duration test of carrying out usually as the environment accelerated test based on heating and humidification etc.

In the past, as the method for the problem of the re-workability of eliminating liquid crystal panel, proposed in the acrylic acid polymer as base polymer of acrylic adhesive, to contain the method (patent documentation 1) of softening agent or oligopolymer composition.But, with regard to this acrylic adhesive, still can't satisfy re-workability, as the workability of adhesive optical film, with respect to the operation of distance piece with respect to above-mentioned slim liquid crystal panel.

Except above-mentioned,, propose to have the material (patent documentation 2) that in acrylic acid polymer, is added with superoxide as the acrylic adhesive that in optical thin film, uses; As the monomer component of acrylic acid polymer, except (methyl) alkyl acrylate, also use intramolecularly to have the monomer of hydroxyl and the monomeric material (patent documentation 3,4) that intramolecularly has functional groups such as carboxyl, amide group, amino; Monomer component as acrylic acid polymer, except (methyl) alkyl acrylate, still with containing nitrogen containing monomers such as imide monomer, amide-containing monomer, and then still used the material (patent documentation 5) of superoxide and isocyanate compound.But, the acrylic adhesive of putting down in writing in these patent documentations all can improve the weather resistance at initial stage, but can't satisfy secular weather resistance, but also can't fully satisfy re-workability, as the workability of adhesive optical film, with respect to the operation of distance piece.

Patent documentation 1: the spy opens communique 2003-No. 329837

Patent documentation 2: the spy opens communique 2006-No. 183022

Patent documentation 3: the spy opens communique 2004-No. 091499

Patent documentation 4: the spy opens communique 2004-No. 091500

Patent documentation 5: the spy opens communique 2007-No. 138147

Summary of the invention

The objective of the invention is to, a kind of optical thin film binder composition that can form the binder layer that can satisfy re-workability and workability is provided, described re-workability is meant and can easily do not peel off optical thin film from liquid crystal panel when having residual paste, and described workability is meant when form binder layer on optical thin film after and can processes under the situation that can not produce the pollution of tackiness agent or come off etc.And then its purpose also is, provides a kind of and can form the optical thin film binder composition that has the good binder layer of the operation of light separability with respect to distance piece.

In addition, the present invention also aims to, the binder layer and the manufacture method thereof that form with binder composition by above-mentioned optical thin film are provided.And then, the present invention also aims to, a kind of adhesive optical film with this binder layer is provided, and then the image display device that has used above-mentioned adhesive optical film also is provided.

The inventor etc. concentrate on studies to above-mentioned problem, found that following optical thin film binder composition, to such an extent as to finished the present invention.

Promptly, the present invention relates to a kind of optical thin film binder composition, it is characterized in that, it is the tackiness agent that contains (methyl) acrylic acid polymer and form as the superoxide of linking agent, with respect to (methyl) acrylic acid polymer 100 weight parts, contain described superoxide 0.01～2 weight part, described (methyl) acrylic acid polymer contains (methyl) alkyl acrylate 45～99.99 weight % as monomeric unit and tertiary-amino-containing monomer 0.01～2 weight % forms.

With in the binder composition,, preferably also contain isocyanate-based linking agent 0.01～2 weight part at above-mentioned optical thin film as linking agent with respect to above-mentioned (methyl) acrylic acid polymer 100 weight parts.

,, preferably also contain silane coupling agent 0.01～2 weight part and form with in the binder composition at above-mentioned optical thin film with respect to above-mentioned (methyl) acrylic acid polymer 100 weight parts.

With in the binder composition, above-mentioned (methyl) acrylic acid polymer as monomeric unit, also contains carboxylic monomer 0.01～5 weight % and/or hydroxyl monomer 0.01～5 weight % at above-mentioned optical thin film.

Use in the binder composition at above-mentioned optical thin film, as the tertiary-amino-containing monomer, preferred (methyl) vinylformic acid N, N-dimethylamino ethyl ester and/or N, N-dimethylaminopropyl (methyl) acrylamide.

With in the binder composition, the weight-average molecular weight of preferably above-mentioned (methyl) acrylic acid polymer is 1,000,000～3,000,000 at above-mentioned optical thin film.

In addition, the present invention relates to the optical thin film binder layer that forms with binder composition by above-mentioned optical thin film.

Above-mentioned optical thin film is 50～95 weight % with the preferred gel fraction of binder layer.

In addition, the present invention relates to above-mentioned optical thin film manufacture method, it is characterized in that, above-mentioned optical thin film is coated on the base material with binder composition, under 70～160 ℃ of temperature, handled to make its curing with 30～240 seconds time with binder layer.

In addition, the present invention relates to adhesive optical film, it is characterized in that, be formed with the binder layer that forms with binder composition by above-mentioned optical thin film at least one side of optical thin film.

In addition, the present invention relates to use the above-mentioned adhesive optical film image display device of a slice at least.

With regard to binder composition,, contain the tertiary-amino-containing monomer as monomeric unit with regard to the optical thin film of the invention described above with a small amount of ratio of 0.01～2 weight % about (methyl) acrylic acid polymer as the base polymer of tackiness agent.By having adopted the optical thin film binder composition of this structure, can form binder layer as follows, be that described binder layer can improve workability and re-workability, can suppress to add the disappearance or the pollution of tackiness agent in man-hour, in addition, even if with optical thin film under slim liquid crystal panel, situation about particularly peeling off from the liquid crystal panel that has used through the glass of chemical milling, can easily peel off under the residual situation of paste not having.In addition, this binder layer can be peeled off from liquid crystal panel under the situation that does not make the optical thin film fracture.Its result can effectively carry out the utilization again of liquid crystal panel under the situation of not damaging slim optical thin film.

With regard to regard to the tertiary-amino-containing monomer that contains with above-mentioned a small amount of ratio in (methyl) acrylic acid polymer, consideration can improve the compound that has formed binder layer crosslinked stability afterwards, this binder layer by the crosslinking reaction based on linking agent.As linking agent, when the ratio with afore mentioned rules contains superoxide, especially, can improve above-mentioned crosslinked stability by using the tertiary-amino-containing monomer.In addition, as linking agent, except superoxide, can also use isocyanate compound.Can in the scope of afore mentioned rules, use silane coupling agent.Particularly under superoxide and the situation with isocyanate compound or silane coupling agent, above-mentioned crosslinked stability improves, and can improve re-workability, workability.In the past, the binder layer that is formed by the binder composition that is combined with additives such as silane coupling agent was because As time goes on silane coupling agent etc. dispersed from binder layer, so be difficult to stably keep the characteristic of binder layer.By binder composition of the present invention, As time goes on, the residual of the silane coupling agent in the binder layer increases, and the stability of product performance improves, and can satisfy secular weather resistance.

In addition, in (methyl) acrylic acid polymer,, can improve weather resistance, and then improve re-workability by also containing carboxylic monomer or hydroxyl monomer as monomeric unit.Contain carboxylic monomer, hydroxyl monomer (methyl) acrylic acid polymer as copolymer composition, because effects such as the soda acid interaction of these copolymer compositions, hydrogen bond, can be when improving re-workability, improve weather resistance, under heating condition or under the humidified condition, can realize the inhibition of floating or peeling off etc. unfavorable condition to tackiness agent.

In addition, by binder composition of the present invention, with respect to the uncle's amino that is directed in (methyl) acrylic acid polymer, use superoxide as linking agent, form binder layer advantageous point, that have good productivity, workability thus as peroxide crosslinking, simultaneously can inhibitory phase for the rising of the peeling force of distance piece (mould release film).For this reason, with regard to this binder layer, with respect to distance piece, also can As time goes on gently peel off distance piece, operation improves, and can further enhance productivity.In (methyl) acrylic acid polymer, the decomposition rate of the combination of uncle's amino and superoxide is fast, compare with the crosslinking reaction of (methyl) acrylic acid polymer with distance piece, make each other more preferably crosslinked of (methyl) acrylic acid polymer, thus can inhibitory phase for the rising of the peeling force of distance piece.

Embodiment

Optical thin film binder composition of the present invention uses and to contain (methyl) acrylic acid polymer that (methyl) alkyl acrylate 45～99.99 weight % and tertiary-amino-containing monomer 0.01～2 weight % form as base polymer.

As (methyl) alkyl acrylate, the carbonatoms that is the alkyl of (methyl) alkyl acrylate is about 2～18 compound.Alkyl can be any of straight chain, side chain.The average carbon atom number of abovementioned alkyl is preferably 2～14, and further preferred average carbon atom number is 3～12, and further preferred average carbon atom number is 4～9.Wherein, (methyl) acrylate is meant acrylate and/or methacrylic ester, and is equivalent in meaning with (methyl) of the present invention.

As the object lesson of (methyl) alkyl acrylate, can enumerate (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid n-pentyl ester, (methyl) vinylformic acid isopentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) vinylformic acid isopentyl ester, (methyl) vinylformic acid 2-ethylhexyl, (methyl) vinylformic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, (methyl) isodecyl acrylate, (methyl) vinylformic acid dodecyl ester, the different myristin of (methyl) vinylformic acid, (methyl) vinylformic acid n-tridecane base ester, (methyl) vinylformic acid n-tetradecane base ester, (methyl) vinylformic acid octadecane alcohol ester, (methyl) vinylformic acid isooctadecane alcohol ester etc.Wherein, can illustration (methyl) n-butyl acrylate, (methyl) vinylformic acid 2-ethylhexyl etc., they can be used alone or in combination.

In the present invention, above-mentioned (methyl) alkyl acrylate is 45～99.99 weight % with respect to all monomer components of (methyl) acrylic acid polymer.Be preferably 85～99.99 weight %, 87～99.99 weight % more preferably, further preferred 90～99.99 weight %, further more preferably 98～99.99 weight %.If above-mentioned (methyl) acrylic monomer is very few, so the shortage that becomes cementability is not preferred.

In addition, as the tertiary-amino-containing monomer, can enumerate the monomer that contains uncle's amino and (methyl) acryl.As uncle's amino, be preferably uncle's aminoalkyl group.As this tertiary-amino-containing monomer, can enumerate N, N-dialkyl aminoalkyl (methyl) acrylamide, (methyl) vinylformic acid N, N-dialkyl aminoalkyl ester.As the monomeric object lesson of tertiary-amino-containing, for example can enumerate N, N-dimethyl aminoethyl (methyl) acrylamide, N, N-dimethylaminopropyl (methyl) acrylamide, N, N-diethylamino ethyl (methyl) acrylamide, N, N-diethylamino propyl group (methyl) acrylamide, (methyl) vinylformic acid N, N-dimethylamino ethyl ester, (methyl) vinylformic acid N, N-dimethylamino propyl ester, (methyl) vinylformic acid N, N-diethylamino ethyl ester, N, N-diethylamino propyl group (methyl) acrylamide.In addition, in the middle of these tertiary-amino-containing monomers, preferred (methyl) vinylformic acid N, N-dimethylamino ethyl ester and/or N, N-dimethylaminopropyl (methyl) acrylamide.

Wherein, even if use nitrogen containing monomer and be the monomer beyond the tertiary-amino-containing monomer, for example maleimides such as maleimide, N-cyclohexyl maleimide, N-phenyl maleimide are monomer; N-(methyl) acryloyl-oxy methylene succinimide or N-(methyl) acryl-6-oxygen base hexa-methylene succinimide, N-(methyl) acryl-succinimides such as 8-oxygen base, eight methylene radical succinimides are monomer; (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-substituted amides such as N-diethyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-methoxymethyl (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide are monomer; (methyl) vinylformic acid tertiary butyl amino ethyl ester etc. has the monomer of secondary amino group; Diacetone (methyl) acrylamide, N-vinyl acetamide, N; N '-methylene-bis (methyl) acrylamide, N-caprolactam, N-acryloyl morpholine, N-acryl piperidines, N-methacryloyl phenylpiperidines, N-acryl tetramethyleneimine etc. also are difficult to improve re-workability, workability.

