CN106318282A - Adhesive, adhesive sheet and optical film with adhesive layer - Google Patents

Abstract

The invention provides an adhesive which prevents a transparent conducting film from being corroded, is good in antistatic property and excellent in endurance, and enables a display panel not to be easily warped and not to be prone to uneven heating, an adhesive sheet and an optical film with adhesive layer. The adhesive is obtained by an adhesive composition which comprises (methyl) acrylate copolymer (A), isocyanate cross-linking agent (B) and antistatic agent (C), wherein the (methyl) acrylate copolymer comprises monomers (a1) including alicyclic ring structures, monomers (a2) including aromatic nucleus and monomers (a3) including hydroxyl serving as monomer units of copolymer, the hydroxyl value is 5-20mgKOH/g, the acid value is below 5mgKOH/g, and the weight-average molecular weight is 130-300 million; and the gel fraction of the adhesive is 62-90%, and the antistatic agent (C) is an ionic compound including fluorosulfonyl imide as negative ions.

Description

Sticker, adhesive sheet and the optical thin film with adhering agent layer

Technical field

The present invention relates to sticker, adhesive sheet and the optical thin film with adhering agent layer, particularly to It is suitable for the sticker of the optical thin film such as polaroid or composite polarizing plate, adhesive sheet and has adhesion The optical thin film of oxidant layer.

Background technology

In recent years, as the display floater of various electronic equipments, more use and have display device concurrently And the touch panel of input equipment.The kind of touch panel mainly has resistance membrane type, condenser type, light Formula and ultrasonic type, resistance membrane type has artifical resistance membrane type and resistance matrix membrane type, and condenser type has Surface type and projection type.

Touch surface in the electronic apparatus such as the intelligent mobile phone received publicity recently and panel computer In plate, more use projection type capacitive touch panels.As the throwing in this electronic apparatus Shadow type capacitive touch panels, such as, propose it and start from down to be sequentially laminated with liquid crystal display (LCD), adhering agent layer, nesa coating (tin-doped indium oxide: ITO), glass substrate, The protection boards such as nesa coating (ITO) and strengthening glass.

As the optical module of the above-mentioned liquid crystal display of composition, generally use liquid crystal cells.Liquid crystal Unit generally using form oriented layer the oriented layer of two transparent electrode substrates as inner side, by Parting is configured to predetermined distance, and seals its periphery, seizes liquid on both sides by the arms between two transparent electrode substrates Brilliant material.Generally, the outside of two transparent electrode substrates in liquid crystal cells is respectively via adhesion The bonding polaroid of agent and the composite polarizing plate with polarizer.

As the sticker of optics, the such as sticker shown in known patent document 1.This adhesion Agent contains: (methyl) acrylic polymer, relative to having carbon atom as monomeric unit Alkyl (methyl) alkyl acrylate 100 mass parts of the alkyl of several 4～14, containing 0.2～20 The carboxyl group-containing monomer of mass parts forms as copolymer composition；And relative to (methyl) acrylic compounds Polymer 100 mass parts, as the peroxide and 0.005～5 of 0.02～2 mass parts of cross-linking agent The epoxies cross-linking agent of mass parts.

But, the durability of the sticker that patent documentation 1 grade is conventional is the most insufficient, in hot conditions Descend or under wet heat condition it some times happens that float or sur-face peeling.Further, along with mobile electric in recent years The slimming of subset, the optical thin film such as polaroid is also by filming, but the polaroid of thin film is because of warm Higher etc. the shrinkage factor caused, for conventional sticker, display floater occurs warpage.Especially, In order to improve the durability of sticker, make the constituent as (methyl) acrylic polymer , the monomer copolymerization with relatively high-vitrification branchpoint (Tg) time, produce relatively under heat conditions Big shrinkage stress, the warpage of display floater becomes big.Also indicate that, due to the thermal contraction of optical thin film Time stress, the optic axis deviation of optical thin film, thus light leak (so-called heat uneven) occurs Problem.

But, it is laminated with stripping film or the optics such as polaroid, composite polarizing plate of above-mentioned sticker Thin film is generally molded of plastic material.Therefore, electrical insulating property is high, when peeling off stripping film etc., easily Produce electrostatic.If polaroid or composite polarizing plate being pasted when the electrostatic remaining so produced Together in liquid crystal cells, it is likely that produce disorder in the orientation of liquid crystal molecule, and, electrostatic Existence can cause the attraction problem such as flying dust or dust and dirt.

Therefore, in order to obtain effective antistatic property, propose adhesion agent composition interpolation anti-quiet Electricity agent (such as patent documentation 2,3).