Above-mentioned tertiary-amino-containing monomer preferably uses the ratio of 0.01～2 weight % with respect to the total amount of the monomer component that forms (methyl) acrylic acid polymer.The monomeric ratio of tertiary-amino-containing is preferably 0.01～1.5 weight %, more preferably 0.01～1 weight %, further preferred 0.01～0.5 weight %, more preferably 0.05～0.45 weight %, more preferably 0.05～0.2 weight %.If the monomeric ratio of tertiary-amino-containing is less than 0.01 weight %, the crosslinked stability of binder layer worsens, and can't satisfy re-workability, workability, and is in addition from the weather resistance aspect, not preferred.In addition, can fully not promote crosslinkedly, be difficult to reduce the gel fraction of binder layer, improve with respect to the separability of distance piece, not preferred.On the other hand, from the viewpoint of re-workability, weather resistance, the not preferred monomeric ratio of tertiary-amino-containing is too much, can the monomeric ratio control of tertiary-amino-containing be become below the 2 weight % according to the mode of the cohesive force that does not improve binder layer.

As the monomer component that forms above-mentioned (methyl) acrylic acid polymer, except above-mentioned monomer, owing to contain carboxylic monomer and/or the hydroxyl monomer can improve weather resistance etc., so preferred.Especially preferably use the hydroxyl monomer.

As containing carboxylic monomer, can use to have (methyl) acryl or have the polymerizability functional group of unsaturated double-bonds such as vinyl and have the compound of carboxyl with being not particularly limited.As containing carboxylic monomer, for example can enumerate (methyl) vinylformic acid, (methyl) vinylformic acid carboxylic ethyl ester, (methyl) vinylformic acid carboxylic pentyl ester, methylene-succinic acid, toxilic acid, fumaric acid, Ba Dousuan etc.Wherein, preferred (methyl) vinylformic acid, preferred especially vinylformic acid.

Contain carboxylic monomer, preferably use the ratio of 0.01～5 weight % with respect to the total amount of the monomer component that forms (methyl) acrylic acid polymer.The ratio that contains carboxylic monomer is preferably 0.01～2 weight %, more preferably 0.01～1 weight %, more preferably 0.05～0.5 weight %.In order to improve weather resistance, preferably contain more than the carboxylic monomer 0.01 weight %.On the other hand, surpass 5 weight % if contain the ratio of carboxylic monomer, then bonding force strengthens, and peels off to become heavy, can't satisfy re-workability, so not preferred.

As the hydroxyl monomer, can use to have (methyl) acryl or have the polymerizability functional group of unsaturated double-bonds such as vinyl and have the compound of hydroxyl with being not particularly limited.As the hydroxyl monomer, for example can enumerate (methyl) vinylformic acid hydroxyalkyl acrylates such as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 8-hydroxyl monooctyl ester, (methyl) vinylformic acid 10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) vinylformic acid 12-hydroxyl lauryl, hydroxyethyl (methyl) acrylamide; Can also enumerate (4-hydroxymethyl cyclohexyl) methacrylic ester, N-methylol (methyl) acrylamide, N-hydroxyl (methyl) acrylamide, vinyl carbinol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, Diethylene Glycol mono vinyl ether, acrylic acid caprolactone affixture, (methyl) polyalkylene glycol acrylate ester, (methyl) vinylformic acid polypropylene glycol ester etc. in addition.Wherein, preferred (methyl) vinylformic acid hydroxyalkyl acrylate.

The hydroxyl monomer preferably uses the ratio of 0.01～5 weight % with respect to the total amount of the monomer component that forms (methyl) acrylic acid polymer.The monomeric ratio of hydroxyl is preferably 0.01～2 weight %, more preferably 0.01～1.5 weight %, more preferably 0.01～1 weight %, more preferably 0.05～0.5 weight %.In order to improve weather resistance, preferably contain more than the hydroxyl monomer 0.01 weight %.Especially using under the situation of isocyanate-based linking agent as linking agent, in order to ensure with the cross-linking set of isocyanate group, preferably contain more than the hydroxyl monomer 0.01 weight %.On the other hand, if the monomeric ratio of hydroxyl surpasses 5 weight %, then bonding force strengthens, and peels off to become heavy, can't satisfy re-workability, so not preferred.

As the monomer component that forms above-mentioned (methyl) acrylic acid polymer, except above-mentioned monomer, in the scope of not damaging purpose of the present invention, can in the scope below the 50 weight % of monomer total amount, use above-mentioned monomer in addition.Any monomeric ratio is preferably below the 48 weight %, more preferably below the 45 weight %.As this any monomer, for example can enumerate have (methyl) acryl or have the polymerizability functional group of unsaturated double-bonds such as vinyl and have an aromatic ring contain the aromatic ring monomer.As containing the monomeric object lesson of aromatic ring, can enumerate (methyl) vinylformic acid phenoxy ethyl, (methyl) benzyl acrylate, phenol ring oxidative ethane modification (methyl) acrylate, (methyl) vinylformic acid 2-naphthalene ethyl ester, (methyl) vinylformic acid 2-(4-methoxyl group-1-naphthyloxy) ethyl ester, (methyl) vinylformic acid phenoxy group propyl ester, (methyl) vinylformic acid phenoxy group binaryglycol ester, (methyl) vinylformic acid mercaptan ester, (methyl) phenyl acrylate, polystyrene-based (methyl) acrylate etc.

As any monomer beyond above-mentioned, can enumerate maleic anhydride, itaconic anhydride etc. and contain the anhydride group monomer; Styrene sulfonic acid or allyl sulphonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic acid, (methyl) acrylamide propane sulfonic acid, (methyl) vinylformic acid sulfo group propyl ester, (methyl) acryloxy naphthene sulfonic acid etc. contain the sulfonic group monomer; Phosphorous acidic group monomers such as 2-hydroxyethyl acryl phosphoric acid ester; (methyl) alkoxyalkyl acrylates such as (methyl) vinylformic acid methoxyl group ethyl ester, (methyl) vinylformic acid ethoxy ethyl ester etc.

And then, can also use ethene base system monomers such as vinyl-acetic ester, propionate, vinylbenzene, α-vinyl toluene, N-caprolactam; (methyl) glycidyl acrylate etc. contains the epoxy group(ing) acrylic monomer; Glycol such as (methyl) vinylformic acid methoxyl group glycol ester, (methyl) vinylformic acid methoxyl group polypropylene glycol ester are acrylate monomer; Acrylic ester monomers such as (methyl) tetrahydrofurfuryl acrylate, fluoro (methyl) acrylate, silicone (methyl) acrylate or vinylformic acid 2-methoxyl group ethyl ester etc.

(methyl) of the present invention acrylic acid polymer, using weight-average molecular weight usually is 1,000,000～3,000,000 polymkeric substance.If the consideration weather resistance is particularly considered thermotolerance, preferably using weight-average molecular weight is 1,500,000～2,500,000 polymkeric substance.And then more preferably 1,700,000～2,500,000, further preferred 1,800,000～2,500,000.If weight-average molecular weight is not preferred from thermotolerance less than 1,500,000.In addition, if weight-average molecular weight greater than 3,000,000, it is not preferred then to reduce this point in stickiness, bounding force yet.Wherein, weight-average molecular weight is meant the value of measuring and calculating by polystyrene conversion by GPC (gel permeation chromatography).

Known manufacture method such as solution polymerization, mass polymerization, letex polymerization, various radical polymerizations can be suitably selected in the manufacturing of (methyl) acrylic acid polymer like this.In addition, (methyl) acrylic acid polymer that obtains can be in random copolymers, segmented copolymer, the graft copolymer etc. arbitrarily.

Wherein, in solution polymerization,, for example use ethyl acetate, toluene etc. as polymer solvent.As concrete solution polymerization example, reaction is to add polymerization starter under inert nitrogen air-flows such as nitrogen, usually about 50～70 ℃, carry out under about 5～30 hours the reaction conditions.

The polymerization starter that uses in radical polymerization, chain-transfer agent, emulsifying agent etc. are not particularly limited, can suitably select to use.Wherein, the weight-average molecular weight of (methyl) acrylic acid polymer can be controlled by usage quantity, the reaction conditions of polymerization starter, chain-transfer agent, regulates suitable usage quantity according to their kind.

As polymerization starter, for example can enumerate 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2-amidine propane) dihydrochloride, 2,2 '-azo two [2-(5-methyl-2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride, 2,2 '-azo two (2-methyl-prop amidine) dithionate, 2,2 '-azo, two (N, N '-dimethylene isobutyl amidine), 2,2 '-azo two [N-(2-carboxy ethyl)-2-methyl-prop amidine] hydrate is (with the pure medicine corporate system of light, VA-057) azo series initiators such as, Potassium Persulphate, persulphates such as ammonium persulphate, peroxy dicarbonate two (2-ethylhexyl) ester, peroxy dicarbonate two (4-tert-butylcyclohexyl) ester, peroxide-butyl carbonate, new peroxide tert-butyl caprate, the own ester of peroxidation trimethylacetic acid uncle, peroxidation trimethylacetic acid tertiary butyl ester, dilauroyl peroxide, peroxidation two positive decoyls, peroxidation-2-thylhexoic acid (1,1,3,3-tetramethyl butyl) ester, peroxidation two (4-toluyl), dibenzoyl peroxide, the peroxidation tert-butyl isobutyrate, 1,1-two (peroxidation of uncle's hexyl) hexanaphthene, tertbutyl peroxide, superoxide series initiators such as hydrogen peroxide, the combination of persulphate and sodium bisulfite, the redox series initiators of combination superoxide such as the combination of superoxide and sodium ascorbate and reductive agent etc., but do not limited by these.

Described polymerization starter can use or mix two or more uses separately, content as a whole, and monomer 100 weight parts relatively are about preferred 0.005～1 weight part, more preferably about 0.02～0.5 weight part.

Wherein, in order for example to use 2,2 '-Diisopropyl azodicarboxylate is as polymerization starter, make (methyl) acrylic acid polymer of above-mentioned weight-average molecular weight, the usage quantity of polymerization starter is with respect to total amount 100 weight parts of monomer component, be preferably about 0.06～0.2 weight part, more preferably about 0.08～0.175 weight part.

As chain-transfer agent, for example can enumerate dodecyl mercaptans, glycidyl mercaptan, Thiovanic acid, 2-mercaptoethanol, Thiovanic acid, Thiovanic acid-2-ethylhexyl, 2,3-dimercapto-1-propyl alcohol etc.Chain-transfer agent can be used alone or in mixture of two or more, content as a whole, total amount 100 weight parts of monomer component relatively, be about 0.1 weight part below.

In addition, as the emulsifying agent that in letex polymerization, uses, for example can enumerate negatively charged ion such as Sodium Lauryl Sulphate BP/USP, Texapon Special, Sodium dodecylbenzene sulfonate, polyethylene oxide alkyl ethers ammonium sulfate, polyoxyethylene alkyl phenyl ether sodium sulfate is emulsifying agent, and polyethylene oxide alkyl ethers, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-nonionics such as polyoxytrimethylene block polymer are emulsifying agent etc.These emulsifying agents can use separately or and with two or more.

And then, as reactive emulsifier, as the emulsifying agent of introducing free-radical polymerised functional groups such as propenyl, allyl ether, particularly, A Kualun (ア Network ア ロ Application) HS-10, HS-20, KH-10, BC-05, BC-10, BC-20 (more than be the first industrial drugmaker system), the A Daikaliasuopu (SE10N (rising sun electrification worker corporate system) of ア デ カ リ ア ソ-プ) etc. are for example arranged.Reactive emulsifier is owing to be brought in the polymer chain after polymerization, thus water tolerance improve, so preferably.Total amount 100 weight parts of the relative monomer component of usage quantity of emulsifying agent are preferably 0.3～5 weight part, from polymerization stability or mechanical stability, and 0.5～1 weight part more preferably.

In addition, binder composition of the present invention contains superoxide as linking agent.

As superoxide of the present invention, thereby as long as issue base polymer crosslinked that living free radical spike promotes binder composition in heating or rayed, just can suitably use, consider operability or stability, preferred to use 1 minute half life temperature be 80 ℃～160 ℃ superoxide, more preferably uses 90 ℃～140 ℃ superoxide.If half life temperature was low excessively in 1 minute, carry out when then being reflected at the preservation of coating before dry sometimes, viscosity uprises, and coating becomes impossible, on the other hand, if half life temperature was too high in 1 minute, then the temperature during crosslinking reaction uprises, so side reaction takes place sometimes, perhaps unreacted superoxide is too much residual, through the time carry out crosslinked, so not preferred.

As the superoxide that uses in the present invention, for example can enumerate peroxy dicarbonate two (2-ethylhexyl) ester (1 minute half life temperature: 90.6 ℃), peroxy dicarbonate two (4-tert-butylcyclohexyl) ester (1 minute half life temperature: 92.1 ℃), peroxide-butyl carbonate (1 minute half life temperature: 92.4 ℃), new peroxide tert-butyl caprate (1 minute half life temperature: 103.5 ℃), the own ester of peroxidation trimethylacetic acid uncle (1 minute half life temperature: 109.1 ℃), the peroxidation trimethylacetic acid tert-butyl ester (1 minute half life temperature: 110.3 ℃), dilauroyl peroxide (1 minute half life temperature: 116.4 ℃), peroxidation two positive decoyls (1 minute half life temperature: 117.4 ℃), peroxidation-2-thylhexoic acid (1,1,3,3-tetramethyl butyl) ester (1 minute half life temperature: 124.3 ℃), peroxidation two (4-toluyl) (1 minute half life temperature: 128.2 ℃), dibenzoyl peroxide (1 minute half life temperature: 130.0 ℃), peroxidation tert-butyl isobutyrate (1 minute half life temperature: 136.1 ℃), 1,1-two (peroxidation of uncle's hexyl) hexanaphthene (1 minute half life temperature: 149.2 ℃) etc.Wherein, preferably use peroxy dicarbonate two (4-tert-butylcyclohexyl) ester (1 minute half life temperature: 92.1 ℃), dilauroyl peroxide (1 minute half life temperature: 116.4 ℃), dibenzoyl peroxide (1 minute half life temperature: 130.0 ℃) etc. from crosslinking reaction efficient especially remarkably.

Wherein, the transformation period of superoxide is the index of the decomposition rate of expression superoxide, is meant the time that becomes a half until the residual quantity of superoxide.Be used to obtain the decomposition temperature of transformation period or the associated viscera of time transformation period under arbitrary temp when in manufacturer's catalogue (maker catalog) etc., having put down in writing at any time, for example be recorded in " the organo-peroxide catalogue the 9th edition (in May, 2003) " etc. of NOF Corp.

Described superoxide can use a kind separately, it is two or more also can to mix use, and content as a whole, described relatively (methyl) acrylic acid polymer 100 weight parts, contain the described superoxide of 0.01～2 weight part, preferably contain 0.04～1.5 weight part, and then preferably contain 0.05～1 weight part.During less than 0.01 weight part, be cross-linked to form and become insufficient, can't improve crosslinked stability, from re-workability, workability aspect, not preferred.On the other hand, if surpass 2 weight parts, relatively more difficult from the separability of distance piece, perhaps the binder layer hardening is peeled off thus easily owing to have weather resistance, so not preferred.

In addition, using under the situation of superoxide as polymerization starter, also the residual superoxide that does not use in the polyreaction can be used for crosslinking reaction, in this case, can residual quantity is quantitative, add again as required, the amount of peroxides that becomes regulation uses.

Wherein, as the measuring method of the residual peroxide breakdown amount after reaction treatment, for example can utilize HPLC (high performance liquid chromatography) to measure.

More specifically, for example can take out the binder composition after the reaction treatment of about 0.2g at every turn, impregnated among the ethyl acetate 10ml, extract 3 hours, at room temperature leave standstill then 3 days with bobbing machine vibration under 25 ℃, 120rpm.Then, add the 10ml acetonitrile, vibration is 30 minutes under 25 ℃, 120rpm, will utilize membrane filter (0.45 μ m) to filter the about 10 μ l of extracting solution that obtain and be injected among the HPLC, analyzes, and becomes the amount of peroxides after the reaction treatment.

In addition, as above-mentioned linking agent, can use organic system linking agent or multi-functional metallo-chelate with superoxide.As the organic system linking agent, can enumerate epoxy and be linking agent, isocyanate-based linking agent, imines is linking agent etc.Multi-functional metallo-chelate is polyvalent metal and organic compound covalent attachment or complex bound compound.As polyvalent metal atom, can enumerate Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti etc.As the atom in covalent attachment or the complex bound organic compound, can enumerate Sauerstoffatom etc., as organic compound, can enumerate alkyl ester, alkylol cpd, carboxylic acid cpd, ether compound, ketone compound etc.In the middle of above-mentioned linking agent, preferred isocyanate is a linking agent.

As the isocyanate-based linking agent, can enumerate aromatic isocyanates such as benzylidene vulcabond, eylylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, aliphatic isocyanates such as hexamethylene diisocyanate etc.

More specifically, for example can enumerate the butylidene vulcabond, lower aliphatic polymeric polyisocyanate classes such as hexamethylene diisocyanate, ring pentylidene vulcabond, the cyclohexylene vulcabond, alicyclic isocyanate classes such as isophorone diisocyanate, 2,4-benzylidene vulcabond, 4,4 '-diphenylmethanediisocyanate, the xylylene vulcabond, aromatic diisocyanate classes such as polymethylene polyphenyl isocyanate, TriMethylolPropane(TMP)/benzylidene vulcabond 3 aggressiveness affixtures (Japanese polyurethane industrial system, trade(brand)name Coronate L), TriMethylolPropane(TMP)/hexamethylene diisocyanate 3 aggressiveness affixtures (Japanese polyurethane industrial system, trade(brand)name CoronateHL), the isocyanuric acid ester body of hexamethylene diisocyanate isocyanate addition products such as (Japanese polyurethane industrial system, trade(brand)name Coronate HX), the polyethers polymeric polyisocyanate, the affixture of polyester polymeric polyisocyanate and they and various polyols, use the tricarbimide ester bond, biuret linkage, the polymeric polyisocyanate that allophanic acid ester bond etc. are multiple functionalized etc.

Described isocyanate-based linking agent can use a kind separately, also can mix two or more uses, content as a whole, described relatively (methyl) acrylic acid polymer 100 weight parts, preferably contain the described isocyanate-based linking agent of 0.01～2 weight part, more preferably contain 0.04～1.5 weight part, and then preferably contain 0.05～1 weight part.Less than 0.01 weight part the time, the cohesive force deficiency on the other hand, if surpass 2 weight parts, is then peeled off in endurance test, so not preferred easily sometimes.

By above-mentioned linking agent, form binder layer, but when forming binder layer, when using superoxide or isocyanate-based linking agent as linking agent, need in the addition of adjusting them, take into full account the influence of crosslinking Treatment temperature or crosslinking Treatment time.

The adjustment of crosslinking Treatment temperature or crosslinking Treatment time is for example preferably set the decomposition amount of the superoxide that contains in the binder composition more than the 50 weight % for, more preferably sets for more than the 60 weight %, and then preferably sets into more than the 70 weight %.If the decomposition amount of superoxide is less than 50 weight %, then the quantitative change of residual superoxide is many in the binder composition, sometimes also can take place after the crosslinking Treatment through the time crosslinking reaction etc., so not preferred.

More specifically, for example, under the crosslinking Treatment temperature was 1 minute half life temperature, the decomposition amount of superoxide was 50 weight % after 1 minute, and the decomposition amount of superoxide is 75 weight % after 2 minutes, needs the crosslinking Treatment time more than 1 minute.In addition, for example, the transformation period of the superoxide under the crosslinking Treatment temperature (partly declining the time) is if be 30 seconds, then need the above crosslinking Treatment time in 30 seconds, in addition, for example, the transformation period of the superoxide under the crosslinking Treatment temperature (partly declining the time) then needs the crosslinking Treatment time more than 5 minutes if be 5 minutes.

Like this, because the superoxide difference of using, suppose that crosslinking Treatment temperature or crosslinking Treatment time becomes ratio one time with superoxide, can be from transformation period (partly declining the time), utilize Theoretical Calculation to calculate crosslinking Treatment temperature or crosslinking Treatment time, can suitably regulate addition.On the other hand, become high temperature more, the possibility that side reaction then takes place is high more, so the crosslinking Treatment temperature is preferably below 170 ℃.

In addition, this crosslinking Treatment can be carried out under the temperature when the drying process of binder layer, also can the crosslinking Treatment operation be set in addition after drying process and carry out.

In addition,, can consider productivity or operability and set, be generally about 0.2～20 minute, be preferably about 0.5～10 minute about the crosslinking Treatment time.

In addition, in order to improve bonding force, resisting power, can in binder composition of the present invention, use silane coupling agent.As silane coupling agent, can be not particularly limited ground and suitably use known silane coupling agent.

Particularly, for example can enumerate 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyldiethoxysilane, 2-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane etc. and contain the epoxy radicals silicone hydride coupler; 3-aminopropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl butylidene) propylamine, N-phenyl-γ-aminopropyl trimethoxysilane etc. contain aminosilane coupling agent; 3-acryloxy propyl trimethoxy silicane, 3-methacryloxypropyl triethoxyl silane etc. contain (methyl) acryl silane coupling agent; 3-isocyanic ester propyl-triethoxysilicane etc. contains isocyanato silanes coupler etc.From the raising of weather resistance, preferably use such silane coupling agent.

Described silane coupling agent can use separately, it is two or more also can to mix use, content as a whole, described relatively (methyl) acrylic acid polymer 100 weight parts, preferably contain the described silane coupling agent of 0.01～2 weight part, more preferably contain 0.02～0.6 weight part, and then preferably contain 0.05～0.3 weight part.Less than 0.01 weight part the time, be inadequate for improving weather resistance.On the other hand, when surpassing 2 weight parts, the bonding force to optical components such as liquid crystal cells too increases sometimes, the possibility that exists re-workability to reduce.

And then, in binder composition of the present invention, also can contain other known additives, for example according to employed purposes, can suit to add powders such as tinting material, pigment, dyestuff, tensio-active agent, softening agent, tackifier, surface lubricant, flow agent, tenderizer, antioxidant, protective agent, photostabilizer, UV light absorber, stopper, inorganic or organic weighting agent, metal powder, particle shape, paper tinsel shape thing etc.In addition, in the scope that can control, can adopt the reducto oxydative system that has added reductive agent.

Optical thin film binder layer of the present invention forms with binder composition by above-mentioned optical thin film.In the present invention, from satisfying the viewpoint with respect to the operation of the light separability of distance piece, the gel fraction of this binder layer is preferably 50～95 weight %.Gel fraction is preferably 55～90 weight %, more preferably 60～90 weight %.Gel fraction is to measure the value that obtains by the method for embodiment record.

Above-mentioned optical thin film can be heat-treated, be solidified to form after be coated on the base material with binder layer.Adhesive optical film of the present invention is the film that is formed with binder layer in the one side at least of optical thin film by above-mentioned tackiness agent.

As the method that forms above-mentioned binder layer, for example can enumerate distance piece that use has been implemented the lift-off processing face etc. as base material, above-mentioned binder composition is coated on this distance piece, when drying is removed polymer solvent etc., make it be solidified to form binder layer, be transferred to the method on the optical thin film then.In addition, as the method that forms above-mentioned binder layer, for example can enumerate and use optical thin film as base material, the direct above-mentioned binder composition of coating on optical thin film makes its curing and form the method for binder layer on optical thin film when drying is removed polymer solvent etc.Wherein, when coating adhesive, can suitably newly add more than one the solvent beyond the polymer solvent.

With regard to the formation of above-mentioned binder layer, preferably after being coated on base material on binder composition above-mentioned optical thin film, for example handling and make its curing (drying) with 70～160 ℃ of temperature, 30～240 seconds time, carry out thus.Above-mentioned solidification value is preferably 80～160 ℃, more preferably 100～155 ℃.In addition, above-mentioned setting time is 30～180 seconds, more preferably 30～120 seconds.

Optical thin film binder composition of the present invention, (methyl) acrylic acid polymer as base polymer contains uncle's amino, on the other hand, use superoxide as linking agent, thus when binder composition is solidified, even if under aforesaid low temperature (below 120 ℃), also can be cured processing fast.In the past, when optical thin film contains superoxide as linking agent with binder composition, if under above-mentioned low temperature, this binder composition is implemented solidification treatment, then there is superoxide residual, generation through the time change, for example increase with respect to the separability of distance piece, even if but binder composition of the present invention also can be cured processing fast under above-mentioned low temperature, can keep with respect to distance piece through the time light separability.