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2009-242786 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2007-316377 publication

Patent documentation 3: Japanese Unexamined Patent Publication 2009-155585 publication

Summary of the invention

The technical problem to be solved in the present invention

But, when adhesion agent composition is added antistatic additive described above, there is obtained gluing The durability of agent than the problem generally more declined.Further, sticker and transparent electrode substrate is saturating During the contact of bright conducting film, according to the kind of antistatic additive, exist outside making electrically conducting transparent erosion make See the problem deteriorated.Especially, instead the conductive material of ITO and be expected to silver, copper, aluminum Deng, there is the tendency that corrosion becomes serious.

The present invention completes in view of above-mentioned practical situation, and its purpose will not make transparent leading for providing one Electrolemma burn into plays antistatic behaviour well, excellent in te pins of durability, display floater are difficult to warpage and not Easily there is sticker, adhesive sheet and the optical thin film with adhering agent layer that heat is uneven.

Solve the technological means of technical problem

To achieve these goals, first, the present invention provides a kind of sticker, and it is by cohesiveness group Compound obtains, and described cohesiveness compositions comprises: (methyl) acrylate copolymer (A), its Containing containing ester ring type structures alone (a1), containing aromatic rings monomer (a2) and hydroxyl monomer (a3) As the monomeric unit of composition polymer, hydroxyl value is 5～20mgKOH/g, and acid number is 5mgKOH/g Hereinafter, weight average molecular weight is 1,300,000～3,000,000；Isocyanates cross-linking agent (B)；And it is anti-quiet Electricity agent (C), wherein, the gel fraction of described sticker is 62～90%, described antistatic additive (C) For comprising the fluorine sulfimide ionic compound (invention 1) as anion.

According to foregoing invention (invention 1), even if being attached at the nesa coatings such as ITO, silver, copper, aluminum On, also will not make this electrically conducting transparent erosion, play antistatic behaviour well, excellent in te pins of durability, Display floater is difficult to warpage, and it is uneven to be not susceptible to heat.

In foregoing invention (invention 1), described containing the ester ring type in ester ring type structures alone (a1) Structure is preferably multi-ring ester ring type structure (invention 2).

In foregoing invention (invention 1,2), described cohesiveness compositions is preferably possibly together with containing epoxy Base silane coupling agent (D1) (invention 3).

In foregoing invention (invention 1～3), described cohesiveness compositions is preferably possibly together with containing sulfydryl silicon Alkane coupling agent (D2) (invention 4).

In foregoing invention (invention 1～4), described isocyanates cross-linking agent (B) is preferably tool There is the compound (invention 5) of aromatic rings.

Second, the present invention provides a kind of adhesive sheet, it is characterised in that it possesses by described sticker The adhering agent layer (invention 6) that (invention 1～5) is constituted.

3rd, the present invention provides a kind of optical thin film with adhering agent layer, it is characterised in that its Possess: optical thin film；And adhering agent layer, this adhering agent layer is by being laminated in described optical thin film extremely The described sticker (invention 1～5) of few one side constitutes (invention 7).

Invention effect

Sticker under this invention, adhesive sheet and the optical thin film with adhering agent layer, even if attaching In the new nesa coating (such as, silver, copper, aluminum etc.) of replacement ITO, this also will not be made saturating Bright conducting film corrodes, and plays antistatic behaviour, excellent in te pins of durability, and display floater well and is difficult to Warpage, and it is uneven to be not susceptible to heat.

Accompanying drawing explanation

Fig. 1 is the sectional view of the optical thin film with adhering agent layer of one embodiment of the present invention.

Fig. 2 is the sectional view of the optical thin film with adhering agent layer of another embodiment of the present invention.

Fig. 3 is the sectional view of the configuration example representing polarizer.

Fig. 4 is the heat-resisting not uniformity trial (visually) representing the optical thin film with adhering agent layer The figure (colored) of evaluation criterion.

Description of reference numerals

10A, 10B: with the optical thin film of adhering agent layer；1: adhering agent layer；2A: polaroid； 2B: composite polarizing plate；21: polarizer；22: the first protective layers；23: the second protective layers；24: First phase difference plate；241: the first acrylic resin；242: phase contrast presentation layer；243: Second acrylic resin；25: second phase difference plate；26: the second adhering agent layers；27: protect Sheath.

Detailed description of the invention

Hereinafter, embodiments of the present invention are illustrated.