Particularly contain with binder composition under the situation of silane coupling agent at optical thin film of the present invention, above-mentioned treatment condition are suitable.In the past, with respect to the binder composition that contains silane coupling agent,, surpass 120 seconds solidification treatment surpassing under 140 ℃ the high temperature, at this moment, the silane coupling agent evaporation, residual quantity reduces, and secular durability not insufficient is abundant, even if but binder composition of the present invention also can be cured processing fast under above-mentioned low temperature, can through the time keep the residual of silane coupling agent, can the long term maintenance weather resistance, can prolong the life-span of product.

In addition, when making adhesive optical film of the present invention, can form adhesion promoting layer, perhaps after having implemented various easy bonding processing such as corona treatment, plasma treatment, form binder layer on the surface of optical thin film.In addition, can carry out easy bonding processing on the surface of binder layer.

Formation method as binder layer can adopt the whole bag of tricks.Particularly, for example can enumerate that roller coat, roller lick that formula coating, gravure coating, oppositely coating, roller brush, spraying, dipping roller coat, rod are coated with, blade coating, air-blade type coating process, curtain are coated with, lip formula coating (lip coat), utilize the methods such as extrusion coating method of mold coating machine (die coater) etc.

Thickness to binder layer is not particularly limited, and for example is about 1～100 μ m.Preferred 5～50 μ m, more preferably 10～30 μ m.

Under the situation that above-mentioned binder layer exposes, until for can be with the sheet material of implementing lift-off processing (distance piece) protection binder layer in using.

Constituent material as distance piece, for example can enumerate plastics films such as polyethylene, polypropylene, polyethylene terephthalate, polyester film, porous materials such as paper, cloth, non-woven fabrics, reticulation, foam sheet, tinsel, and suitable thin slice body such as the duplexer of these materials etc., and, preferably use plastics film from the outstanding point of surface smoothing.

As this plastics film; as long as can protect above-mentioned binder layer; just be not particularly limited, for example can enumerate polyethylene film, polypropylene film, polybutene film, polyhutadiene film, poly-methyl pentene film, polyvinyl chloride film, vinyl chloride copolymer film, pet film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate ester copolymer film etc.

The thickness of described distance piece is generally 5～200 μ m, is preferably about 5～100 μ m.As required, also can to described distance piece implement releasing agent by silicone-based, fluorine system, chain alkyl system or fatty amide system, silicon dioxide powder etc. the demoulding and antifouling processing or application type, sneak into anti-electrostatics such as type, evaporation type and handle.Especially can further improve separability by suitably carry out lift-off processing such as silicone-treated, chain alkyl processing, fluorine processing on the surface of described distance piece from described binder layer.Binder layer of the present invention is fit to for the member that distance piece has been implemented demoulding processing, is suitable for the member that has carried out demoulding processing by silicone-treated particularly.

Wherein, the sheet material of implementing lift-off processing that uses when having made above-mentioned adhesive optical film can be simplified aspect operation directly as the distance piece of adhesive optical film.

As optical thin film, use the optical thin film that in the formation of image display devices such as liquid crystal indicator, uses, its kind is not particularly limited.For example, as optical thin film, can enumerate polarization plates.Polarization plates is used the member that has transparent protective film at the one or both sides of polaroid usually.

Polaroid is not particularly limited, can uses various polaroids.As polaroid, can enumerate, for example divide on the hydrophilic macromolecule film such as saponification film the film of dichroic substance such as absorption iodine or dichroic dye and unilateral stretching at polyvinyl alcohol film, the ethylene-vinyl acetate ester copolymer pastern of polyvinyl alcohol film, part methylalization; The processed thing of polyvinyl alcohol or the polyenes such as dehydrochlorination handled thing of polyvinyl chloride are oriented film etc.In these polaroids, the preferred polaroid that constitutes by dichroic substance such as polyvinyl alcohol film and iodine.Thickness to these polaroids is not particularly limited, and is generally about 5～80 μ m.

With polyvinyl alcohol film with iodine staining after the polaroid that unilateral stretching forms for example, after can dyeing by the aqueous solution that polyvinyl alcohol be impregnated in iodine, make for 3～7 times that are stretched to raw footage.As required, but also can impregnated in the aqueous solution of potassiumiodide etc. of boronic acid containing or zinc sulfate, zinc chloride etc.In addition, as required, also can be before dyeing polyvinyl alcohol film be impregnated in the water and wash.By the washing polyvinyl alcohol film, except can the lip-deep dirt of flush away polyvinyl alcohol film and anti, can be by making the polyvinyl alcohol film swelling, the effect of non-uniform phenomenon such as stain of preventing is also arranged.Stretch and both can after with iodine staining, carry out,, perhaps also can after stretching, dye with iodine on one side also can stretch by an Edge Coloring.Also can or stretch in the water-bath in the aqueous solution of boric acid or potassiumiodide etc.

Material as constituting transparent protective film for example uses the thermoplastic resin that has good character in each side such as the transparency, physical strength, thermostability, moisture barrier, isotropy.As the object lesson of such thermoplastic resin, can enumerate celluosic resin, vibrin, polyethersulfone resin, polysulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (methyl) acrylic resin, cyclic polyolefin resin (norbornene resin), polyarylate resin, polystyrene resin, polyvinyl alcohol resin and their mixtures such as triacetyl cellulose.Wherein, utilize the side applying transparent protective film of adhesive layer at polaroid; but, can use heat-curing resins such as (methyl) acrylic acid series, carbamate system, propenoic methyl carbamate system, epoxy system, silicone-based or ultraviolet curing resin as transparent protective film at opposite side.Can contain any suitable additive in the transparent protective film more than a kind.As additive, for example can enumerate UV light absorber, antioxidant, lubricant, softening agent, releasing agent, painted agent, fire retardant, nucleator, antistatic agent, pigment, the tinting material etc. of preventing.The content of the above-mentioned thermoplastic resin in the transparent protective film is preferably 50～100 weight %, 50～99 weight % more preferably, and then be preferably 60～98 weight %, be preferably 70～97 weight % especially.The content of the above-mentioned thermoplastic resin in transparent protective film is under the situation below the 50 weight %, may fully show high transparent that thermoplastic resin had originally etc.

In addition; as transparent protective film; can enumerate as the spy and open the polymeric film described in 2001-No. 343529 communiques (WO01/37007), as for contain have on (A) side chain replace and/or not the substituted imides base thermoplastic resin and (B) have the resin combination of the thermoplastic resin of replacement and/or unsubstituted phenyl and itrile group on the side chain.As concrete example, can be exemplified as and contain by iso-butylene and the N-alternating copolymer of methyl maleimide formation and the resin combination film of acrylonitrile styrene copolymer.Film can use the film that is made of mixing extruded product of resin combination etc.About these films, because phase differential is little, and photoelastic coefficient is little, thus can eliminate the unequal unfavorable condition that the distortion by polarization plates causes, in addition, because Water Vapour Permeability is little, so the humidification weather resistance is outstanding.

Can suit to determine the thickness of transparent film, but, be about 1～500 μ m usually from aspects such as operations such as intensity or operability, thin layers.Preferred especially 1～300 μ m, more preferably 5～200 μ m.Transparent protective film is very suitable when being 5～150 μ m.

Wherein, when the both sides at polaroid are provided with transparent protective film, both can use the protective film of forming by the same polymer material, also can use the protective film of forming by different polymer materials etc. at its pros and cons.

As transparent protective film of the present invention, preferred use is optional at least a from celluosic resin, polycarbonate resin, cyclic polyolefin resin and (methyl) acrylic resin.

Celluosic resin is the ester of Mierocrystalline cellulose and lipid acid.As such cellulose ester is the concrete example of resin, can enumerate triacetyl cellulose, diacetyl cellulose, three propionyl Mierocrystalline celluloses, two propionyl Mierocrystalline celluloses etc.Wherein, preferred especially triacetyl cellulose.Triacetyl cellulose has a lot of goods to sell, is easy to get calmly or the angle of cost is set out, and be favourable.As the example of the commercially available product of triacetyl cellulose, can enumerate trade(brand)name " UV-50 ", " UV-80 ", " SH-80 ", " TD-80U ", " TD-TAC " of Fuji Photo Film Co., Ltd.'s system, " KC series (series) " of " UZ-TAC " or Konica (コ ニ カ) corporate system etc.Usually with regard to these triacetyl celluloses, phase differential (Re) is roughly 0 in the face, thickness direction phase differential (Rth) be below the 60nm about.

In addition, the celluosic resin film that the thickness direction phase differential is little for example can obtain by handling above-mentioned celluosic resin.For example can enumerate base material films such as the polyethylene terephthalate that will be coated with cyclopentanone, ethyl methyl ketone equal solvent, polypropylene, stainless steel and fit in common cellulose-based film, heat drying is (for example with 80～150 ℃, about 3～10 minutes) after, the method for base material film peeled off; The solution that will be dissolved with norbornene resin, (methyl) acrylic resin etc. in cyclopentanone, ethyl methyl ketone equal solvent is coated on common celluosic resin film, heat drying is (for example with 80～150 ℃, about 3～10 minutes) after, the method for coating film etc. peeled off.

In addition, as the little celluosic resin film of thickness direction phase differential, can use the fatty acid cellulose based resin film of having controlled fatty substitution value.In normally used triacetyl cellulose, be about 2.8 by control acetic acid substituted degree, be preferably 1.8～2.7, can reduce Rth.By being to add softening agent such as dibutyl phthalate, tolysulfonyl aniline, Triethyl citrate acetate in the resin to above-mentioned lipid acid substituted cellulose, can control Rth is little value.With respect to fatty acid cellulose is resin 100 weight parts, and the addition of softening agent is preferably below 40 weight parts, 1～20 weight part more preferably, and then be preferably 1～15 weight part.

Concrete example as cyclic polyolefin resin is preferably norbornene resin.Cyclic polyolefine hydrocarbon system resin is that cyclic olefin is made the general name of its polymeric resin as polymerized unit, for example, can enumerate the spy and open flat 1-No. 240517 communiques, spies and open the resin that flat 3-No. 14882 communiques, spies open record in flat 3-No. 122137 communiques etc.As concrete example, can enumerate open loop (being total to) polymkeric substance of cyclic olefin, the addition polymer of cyclic olefin, the multipolymer of α-alkene such as cyclic olefin and ethene, propylene (representative for random copolymers) and they are carried out the graft copolymer of modification with the unsaturated carboxylic acid or derivatives thereof, and their hydride etc.As the concrete example of cyclic olefin, can enumerate the norborneol alkene monomer.

As cyclic polyolefin resin, there is various products to sell.As concrete example, can enumerate the trade(brand)name " ZEONEX ", " ZEONOR ", the trade(brand)name " ARTON " of JSR Corp.'s system, the trade(brand)name " TOPAS " of TICONA corporate system, the trade(brand)name " APEL " of Mitsui Chemicals, Inc's system of Japanese Zeon Co., Ltd. system.

As (methyl) acrylic resin, Tg (second-order transition temperature) is preferably more than 115 ℃, more preferably more than 120 ℃, and then is preferably more than 125 ℃, is preferably especially more than 130 ℃.By making Tg is more than 115 ℃, can make the weather resistance of polarization plates outstanding.Higher limit to the Tg of above-mentioned (methyl) acrylic resin is not particularly limited, but from the viewpoint of plasticity, is preferably below 170 ℃.From (methyl) acrylic resin, the interior phase differential (Re) of the face that can obtain, thickness direction phase differential (Rth) are roughly 0 film.

As (methyl) acrylic resin,, can adopt suitable (methyl) acrylic resin arbitrarily as long as in the scope of not damaging effect of the present invention.For example can enumerate poly-(methyl) acrylate such as polymethylmethacrylate, methyl methacrylate-(methyl) acrylic copolymer, methyl methacrylate-(methyl) acrylate copolymer, methyl methacrylate-acrylate-(methyl) acrylic copolymer, (methyl) methyl acrylate-styrol copolymer (MS resin etc.), polymkeric substance (methyl methacrylate-cyclohexyl methacrylate multipolymer for example with alicyclic alkyl, methyl methacrylate-(methyl) vinylformic acid norborneol ester copolymer etc.).Preferably enumerate poly-(methyl) vinylformic acid C1～6 alkyl esters such as poly-(methyl) methyl acrylate.More preferably enumerate with the methyl methacrylate is that the methyl methacrylate of main component (50～100 weight % are preferably 70～100 weight %) is a resin.

As the concrete example of (methyl) acrylic resin, for example can enumerate the Acrypet VH of Rayon Co., Ltd. of Mitsubishi system or Acrypet VRL20A, spy and open the intramolecularly of putting down in writing in 2004-No. 70296 communiques and have (methyl) acrylic resin of ring structure, high Tg (methyl) acrylic resin that utilizes intramolecular crosslinking or intramolecular cyclization reaction to obtain.

As (methyl) acrylic resin, also can use (methyl) acrylic resin with lactonic ring structure.This is because have high heat resistance, high transparent, utilize the high mechanical strength of two-way stretch.

As (methyl) acrylic resin, can enumerate the spy and open 2000-No. 230016 communiques, spies and open 2001-No. 151814 communiques, spies and open 2002-No. 120326 communiques, spies and open (methyl) acrylic resin that 2002-No. 254544 communiques, spies open record in 2005-No. 146084 communiques etc. with lactonic ring structure with lactonic ring structure.

(methyl) acrylic resin with lactonic ring structure preferably has the false ring structure that following general formula (changing 1) is represented.

[changing 1]

In the formula, R ¹, R ²And R ³Independently of one another, expression hydrogen atom or carbonatoms are organic residue of 1～20.In addition, organic residue also can comprise Sauerstoffatom.

Have in the structure of (methyl) acrylic resin of lactonic ring structure, proportional 5～90 weight % that are preferably that contain with the lactonic ring structure of general formula (change 1) expression, 10～70 weight % more preferably, and then be preferably 10～60 weight %, be preferably 10～50 weight % especially.Have in the structure of (methyl) acrylic resin of lactonic ring structure, with general formula (changing 1) if the lactonic ring structure of expression contain the proportional 5 weight % that are less than, thermotolerance, solvent resistance, surface hardness can become insufficient so.Have in the structure of (methyl) acrylic resin of lactonic ring structure, if containing of the lactonic ring structure of expression is proportional more than 90 weight %, shortage shaping processability so can become with general formula (changing 1).

Matter average molecular weight (being also referred to as weight-average molecular weight sometimes) with (methyl) acrylic resin of lactonic ring structure is preferably 1000～2000000, more preferably 5000～1000000, and then be preferably 10000～500000, be preferably 50000～500000 especially.If it is not the matter average molecular weight exceeds above-mentioned scope, from the viewpoint of shaping processability, preferred so.

Have (methyl) acrylic resin of lactonic ring structure, Tg is preferably more than 115 ℃, more preferably more than 120 ℃, and then is preferably more than 125 ℃, is preferably especially more than 130 ℃.Because Tg more than 115 ℃, so for example bringing under the situation of polarization plates as transparent protective film, becomes the outstanding polarization plates of weather resistance.Higher limit to the Tg of (methyl) acrylic resin with above-mentioned lactonic ring structure is not particularly limited, and from viewpoints such as plasticities, is preferably below 170 ℃.

(methyl) acrylic resin with lactonic ring structure, total light penetration molding, that utilization is measured based on the method for ASTM-D-1003 that utilizes injection molding forming to obtain is high more preferred more, be preferably more than 85%, more preferably more than 88%, and then be preferably more than 90%.Total light penetration is the benchmark of the transparency, if always light penetration is less than 85%, the transparency may reduce so.

Above-mentioned transparent protective film uses the front phase differential less than 40nm and the thickness direction phase differential film less than 80nm usually.(nx-ny) * d represents front phase differential Re with Re=.(nx-nz) * d represents thickness direction phase differential Rth with Rth=.In addition, the Nz coefficient is with Nz=(nx-nz)/(nx-ny) expression.[wherein, the specific refractory power of the slow axis direction of film, heading direction of principal axis and thickness direction is respectively nx, ny, nz, and d (nm) is the thickness of film.The slow axis direction is that the specific refractory power in the pellicular front becomes maximum direction.]。In addition, transparent protective film is preferably not painted as far as possible.Preferably the phase difference value of used thickness direction be-90nm～+ protective film of 75nm.Phase difference value (Rth) by using this thickness direction for-90nm～+ protective film of 75nm, can roughly eliminate painted (optic painted) of the polarization plates that transparent protective film causes.Thickness direction phase difference value (Rth) and then be preferably-80nm～+ 60nm, be preferably especially-70nm～+ 45nm.

On the other hand, as above-mentioned transparent protective film, can use have the front phase differential as more than the 40nm and/or the thickness direction phase differential be the polarizer of the phase differential more than the 80nm.The front phase differential is controlled at the scope of 40～200nm usually, and the thickness direction phase differential is controlled at the scope of 80～300nm usually.Using under the situation of polarizer as transparent protective film, this polarizer also plays the function of transparent protective film, so can realize slimming.

As polarizer, can enumerate and macromolecular material is implemented unidirectional or two-way stretch handle the oriented film of the birefringent film that forms, liquid crystalline polymers, the oriented layer of liquid crystalline polymers is supported in polarizer on the film etc.Thickness to polarizer is not particularly limited, and is generally about 20～150 μ m.

As macromolecular material, for example can enumerate polyvinyl alcohol, polyvinyl butyral acetal, poly-ethylene methacrylic ether, the polyacrylic acid hydroxyethyl ester, Natvosol, hydroxypropylcellulose, methylcellulose gum, polycarbonate, polyarylester, polysulfones, polyethylene terephthalate, PEN, polyethersulfone, polyphenylene sulfide, polyphenylene oxide, polyene propyl group sulfone, polymeric amide, polyimide, polyolefine, polyvinyl chloride, celluosic resin, cyclic polyolefin resin (norbornene resin) or their two component system, the various multipolymers of three component system, graft copolymer, mixture etc.These macromolecular materials can wait by stretching becomes orientation thing (oriented film).

As liquid crystalline polymers, for example can enumerate the backbone chain type of the linearity atomic group (mesogene) that on the main chain of polymkeric substance or side chain, has imported the conjugacy of giving liquid crystal aligning or various polymkeric substance of side chain type etc.Object lesson as the backbone chain type liquid crystal polymkeric substance, can enumerate the polymkeric substance that has giving the structure that combines liquid crystal (mesogene) base on the spacer portion of bendability, for example the polyester to the row orientation is liquid-crystalline polymer, discoid polymkeric substance or cholesteric polymers etc.Object lesson as side chain liquid crystalline polymer, can enumerate following compound etc., promptly, as main chain backbone, the spacer portion that constitutes by the atomic group by conjugacy as side chain has polymkeric substance of liquid crystal (mesogene) portion that is made of the para-orientation ring-type compound unit of giving to the row orientation etc. with polysiloxane, polyacrylic ester, polymethacrylate or poly-malonic ester.These liquid crystalline polymerss are for example handled by the following method, promptly, material after carrying out friction treatment, oblique evaporation for the surface that is formed on films such as polyimide on the sheet glass or polyvinyl alcohol on the orientation process face of oxide materials etc., heat-treat after sprawling the solution of liquid-crystalline polymer.

Polarizer can be that for example various wavelength plates or the be used to material that compensates the painted or visual angle that the double refraction by liquid crystal layer causes etc. etc. has the material corresponding to the suitable phase differential of application target, also can be stacked more than 2 kinds polarizer and controlled the material of optical characteristics such as phase differential.

Polarizer satisfies nx=ny〉nz, nx〉ny〉nz, nx〉ny=nz, nx〉nz〉ny, nz=nx〉ny, nz〉nx〉ny, nz〉relation of nx=ny, can select to use according to various uses.In addition, ny=nz not only is meant ny and the identical situation of nz, also comprises the in fact ny situation identical with nz.

For example, satisfy nx〉ny〉polarizer of nz, preferably use that to satisfy the front phase differential be that 40～100nm, thickness direction phase differential are that 100～320nm, Nz coefficient are 1.8～4.5 polarizer.For example, satisfying nx〉(positive A plate, positive A-plate), the preferred use satisfied the polarizer that the front phase differential is 100～200nm for the polarizer of ny=nz.For example satisfying nz=nx〉(negative A plate, negative A-plate), the preferred use satisfied the polarizer that the front phase differential is 100～200nm for the polarizer of ny.For example, satisfy nx〉nz〉polarizer of ny, preferably use that to satisfy the front phase differential be 150～300nm, Nz coefficient for surpassing 0 and be polarizer below 0.7.In addition, as mentioned above, for example can use and satisfy nx=ny nz, nz nx ny or nz the polarizer of nx=ny.

Transparent protective film can suitably be selected according to applied liquid crystal indicator.Be under VA (arranged vertical) situation of (Vertical Alignment comprises MVA, PVA) for example, at least one side's (cell side) of preferred polarization plates transparent protective film has phase differential.As concrete phase differential, preferably in the scope of Re=0～240nm, Rth=0～500nm.With regard to three-dimensional refractive index, preferred nx〉ny=nz, nx〉ny〉nz, nx〉nz〉ny, nx=ny〉situation of nz (positive A plate, two-way, negative C plate).About the VA type, preferably use 1 of the combination of positive A plate and negative C plate or bidirectional thin.When the use polarization plates up and down of liquid crystal cells, can for liquid crystal cells all have phase differential up and down, perhaps also can for up and down arbitrarily transparent protective film have phase differential.

For example be IPS when (In-Plane Switching comprises FFS), having under the situation of phase differential, the situation about not having, all can use at a side's of polarization plates transparent protective film.For example, under the situation that does not have phase differential, preferably (cell side) all do not have the situation of phase differential about liquid crystal cells.Have under the situation of phase differential, preferably liquid crystal cells all have up and down the situation of phase differential, up and down any one party have phase differential situation (for example upside is to satisfy nx〉nz the bidirectional thin, the situation that downside does not have phase differential of relation of ny, or the situation of the positive A plate of upside, the positive C plate of downside).Have under the situation of phase differential, preferably in the scope of Re=-500～500nm, Rth=-500～500nm.With regard to three-dimensional refractive index, preferred nx〉ny=nz, nx〉nz〉ny, nz〉nx=ny, nz〉nx〉ny (positive A plate, two-way, positive C plate).

In addition, above-mentioned film with phase differential can make it fit in the transparent protective film with phase differential in addition, thereby give above-mentioned functions.

About above-mentioned transparent protective film, before adhesive coating,, can carry out surface modification treatment in order to improve the cementability with polaroid.As concrete processing, can enumerate corona treatment, plasma treatment, flame treating, ozonize, primary coat processing, aura processing, saponification processing, pass through the processing of coupler etc.In addition, can suitably form antistatic backing.

In the one side that does not have bonding polaroid of above-mentioned transparent protective film, can carry out that hard coat or antireflection are handled, anti is handled, with diffusion or anti-dazzle be the processing of purpose.

Implement purpose that hard coat handles and be to prevent the surface distress of polarization plates etc., mode that for example can be by the curing tunicle that the additional hardness that is made of suitable ultraviolet curing resin such as acrylic acid series, silicone-based, sliding properties etc. are good on the surface of transparent protective film etc. forms.Implementing the purpose that antireflection handles is to prevent the reflection of outer light on the polarization plates surface, can wait based in the past antireflection film by formation and finish.In addition, implementing purpose that anti handles is the adhesion that prevents with adjacent layers (for example diffuser plate of backlight side).

In addition; the purpose of implementing non-glare treated is to prevent that outer light from disturbing polarization plates to see through the identification etc. of light in the polarization plates surface reflection; for example; can give the micro concavo-convex structure to the transparent protective film surface and form by adopting sandblast mode or the mode of slightly coming to the surface of embossing processing mode and the suitable modes such as mode that cooperate transparent particulate.As the particulate that in the formation of above-mentioned surperficial micro concavo-convex structure, contains, for example, can use median size is the inorganic transparent particulates of being made up of silicon oxide, aluminum oxide, titanium oxide, zirconium white, stannic oxide, Indium sesquioxide, Cadmium oxide, weisspiessglanz etc. such as organic system particulate that are particulate, are made up of crosslinked or uncrosslinked polymkeric substance etc. that often have electroconductibility of 0.5～20 μ m.When forming surperficial micro concavo-convex structure, the usage quantity of particulate is generally about 2～70 weight parts with respect to transparent resin 100 weight parts that form surperficial micro concavo-convex structure, is preferably 5～50 weight parts.Antiglare layer also can be held concurrently to work as and be used for the polarization plates transmitted light is spread and the diffusion layer (visual angle expanded functionality etc.) at expansion visual angle etc.