(sticker)

The sticker of present embodiment is (below, to be sometimes referred to as " cohesiveness group by cohesiveness compositions Compound P ") sticker that obtains, described cohesiveness compositions contains: (methyl) acrylate is common Polymers (A), it contains containing ester ring type structures alone (a1), containing aromatic rings monomer (a2) and contain Carboxylic monomer (a3) is as the monomeric unit of composition polymer, and hydroxyl value is 5 (5.0 is preferred) ～20mgKOH/g, acid number is below 5mgKOH/g, and weight average molecular weight is 1,300,000～3,000,000； Isocyanates cross-linking agent (B)；And antistatic additive (C), wherein, the gel of described sticker Point rate is 62～90%.Further, antistatic additive (C) is for comprise fluorine sulfimide as anion Ionic compound.It addition, in this specification, (methyl) acrylate represents acrylate and first Both base acrylate.Other similar terms are the most identical.

Even if the sticker meeting above-mentioned important document is attached at the new nesa coating replacing ITO, example Such as the nesa coating being made up of silver, copper, aluminum etc., this electrically conducting transparent erosion also will not be made, good Playing antistatic behaviour well, when being used in display floater, excellent in te pins of durability, even if in hot conditions Under, under wet heat condition or under thermal shock, also suppression float or sur-face peeling.Further, use Even if the display floater of above-mentioned sticker is not easy to warpage under the high temperature conditions, and is not susceptible to heat Uneven.

If the hydroxyl value of (methyl) acrylate copolymer (A) is less than 5mgKOH/g, then crosslinking points Very few and cohesiveness declines, and obtained sticker does not play the durability of excellence.If it addition, The hydroxyl value of (methyl) acrylate copolymer (A) is more than 20mgKOH/g, then crosslinking points is too much, Obtained sticker is the most soft, and stress relaxation declines, thus, under the high temperature conditions, aobvious Show panel generation warpage or occur heat uneven.

From the point of view, the lower limit of the hydroxyl value of (methyl) acrylate copolymer (A) is excellent Elect more than 5.0mgKOH/g as, more preferably more than 8mgKOH/g, particularly preferably More than 10mgKOH/g.It addition, the upper limit of the hydroxyl value of (methyl) acrylate copolymer (A) Value is preferably below 18mgKOH/g, particularly preferably below 16mgKOH/g.

On the other hand, if the acid number of (methyl) acrylate copolymer (A) is 5mgKOH/g Hereinafter, though then sticker attach object be due to acid produce unfavorable condition such as ITO, During the nesa coating of silver, copper, aluminum etc., it is also possible to this unfavorable condition that suppression acid causes.That is, Can suppress to make this electrically conducting transparent erosion or change the phenomenon of resistance value of this nesa coating.Separately Outward, the metal film such as described silver, copper, aluminum does not the most have light light transmission.But, this technology is led In territory, predetermined metal film carries out graph thinning also by pattern formation and uses.Now, even golden Belonging to film, light also passes through from fine rule gap each other.Therefore, in this specification, by these Metal film is also classified as nesa coating.

From the point of view, the higher limit of the acid number of (methyl) acrylate copolymer (A) is excellent Elect below 2mgKOH/g as, particularly preferably below 1mgKOH/g.It addition, (methyl) third The lower limit of the acid number of olefin(e) acid ester copolymer (A) is the least more preferred, is therefore particularly preferably 0mgKOH/g。

Here, hydroxyl value and acid number in this specification are set to substantially from (methyl) acrylate common The theoretical value that the adding proportion of polymers (A) derives, when this theoretical value cannot be derived, be set to based on The value that JIS K0070 measures.

If the weight average molecular weight of (methyl) acrylate copolymer (A) is less than 1,300,000, then this reality The durability of the sticker executing mode deteriorates.It addition, (if methyl) acrylate copolymer (A) Weight average molecular weight more than 3,000,000, then the sticker of present embodiment stress relaxation decline, Display floater generation warpage or generation heat are uneven under the high temperature conditions.

From the point of view, under the weight average molecular weight of (methyl) acrylate copolymer (A) Limit value is preferably more than 1,500,000, and particularly preferably more than 1,600,000.It addition, (methyl) propylene The higher limit of the weight average molecular weight of acid ester copolymer (A) is preferably less than 2,500,000, particularly preferably Less than 1900000.

Here, the weight average molecular weight in this specification is for utilizing gel permeation chromatography (GPC) method to survey Fixed polystyrene standard scaled value.