Also have, above-mentioned anti-reflection layer, antiblocking layers, diffusion layer or antiglare layer etc. can also be arranged as other optical layers and transparent protective film branch except can being arranged to transparent protective film self.

Tackiness agent is used in the bonding processing of above-mentioned polaroid and transparent protective film.As tackiness agent, can be exemplified as isocyanate-based tackiness agent, polyethenol series tackiness agent, gelatin is that tackiness agent, ethene are latex, waterborne polyester etc.Above-mentioned tackiness agent uses as the tackiness agent that is made of the aqueous solution usually, and the solid state component that contains 0.5～60 weight % usually forms.Except above-mentioned,, can enumerate ultraviolet hardening tackiness agent, electron(beam)curing type tackiness agent etc. as the tackiness agent of polaroid and transparent protective film.The agent of electron(beam)curing type adhesive for polarizing plate demonstrates suitable cementability with respect to above-mentioned various transparent protective films.In addition, in the tackiness agent that the present invention uses, can contain the metallic compound weighting agent.

In addition, as optical thin film, for example can enumerate operable optical layers in the formation of liquid crystal indicator etc. such as reflector or half transmitting plate, above-mentioned polarizer (comprising 1/2 or 1/4 equiwavelength's plate), viewing angle compensation film, brightness improving film.They can be used alone as optical thin film, in addition, can use more than 1 layer or 2 layers stacked during in practical application on the above-mentioned polarization plates.

Particularly preferred polarization plates is reflection type polarizer or the semi-transmission type polarization plates that further stacked reflector or semi-penetration plate form on polarization plates; Further laminated phase-difference plate forms on polarization plates elliptical polarization plate or circularly polarizing plate; The wide visual angle polarization plates that further stacked viewing angle compensation film forms on polarization plates; The perhaps polarization plates that further stacked brightness improving film forms on polarization plates.

Reflection type polarizer is provided with the reflecting layer and forms on polarization plates, can be used for forming the liquid crystal indicator of the type that reflection shows from the incident light of identification side (demonstration side) etc., and can omit built-in light sources such as backlight, thereby have advantages such as being easy to make the liquid crystal indicator slimming.When forming reflection type polarizer, can be undertaken by the suitable modes such as mode of on the one side of polarization plates, setting up the reflecting layer that constitutes by metal etc. by protective clear layer etc. as required.

As the object lesson of reflection type polarizer, can be exemplified as required on the one side of the transparent protective film of handling through delustring, set up the paper tinsel that constitutes by reflective metal such as aluminium or vapor-deposited film and form the polarization plates etc. in reflecting layer.In addition, can also be exemplified as by making above-mentioned transparent protective film contain particulate and form surperficial micro concavo-convex structure, and have the reflection type polarizer etc. in the reflecting layer of micro concavo-convex structure thereon.The reflecting layer of above-mentioned micro concavo-convex structure makes incident light diffusion by diffuse-reflectance, prevents that thus directional property or outward appearance are shinny, has the advantage that can suppress the light and shade inequality etc.In addition, the transparent protective film that contains particulate also has when incident light and reflected light thereof see through it the advantage etc. that can further suppress the light and shade inequality by diffusion.The formation in reflecting layer of the micro concavo-convex structure of the surperficial micro concavo-convex structure of reflection transparent protective film, method that for example can be by directly setting up metal on the surface of protective clear layer with suitable mode such as vacuum evaporation mode, ion plating mode, sputter mode or plating mode etc. is carried out.

Instead reflector directly is attached to the method on the transparent protective film of above-mentioned polarization plates, the reflecting layer can also be set on the suitable film that with this transparent film is benchmark forms that reflector plate etc. is back to be used as reflector.Also have; because the reflecting layer is made of metal usually; so from the decline of the reflectivity that prevents to cause, and then keep the viewpoint of initial reflectance for a long time or the viewpoint avoiding establishing protective layer in addition waits, preferably cover the type of service of its plane of reflection with transparent protective film or polarization plates etc. owing to oxidation.

Also have, in above-mentioned, the semi-transmission type polarization plates can obtain the reflecting layer of the semi-transmission types such as semi-transparent semi-reflecting lens of light transmission when making with reflective layer reflects light.The semi-transmission type polarization plates is located at the rear side of liquid crystal cells usually, can form the liquid crystal indicator of following type etc., promptly, in brighter environment, use under the situation of liquid crystal indicator etc., reflection comes from the incident light of identification side (demonstration side) and display image, in darker environment, use the built-in light sources such as backlight at the back side that is built in the semi-transmission type polarization plates to come display image.Promptly, the semi-transmission type polarization plates is very useful in the formation of liquid crystal indicator of following type etc., promptly, can the save on backlight lamp under bright environment etc. the energy that uses of light source, under darker environment, also can use in the formation of liquid crystal indicator etc. of type of built-in light source very useful.

Elliptical polarization plate or the circularly polarizing plate that further laminated phase-difference plate on the polarization plates is constituted describes below.Rectilinearly polarized light being changed into elliptically polarized light or circularly polarized light, perhaps elliptically polarized light or circularly polarized light are changed into rectilinearly polarized light, perhaps change under the situation of polarization direction of rectilinearly polarized light, can use polarizer etc.Particularly, as rectilinearly polarized light being changed into circularly polarized light or circularly polarized light being changed into the polarizer of rectilinearly polarized light, can use so-called 1/4 wavelength plate (be also referred to as λ/4 slice).1/2 wavelength plate (be also referred to as λ/2 slice) is generally used for changing the situation of the polarization direction of rectilinearly polarized light.

The elliptical polarization plate can be used for following situation etc. effectively, i.e. compensation (preventing) supertwist nematic phase (STN) type liquid crystal indicator painted (blue or yellow) that produce because of the double refraction of liquid crystal layer, thus there is not the described painted white black situation that shows etc.In addition, it is painted that the polarization plates of control three-dimensional refractive index produces in the time of can also compensating (preventing) from the picture of oblique observation liquid crystal indicator, so preferred.Circularly polarizing plate for example can be used for effectively to situation of adjusting with the tone of the image of the reflection-type liquid-crystal display device of color display image etc., but also has the function of reflecting of preventing.

In addition, above-mentioned elliptical polarization plate or reflection-type elliptical polarization plate are by suitably combination and laminated polarizing plate or reflection type polarizer and polarizer form.This class elliptical polarization plate etc. also can form by stacked respectively successively (reflection-type) polarization plates and polarizer in the manufacturing processed of liquid crystal indicator, to constitute the combination of (reflection-type) polarization plates and polarizer, and as mentioned above, be pre-formed member for optical thin films such as elliptical polarization plates, because outstanding, therefore has the advantage of the manufacturing efficient that can improve liquid crystal indicator etc. at aspects such as quality of stability or lamination operation.

The viewing angle compensation film is also to make image seem more clearly, be used to enlarge the film at visual angle under the situation of the picture of observing liquid crystal indicator from the direction that tilts a little that is not orthogonal to picture.As this kind viewing angle compensation polarizer, for example by the oriented film of polarizer, liquid crystalline polymers etc. or in the transparent substrate upper support material etc. of oriented layer such as liquid crystalline polymers constitute.Usually be implemented unilateral stretching, had birefringent polymeric film along its face direction as what polarizer used, relative therewith, as the polarizer that is used as the viewing angle compensation film, can use along its face direction be implemented the birefringent polymeric film of having of two-way stretch, the biaxially oriented film with birefringent polymkeric substance or tilted alignment film and so on of the specific refractory power of the may command thickness direction that also has been stretched by unidirectional stretching and along its thickness direction along its face direction etc.As the tilted alignment film, for example can enumerate behind the bonding heat-shrinkable film on the polymeric film under effect because of the convergent force that adds thermosetting, polymeric film has been carried out stretch processing or/and the material of shrink process, make material that the liquid crystalline polymers tilted alignment forms etc.Starting material polymkeric substance as polarizer, can use with above-mentioned polarizer in the polymer phase that illustrates with polymkeric substance, can use with the painted grade that variation was brought at the identification angle that prevents to form or enlarge the suitable polymer blend as purpose such as the good visual angle of identification based on the phase differential that causes by liquid crystal cells.

In addition, from the viewpoint that realizes the wide visual angle that identification is good etc., can preferably use the optical compensation polarizer that supports the optical anisotropic layer that the tilted alignment layer by the oriented layer of liquid crystalline polymers, particularly discoid liquid crystalline polymers constitutes with triacetylcellulose film.

Polarization plates and the film adhered polarization plates that together forms of brightness improving are located at usually the back side one side of liquid crystal cells.The brightness improving film is the film that shows below characteristic, promptly, when because of the backlight of liquid crystal indicator etc. or from reflection of rear side etc., when natural light incident is arranged, reflect the rectilinearly polarized light of specific polarizing axis or the circularly polarized light of specific direction, and make other light transmissions, therefore the polarization plates that brightness improving film and polarization plates are laminated can make the light incident from light sources such as backlights, and obtain the light that sees through of specific polarization light state, simultaneously, light beyond the described specific polarization light state can not see through, and is reflected.Be reversed in the light that reflects on this brightness improving pellicular front once more by reflecting layer of being located at its rear side etc., make it to incide once more on the brightness improving film, make its part or all light transmission as the specific polarization light state, thereby increase the light quantity that sees through the brightness improving film, simultaneously provide the polarized light that is difficult to absorb to polaroid, can be thereby increase in the light quantity of utilization in the demonstration of liquid crystal display image etc., and can improve brightness thus.Promptly, pass polaroid and make under the light incident situation from the rear side of liquid crystal cells with backlight etc. not using the brightness improving film, have light with the inconsistent polarization direction of polarizing axis of polaroid and be polarized sheet basically and absorb, thereby can't see through polaroid.That is, though can be different because of the characteristic of employed polaroid, about 50% light can be polarized sheet and sponge, and therefore, the light quantity that can utilize in liquid crystal image demonstration etc. causes the image deepening with corresponding minimizing.Because the brightness improving film carries out following operation repeatedly, promptly, making the light with the polarization direction that can be polarized the sheet absorption is not to incide on the polaroid, but such light is reflected on the brightness improving film, and then finish counter-rotating by reflecting layer of being located at its rear side etc., light is incided on the brightness improving film once more, like this, the brightness improving film only makes in the light of the two reflection and counter-rotating, the polarized light that its polarization direction becomes polarization direction that can be by polaroid sees through, provide it to polaroid simultaneously, therefore can in the demonstration of the image of liquid crystal indicator, use the light of backlight etc. effectively, thereby can make picture bright.

Also can between brightness improving film and described reflecting layer etc., diffuser plate be set.Towards described reflecting layer etc., set diffuser plate can spread the light that passes through equably by the light of the polarized light state of brightness improving film reflection, eliminates polarized light state simultaneously and becomes the non-polarized light state.That is, carry out following operation repeatedly: with the light directive reflecting layer of natural light state etc., through reflecting layer etc. and after the reflection, once more by diffuser plate and incide on the brightness improving film.So make polarized light return to the diffuser plate of original natural light state by between brightness improving film and described reflecting layer etc., being provided with, can be in the brightness of keeping display frame, reduce the inequality of the brightness of display frame, thereby even and bright picture can be provided.By this diffuser plate is set, can suitably increase the repeated reflection number of times of first incident light, and utilize the diffusion function of diffuser plate, bright uniformly display frame can be provided.

As described brightness improving film, for example can use: the demonstration of thin-film multilayer duplexer that dielectric multilayer film or specific refractory power anisotropy are different and so on send as an envoy to the rectilinearly polarized light of regulation polarizing axis see through and reflect the characteristic of other light film, cholesteric liquid crystal polymer oriented film or in the film substrate upper support the demonstrating any circularly polarized light reflection that will be in left-handed or the dextrorotation of film and so on of this aligned liquid-crystal layer and film that the film etc. of the characteristic of other light transmissions is suited.

Therefore, make the brightness improving film of the type that the rectilinearly polarized light of described regulation polarizing axis sees through by utilization, make this see through light and directly incide on the polarization plates, can when suppressing the absorption loss that causes by polarization plates, light be seen through effectively along the direction consistent with polarizing axis.On the other hand, utilize the brightness improving film that makes the type that circularly polarized light sees through of cholesteric and so on, though light is incided on the polaroid, but, from suppressing the absorption loss this point, preferably this circularly polarized light carry out rectilinearly polarized lightization, reenter afterwards and be mapped on the polarization plates by polarizer.And, by using 1/4 wavelength plate, circularly polarized light can be transformed to rectilinearly polarized light as this polarizer.

In broad wavelength regions such as visible region, can play the polarizer of 1/4 wavelength plate effect, for example can utilize following mode to obtain, that is, the phase separation layer that will play the phase separation layer of 1/4 wavelength plate effect with respect to the light luminous energy of wavelength 550nm and show other phase difference characteristics for example can play the phase separation layer eclipsed mode of 1/2 wavelength plate effect etc.So the polarizer that is disposed between polarization plates and the brightness improving film can be made of the phase separation layer more than 1 layer or 2 layers.

Also have, with regard to cholesteric, also can make up the material of different reflection wavelengths, constitute overlapping arrangement more than 2 layers or 3 layers, obtain member thus, thereby can obtain the circularly polarized light that sees through of broad wavelength region based on this at the wavelength region reflection circle polarized light of broads such as visible region.

In addition, polarization plates is as described polarized light divergence type polarization plates, can be made of the member of stacked polarization plates and the optical layers more than 2 layers or 3 layers.So, also can be the reflection-type elliptical polarization plate that forms of combination described reflection type polarizer or semi-transmission type polarization plates and polarizer or semi-transmission type elliptical polarization plate etc.

The stacked optical thin film of described optical layers on polarization plates, can utilize that independent successively stacked mode forms in the manufacturing processed of liquid crystal indicator etc., but, therefore has the advantage of the manufacturing process that can improve liquid crystal indicator etc. in advance through being laminated to the polarization plates of optical thin film is good at aspects such as quality of stability or assembly operations.In stacked, can use suitable adhesion means such as bonding coat.When bonding described polarization plates or other optical layers, their optic axis can adopt suitable arrangement angles according to target phase difference characteristic etc.

Also have, on each layers such as the optical thin film of adhesive optical film of the present invention or binder layer, utilize and for example to use mode that salicylate based compound or benzo phenol (benzophenol) based compound, benzotriazole based compound or UV light absorber such as cyanoacrylate based compound, nickel coordination compound based compound handle etc., make it to have ultraviolet absorption ability etc.

Adhesive optical film of the present invention can be preferred for the formation of various image display devices such as liquid crystal indicator etc.Liquid crystal indicator can form according to method in the past.Promptly, in general, liquid crystal indicator can pass through combination of liquid crystals unit and adhesive optical film aptly, and the component parts such as the lighting system that adds as required and the driving circuit of packing into etc. and form, in the present invention, except using adhesive optical film of the present invention, be not particularly limited, can form according to method in the past.For liquid crystal cells, also can use the liquid crystal cells of any types such as TN type for example or STN type, π type, VA type, IPS type.

The one or both sides that can be formed on liquid crystal cells by the present invention have disposed the liquid crystal indicator of adhesive optical film, used the suitable liquid crystal indicators such as device of backlight or reflector in lighting systems.At this moment, optical thin film of the present invention can be arranged on the one or both sides of liquid crystal cells.When optical thin film was arranged on both sides, they both can be identical materials, also can be different materials.In addition, when forming liquid crystal indicator, can be on suitable position suitable parts such as for example diffuser plate of configuration more than 1 layer or 2 layers, antiglare layer, antireflection film, protecting sheet, prism array, lens arra thin slice, light diffusing sheet, backlight.

Then, Organnic electroluminescent device (organic EL display) is described.Optical thin film of the present invention (polarization plates etc.) also can be used for organic EL display.Usually, in organic EL display, on transparency carrier, stack gradually transparency electrode, organic luminous layer and metal electrode and form twinkler (organic electroluminescent body).Here, organic luminous layer is the duplexer of various organic films, and known have: for example duplexer of the duplexer of hole injection layer that is made of triphenylamine derivative etc. and the luminescent layer that is made of epipolic organic solids such as anthracenes or this kind luminescent layer and the electron injecting layer that is made of perylene derivative etc. or the various combinations such as duplexer of these hole injection layers, luminescent layer and electron injecting layer.

Organic EL display carries out luminous according to following principle, promptly, by on transparency electrode and metal electrode, adding voltage, injected hole and electronics in organic luminous layer, the energy excitation fluorescent substance that produces by the compound of these holes and electronics, when the fluorescent substance that is excited is got back to ground state, will radiate bright dipping.The intermediary recombination mechanism is identical with general diode, also can infer thus, and electric current and luminous intensity demonstrate with respect to impressed voltage and follow the stronger non-linear of rectification.

In organic EL display, in order to take out the light that produces in the organic luminous layer, at least one side's electrode must be transparent, will be used as anode by the transparency electrode that tin indium oxide transparent conductive bodies such as (ITO) is made usually.On the other hand, improve luminous efficiency in order to carry out the injection of electronics easily, it is crucial using the less material of work function in negative electrode, uses metal electrodes such as Mg-Ag, Al-Li usually.

In the organic EL display with this kind formation, organic luminous layer is that film as thin as a wafer about 10nm constitutes by thickness.So organic luminous layer is also the same with transparency electrode, light is fully seen through basically.Consequently, when not luminous from the surperficial incident of transparency carrier and see through transparency electrode and organic luminous layer and can be once more penetrating to the face side of transparency carrier at the light of metal electrode reflection, therefore, when carrying out identification from the outside, the display surface of organic El device is as minute surface.

In the organic EL display that comprises organic electroluminescent body as described below, can polarization plates be set in the face side of transparency electrode, simultaneously between these transparency electrodes and polarization plates, polarizer is set, in described organic electroluminescent body, be provided with transparency electrode by applying the face side that voltage carries out luminous organic luminous layer, the rear side at organic luminous layer is provided with metal electrode simultaneously.

Become the effect of polarized light because polarizer and polarization plates have to make from outside incident and at the light of metal electrode reflection, therefore have and make the effect that can't pick out the minute surface of metal electrode from the outside by this polarized light effect.Particularly, adopt 1/4 wavelength plate to constitute polarizer, and the angle of the polarization direction of polarization plates and polarizer is being adjusted into π/4 o'clock, can cover the minute surface of metal electrode fully.

That is, the exterior light that is incident in this organic EL display has only the rectilinearly polarized light composition because of the existence of polarization plates and sees through.This rectilinearly polarized light generally can be converted to elliptically polarized light by polarizer, and when polarizer be the angle of the polarization direction of 1/4 wavelength plate and polarization plates and polarizer when being π/4, will become circularly polarized light.

This circularly polarized light sees through transparency carrier, transparency electrode, organic film, reflects on metal electrode, sees through organic film, transparency electrode, transparency carrier afterwards once more, converts rectilinearly polarized light once more to by polarizer.Because therefore the polarization direction quadrature of this rectilinearly polarized light and polarization plates can't see through polarization plates.Consequently, the minute surface of metal electrode fully can be covered.

Embodiment

Below, specify the present invention by embodiment, but the present invention is not limited by these embodiment.Wherein, part and the % in each example all is weight basis.Measure the assessment item among embodiment etc. as described below.

The mensuration of＜weight-average molecular weight 〉

The weight-average molecular weight of (methyl) acrylic acid polymer that obtains utilizes GPC (gel permeation chromatography) to measure.Sample uses be with sample dissolution in dimethyl formamide, make the solution of 0.1 weight %, it was left standstill after an evening filtrate that obtains with the membrane filter filtration of 0.45 μ m.

Analytical equipment: eastern tosoh corporate system, HLC-8120GPC

Post: eastern tosoh corporate system, SuperAWM-H, AW4000, AW2500

Column dimension: each 6.0mm Φ * 150mm

Eluant: the dimethyl formamide solution of 30mM-lithiumbromide, 30mM-phosphoric acid

Flow: 0.4ml/min

Detector: differential refractometer (RI)

Column temperature: 40 ℃

Injection rate: 20 μ l

(making of polarization plates)

Between the different roller of speed ratio, dyeing is 1 minute in 30 ℃, the iodine solution of 0.3% concentration, carries out 3 times of stretchings simultaneously with the PVA (PVOH) FILM of thick 80 μ m.Subsequently, 60 ℃, contained in the aqueous solution of potassiumiodide of boric acid, 10% concentration of 4% concentration dipping 0.5 minute, stretching simultaneously and making total stretching ratio is 6 times.Then, 30 ℃, contained in the aqueous solution of potassiumiodide of 1.5% concentration dipping 10 seconds, clean thus, then 50 ℃ dry 4 minutes down, obtain polaroid.On the two sides of this polaroid, utilize the applying of polyethenol series tackiness agent to be implemented the triacetylcellulose film of the thickness 80 μ m of saponification processing, make polarization plates.

Production Example 1

The preparation of＜acrylic acid polymer 〉

In the four-hole boiling flask that possesses stirring rake, thermometer, nitrogen ingress pipe, water cooler, put into 99.7 parts of butyl acrylates, vinylformic acid N, 0.1 part of N-dimethylamino ethyl ester, 0.1 part in vinylformic acid, 0.1 part of vinylformic acid 4-hydroxyl butyl ester, as 2 of polymerization starter, 200 parts of 0.1 part of 2 '-Diisopropyl azodicarboxylate and ethyl acetate, the limit is slowly stirred the limit and is imported nitrogen, after carrying out nitrogen replacement, liquid temperature in the flask is retained near 60 ℃, carry out 6 hours polyreaction, preparation acrylic acid polymer solution.The weight-average molecular weight of described acrylic acid polymer is 2,050,000.

Production Example 2～14 and comparison Production Example 1～7

In Production Example 1, the same except at least any one of the kind of change monomer component as shown in table 2 and usage quantity with Production Example 1, preparation acrylic acid polymer solution.But, in Production Example 14,, use toluene to replace ethyl acetate as solvent.The weight-average molecular weight of the acrylic acid polymer that obtains in each example is shown in table 2.

Embodiment 1

(having the making of the polarization plates of binder layer)

With respect to 100 parts of the solids components of the acrylic acid polymer solution that in Production Example 1, obtains, cooperation is as replacement benzoyl peroxide (Japanese grease (strain) system of linking agent, Nai Pa (Na イ パ-) BMT40) 0.3 part, TriMethylolPropane(TMP) benzylidene vulcabond (Japanese polyurethane industry (strain) system, Coronate L) 0.2 part and silane coupling agent (SHIN-ETSU HANTOTAI's chemical industry (strain) system, KBM403) 0.1 part, thus preparation acrylic adhesive solution.

Then, with aforesaid propylene acid is that binder solution is coated on the polyethylene terephthalate of implementing silicone-treated (PET) film (Mitsubishi Chemical's polyester film (strain) system as distance piece, MRF38) on the one side (silicone-treated face), and to make dried binder layer thickness be 20 μ m, 155 ℃ of down dry 3 minutes (180 seconds), formed binder layer.Be fitted in this binder layer on the polarization plates and carry out transfer printing, make the polarization plates that has binder layer.

Embodiment 2～15, comparative example 1～8

In embodiment 1, the usage quantity of the kind of the acrylic acid polymer solution during with preparation acrylic adhesive solution, the kind of linking agent or usage quantity, silane coupling agent changes to shown in the table 3, in addition, the same with embodiment 1, make the polarization plates that has binder layer.Also have, in comparative example 7, during preparation acrylic adhesive solution, except linking agent and silane coupling agent, also cooperated 15 parts of acrylic acid series oligomers (weight-average molecular weight 3000, East Asia synthetic (strain) system, ARFONUP-1000).