If the gel fraction of the sticker of present embodiment is less than 62%, then the durability of this sticker Deteriorate.Further, if the gel fraction of the sticker of present embodiment is more than 90%, then this embodiment party The stress relaxation of the sticker of formula declines, and display floater produces warpage or generation under the high temperature conditions Heat is uneven.

From the point of view, the lower limit of the gel fraction of the sticker of present embodiment is preferably More than 65%, particularly preferably more than 73%.Further, the gel of the sticker of present embodiment divides The higher limit of rate is preferably less than 85%, and particularly preferably less than 78%.It addition, sticker is solidifying Glue divides shown in the assay method of rate test example as be described hereinafter.

The sticker of present embodiment is by containing comprising the ionizing as anion of the fluorine sulfimide The antistatic additive (C) of compound, plays antistatic behaviour well.Further, this antistatic additive (C) Do not hinder the durability of sticker and electrically conducting transparent erosion will not be made.Therefore, containing above-mentioned anti-quiet The sticker of electricity agent (C) can take into account antistatic behaviour and durability, and for nesa coating Excellent corrosion resistance, it is possible to maintain the outward appearance of nesa coating well.

(1) (methyl) acrylate copolymer (A)

In (methyl) acrylate copolymer (A) of present embodiment, as constituting this polymer Monomeric unit, containing containing ester ring type structures alone (a1), containing aromatic rings monomer (a2) and contain Carboxylic monomer (a3).In these monomers, particularly by containing containing ester ring type structures alone (a1) And (a2) Han aromatic rings monomer, obtained sticker can have simultaneously suitable cohesiveness and Stress relaxation, and for the attaching raising of optical thin film or nesa coating, therefore use When display floater, it is possible to play excellent durability, warpage inhibition and heat-resisting inequality.

In (methyl) acrylate copolymer (A), as the monomeric unit of this polymer of composition, Except above-mentioned containing ester ring type structures alone (a1), containing aromatic rings monomer (a2) and hydroxyl monomer (a3), beyond, (methyl) acrylic acid alkyl that carbon number is 1～20 of alkyl is further preferably contained Ester.Additionally, it is possible to according to needing containing other monomers.

(methyl) acrylate copolymer (the A) (first that carbon number is 1～20 containing alkyl Base) alkyl acrylate as constituting the monomeric unit of this polymer, it is possible to performance preferably Cohesiveness.As (methyl) alkyl acrylate that carbon number is 1～20 of alkyl, such as may be used Enumerate (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) propyl acrylate, (first Base) n-butyl acrylate, (methyl) acrylic acid n-pentyl ester, the most own ester of (methyl) acrylic acid, (first Base) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid ester in the positive last of the ten Heavenly stems, (methyl) acrylic acid n-dodecane ester, (methyl) tetradecyl acrylate, (methyl) acrylic acid Hexadecane ester, (methyl) octadecyl ester etc..Wherein, from improving adhesive angle further Degree considers, the preferably carbon number of alkyl is (methyl) acrylate of 1～8, particularly preferably (methyl) n-butyl acrylate or (methyl) 2-EHA.It addition, they are permissible It is used alone, it is also possible to be used in combination of two or more.

In (methyl) acrylate copolymer (A), as the monomeric unit of this polymer of composition, The carbon number of the alkyl preferably comprising 40～97.5 mass % is (methyl) alkyl acrylate of 1～20 Base ester, particularly preferably containing 55～94 mass %, more preferably contains 65～83 mass %. If containing (methyl) alkyl acrylates more than 40 mass %, then (methyl) third can be given The cohesiveness that olefin(e) acid ester copolymer (A) is suitable.It addition, by by (methyl) alkyl acrylate It is set to below 97.5 mass %, it is possible to import required in (methyl) acrylate copolymer (A) Other monomer components of amount.

Carbocyclic ring containing the ester ring type structure in ester ring type structures alone (a1) can be saturated structures, Can also locally have unsaturated bond.It addition, ester ring type structure can be the ester ring type structure of monocycle, It can also be the multi-ring ester ring type structure such as bicyclo-, three rings.From by obtained (methyl) propylene The mutual distance of acid ester copolymer (A) is set to suitably and gives the angle of sticker stress relaxation Degree considers, above-mentioned ester ring type structure is preferably multi-ring ester ring type structure (multiring structure).Further Consider the compatibility of (methyl) acrylate copolymer (A) and other compositions, the most above-mentioned multi-ring knot Structure is particularly preferably bicyclo-to Fourth Ring.It addition, from the angle giving stress relaxation in the same manner as described above Degree considers, the carbon number of ester ring type structure (refer to all carbon numbers of the looped part of shape, When multiple rings are individually present, refer to its carbon number added up to) preferably generally more than 5, the most excellent Elect more than 7 as.On the other hand, the upper limit of the carbon number of ester ring type structure is not particularly limited, But, in the same manner as described above, from the point of view of the compatibility, preferably less than 15, particularly preferably It is less than 10.