Production Example 15～22, and compare Production Example 8～11

The preparation of＜acrylic acid polymer 〉

In Production Example 1, the same except at least any one of the kind of change monomer component as shown in table 2 and usage quantity with Production Example 1, preparation acrylic acid polymer solution.The weight-average molecular weight of the acrylic acid polymer that obtains in each example is shown in table 2.

Embodiment 16

(having the making of the polarization plates of binder layer)

With respect to 100 parts of the solids components of the acrylic acid polymer solution that in Production Example 15, obtains, cooperation is as replacement benzoyl peroxide (Japanese grease (strain) system of linking agent, Nai Pa (Na イ パ-) BMT40) 0.3 part, TriMethylolPropane(TMP) benzylidene vulcabond (Japanese polyurethane industry (strain) system, Coronate L) 0.1 part and silane coupling agent (SHIN-ETSU HANTOTAI's chemical industry (strain) system, KBM403) 0.1 part, thus preparation acrylic adhesive solution.

Then, with aforesaid propylene acid is that binder solution is coated on polyethylene terephthalate (PET) film (Mitsubishi Chemical's polyester film (strain) system of implementing silicone-treated, MRF38) on the one side, and to make dried binder layer thickness be 25 μ m, drying is 80 seconds under 100 ℃, has formed binder layer.Be fitted in this binder layer on the polarization plates and carry out transfer printing, make the polarization plates that has binder layer.

Embodiment 17～28, comparative example 9～19

In embodiment 1, the usage quantity of the kind of the acrylic acid polymer solution during with preparation acrylic adhesive solution, the kind of linking agent or usage quantity, silane coupling agent, drying conditions (temperature, time) changes to shown in the table 3, in addition, the same with embodiment 1, make the polarization plates that has binder layer.

To the polarization plates that has binder layer (sample) that has distance piece that obtains at the foregoing description and comparative example, carry out following evaluation.Evaluation result is shown in table 4 and table 5.

The mensuration of＜initial stage bonding force 〉

After above-mentioned sample severing is become the 25mm width, peel off distance piece, back and forth it is crimped on non-alkali glass (You Ninggu (コ-ニ Application グ) corporate system of thick 0.7mm with the 2kg roller with one then, 1737) on, thereby attach, utilize 50 ℃, the pressure kettle of 0.5MPa to handle 15 minutes, then, 23 ℃ of following healths 1 hour.To measuring with 180 ° of peel angle, bonding force (N/25mm) when peeling rate 300mm/min strips off this sample with the tension stress trier.

The mensuration of the bonding force after＜60 ℃/48 hours 〉

After above-mentioned sample severing is become the 25mm width, peel off distance piece, back and forth it is crimped on non-alkali glass (You Ninggu (コ-ニ Application グ) corporate system of thick 0.7mm with the 2kg roller with one then, 1737) on, thereby attach, utilize 50 ℃, the pressure kettle of 0.5MPa to handle 15 minutes, then, 60 ℃ of following healths 48 hours.To measuring with 180 ° of peel angle, bonding force (N/25mm) when peeling rate 300mm/min strips off this sample with the tension stress trier.

＜re-workability 〉

After above-mentioned sample severing is become the 25mm width, peel off distance piece, back and forth it is crimped on non-alkali glass (You Ninggu (コ-ニ Application グ) corporate system of thick 0.7mm with the 2kg roller with one then, 1737) on, thereby attach, then, 23 ℃ of following healths 1 hour.With following benchmark visual valuation with the tension stress trier with 180 ° of peel angle, bonding force (N/25mm) when peeling rate 300mm/min peels off this sample and the state of glass surface.

◎: do not have paste residual and can peel off (bonding force :) less than 10N/25mm.

Zero: do not have paste residual and can peel off, but peel off slightly and have any problem (bonding force: 10N/25mm above and less than 15N/25mm).

△: do not have paste residual and can peel off, but peel off have any problem (bonding force: more than the 15N/25mm).

*: there is paste residual slightly.

It is residual that paste takes place * *:.

＜weather resistance 〉

Above-mentioned sample is cut into after 320mm * 240mm, peel off distance piece, then it is attached on the non-alkali glass (You Ninggu (コ-ニ Application グ) corporate system, 1737) of thickness 0.7mm, utilize 50 ℃, the pressure kettle of 0.5MPa to handle 15 minutes, above-mentioned sample and non-alkali glass are connected airtight fully.For the sample of implementing this processing, under 80 ℃, 90 ℃, 100 ℃, 60 ℃/90%RH, the condition of 60 ℃/95%RH, implement to handle in 500 hours, then the state that foams, peels off, floats with following benchmark visual valuation.

Zero: do not foam, peel off.

△: the foaming (maximum diameter is less than 100 μ m) that affirmation has pair identification not impact.

*: confirming has foaming (maximum diameter is more than the 100 μ m), peels off.

＜gel fraction 〉

On the pet film of implementing silicone-treated, coating makes each binder composition before the sample, and make dried thickness identical with each example (20 μ m or 25 μ m), the coating back is cured processing with the drying conditions (temperature, time) identical with each example, form binder layer, and then under the condition of 23 ℃ of temperature, humidity 65%RH, placed 1 hour, then this binder layer is measured gel fraction.With regard to gel fraction, get the about 0.2g of above-mentioned binder layer, with the fluoro-resin (TEMISHNTF-1122 of gravimetry (Wa) in advance, eastern electrician of day (strain) system) encases, the binding and binder layer is exposed, measure its weight (Wb) then, with in the ethyl acetate of the about 40ml of its dipping 7 days, extract solvable composition under 23 ℃.Then, take out the fluoro-resin wrapping binder layer, on the aluminium cup,, measure the weight (Wc) of the fluoro-resin that is wrapping binder layer of having removed solvable composition with 130 ℃ of dryings 2 hours.

According to these measured values,, obtain the gel fraction (weight %) of binder layer according to following formula.

Gel fraction (weight %)=(Wc-Wa)/(Wb-Wa) } * 100

＜coating productivity 〉

About gel fraction A, time of drying B and drying temperature C, enclose respectively to estimate according to table 1 and divide, estimate with following benchmark according to the value that derives from A * B * C.

Zero: evaluation is divided into more than 20

△: estimate and to be divided into more than 5 below 19

*: below 4

Table 1

Estimate and divide	Gel fraction A (weight %)	B time of drying (second)	Drying temperature C (℃)
				6	90～95	—	—
5	80～less than 90	30	—
				4	70～less than 80	45	—
3	60～less than 70	80	Below 80
				2	50～less than 60	120	Surpass below 80 and 120
1	Less than 50	180	Surpass below 120 and 160

＜workability 〉

For became an edge lengths at 24 hours with interior stamping-out after making above-mentioned sample is 100 in the foursquare sample of 270mm, and the operator touches by visual, hand and observes, and judges whether the polarization plates side has the adhesion sense.In addition, whether the surface of judging polarization plates is polluted by tackiness agent.There are several samples to have adhesion sense or pollution with following benchmark evaluation.

The sample that the adhesion sense is arranged in zero: 100 or pollute has 0.

△: have the sample of adhesion sense or pollution to have 1～5 in 100.

*: there is the sample of adhesion sense or pollution to have more than 6 in 100.

The peeling force of＜relative spacing spare 〉

After the sample severing is become wide 50mm, long 100mm, to measuring with 180 ° of peel angle, the peeling rate 300mm/min peeling force (N/50mm) when sample strips off distance piece with the tension stress trier.Peeling force is preferably 0.05～0.1N/50mm, more preferably 0.05～0.09N/50mm.If peeling force is less than 0.05, the easy origination interval spare unfavorable condition of floating in the course of processing then from the binder layer of adhesive optical film, on the other hand, when peeling force surpasses 0.1N/50mm, for the panel producer, when peeling off distance piece, gently peeling off the binder layer of adhesive optical film the difficulty that becomes, productivity variation.

The overburden operation of＜distance piece 〉

For 100 samples, observe with the situation of automatic stripper (day eastern electrician (strain) system) when peeling off distance piece, judge with following benchmark.

0 failure is arranged in zero: 100.

*: failure more than 1 is arranged in 100.

[table 2]

[table 2]

In table 2:

BA: butyl acrylate, DMAEA: vinylformic acid N; N-dimethylamino ethyl ester, DMAPAA:N, N-dimethylaminopropyl acrylamide, ACMO:N-acryloyl morpholine, AAM: acrylamide, AA: vinylformic acid, 4HBA: vinylformic acid 4-hydroxyl butyl ester, 2HEA: vinylformic acid 2-hydroxy methacrylate, PEA: vinylformic acid phenoxy ethyl.

[table 3]

[table 3]

In the table 3, superoxide all is to replace benzoyl peroxide (Japanese grease (strain) system, Nai Pa (Na イ パ-) BMT40).With regard to the isocyanate-based linking agent, ^*The 01st, TriMethylolPropane(TMP) benzylidene vulcabond (Japanese polyurethane industry (strain) system, Coronate L), ^*The 02nd, and the inferior Xylene Diisocyanate of TriMethylolPropane(TMP) (the military field urethane of Mitsui (strain) system, Ta Kainaite (D of ケ ネ-ト)-110N).With regard to silane coupling agent, ^*The 11st, the KBM573 of SHIN-ETSU HANTOTAI's chemical industry (strain) system, ^*The 12nd, the KBM403 of SHIN-ETSU HANTOTAI's chemical industry (strain) system, ^*The 13rd, combine the A-100 that grinds chemistry (strain) system.Other additives of comparative example 7 ^*Oligopolymer is 15 parts of acrylic oligomers (weight-average molecular weight 3000, East Asia synthetic (strain) system, ARFONUP-1000).

[table 4]

[table 5]

From table 4, table 5 as can be known, the binder layer by optical thin film of the present invention forms with binder composition can satisfy re-workability, weather resistance, workability, in addition, has light separability with respect to distance piece, has operation.In addition, by the present invention, shown in the coating productivity of table 5, can obtain the above-mentioned binder layer of regulation gel fraction by the drying conditions of low temperature, short period of time.Wherein, though the not concrete coating productivity that shows in the table 4, the evaluation of the embodiment of table 4 is divided into " 5 " or " 6 ", as coating productive being evaluated as " △ ".

Claims (11)

1. an optical thin film binder composition is characterized in that,

Contain (methyl) acrylic acid polymer and as the superoxide of linking agent,

In described (methyl) acrylic acid polymer, contain (methyl) alkyl acrylate 45～99.99 weight % and tertiary-amino-containing monomer 0.01～2 weight % as monomeric unit, with respect to (methyl) acrylic acid polymer 100 weight parts, described superoxide contains 0.01～2 weight part.

2. optical thin film binder composition according to claim 1 is characterized in that,

With respect to described (methyl) acrylic acid polymer 100 weight parts, also contain isocyanate-based linking agent 0.01～2 weight part as linking agent.

3. optical thin film binder composition according to claim 1 is characterized in that,

With respect to described (methyl) acrylic acid polymer 100 weight parts, also contain silane coupling agent 0.01～2 weight part.

4. optical thin film binder composition according to claim 1 is characterized in that,

In described (methyl) acrylic acid polymer,, also contain at least a monomeric unit of from contain carboxylic monomer 0.01～5 weight % and hydroxyl monomer 0.01～5 weight %, selecting as monomeric unit.

5. optical thin film binder composition according to claim 1 is characterized in that,

The tertiary-amino-containing monomer is from (methyl) vinylformic acid N, N-dimethylamino ethyl ester and N, at least a material of selecting in N-dimethylaminopropyl (methyl) acrylamide.

6. optical thin film binder composition according to claim 1 is characterized in that,

The weight-average molecular weight of described (methyl) acrylic acid polymer is 1,000,000～3,000,000.

7. optical thin film binder layer, it is formed with binder composition by any described optical thin film in the claim 1～6.

8. optical thin film binder layer according to claim 7 is characterized in that,

The gel fraction of binder layer is 50～95 weight %.

9. the manufacture method of the described optical thin film usefulness of claim 7 binder layer is characterized in that,

Any described optical thin film in the claim 1～6 is coated on the base material with binder composition, under 70～160 ℃ of temperature, handled to make its curing with 30～240 seconds time.

10. an adhesive optical film is characterized in that,

At least one side at optical thin film is formed with the described optical thin film binder layer of claim 7.

11. an image display device, it uses the described adhesive optical film of a slice claim 10 at least.