As ester ring type structure, such as, can enumerate and comprise the ester ring type structure such as lower skeleton, described bone Frame is cyclohexyl skeleton, bicyclopentadiene skeleton, adamantane framework, isoborneol skeleton, cycloalkanes bone Frame (cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, ring hendecane bone Frame, cyclododecane skeleton etc.), cyclenes skeleton (cycloheptene skeleton, cyclo-octene skeleton etc.), fall ice Sheet alkene skeleton, norbornadiene skeleton, cubane skeleton, basket alkane skeleton, room alkane skeleton, volution Skeletons etc., wherein, preferably comprise the bicyclopentadiene skeleton (fat that can play more excellent durability The carbon number of ring structures: 10), adamantane framework (carbon number of ester ring type structure: 10) Or isoborneol skeleton (carbon number of ester ring type structure: 7), particularly preferably comprise isoborneol skeleton.

As above-mentioned containing ester ring type structures alone (a1), preferably comprise (methyl) of above-mentioned skeleton Acrylate monomer, specifically, can enumerate (methyl) cyclohexyl acrylate, (methyl) propylene Acid bicyclo-pentyl ester, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) isobornyl acrylate, (methyl) Acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl epoxide ethyl ester etc., wherein, preferably (methyl) acrylic acid bicyclo-pentyl ester of more excellent durability, (methyl) acrylic acid gold can be played Just alkyl ester or (methyl) isobornyl acrylate, particularly preferably (methyl) isobomyl acrylate Ester, they may be used singly or in combination of two or more use.

Excellent durability, warpage inhibition and heat-resisting inequality is played from obtained sticker From the point of view of, in (methyl) acrylate copolymer (A), as the list constituting this polymer Body unit, preferably comprise 1～20 mass % containing ester ring type structures alone (a1).In addition to above-mentioned consideration, Also from the point of view of obtained sticker plays good operability again, the most more preferably contain Have 2～15 mass % containing ester ring type structures alone (a1), particularly preferably containing 3～9 mass %.

As containing aromatic rings monomer (a2), preferably there is (methyl) acrylate of aromatic rings.Make For aromatic rings, phenyl ring, naphthalene nucleus, anthracene nucleus, cyclohexyl biphenyl, fluorenes ring etc. can be enumerated, be wherein preferably Phenyl ring.

As containing aromatic rings monomer (a2), such as, can enumerate (methyl) phenyl acrylate, (methyl) Acrylic acid 2-phenyl chlorocarbonate, (methyl) benzyl acrylate, (methyl) acrylic acid naphthalene ester, (methyl) Acrylate, (methyl) acrylic acid phenoxy group butyl ester, ethoxylation o-phenyl phenol third Olefin(e) acid ester, phenoxy group diethylene glycol (methyl) acrylate, ethylene-oxide-modified cresol (methyl) Modified nonyl phenol (methyl) acrylate of acrylate, oxirane (EO) etc., wherein, From the point of view of improving cohesiveness, it is preferably (methyl) acrylic acid 2-phenyl chlorocarbonate.They can To be used alone, it is also possible to be used in combination of two or more.

In (methyl) acrylate copolymer (A), as the monomeric unit of this polymer of composition, Be preferably containing 1～30 mass % containing aromatic rings monomer (a2), particularly preferably containing 3～25 matter Amount %, more preferably contains 12～22 mass %.By containing of aromatic rings monomer (a2) will be contained Amount sets within the above range, it is possible to make obtained sticker play the durability of excellence, warpage presses down Property processed and heat-resisting inequality.

In (methyl) acrylate copolymer (A), as the monomeric unit of this polymer of composition, Containing hydroxyl monomer (a3).The NCO of hydroxyl and isocyanates cross-linking agent (B) Reactive high, by their reaction, (methyl) acrylate copolymer (A) passes through Carbimide. Esters cross-linking agent (B) cross-links.By this cross-linked structure, obtained sticker excellent in te pins of durability.

As hydroxyl monomer (a3), such as, can enumerate (methyl) acrylic acid 2-hydroxy methacrylate, (first Base) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 2- (the first such as hydroxybutyl, (methyl) acrylic acid 3-hydroxybutyl, (methyl) acrylic acid 4-hydroxybutyl Base) hydroxyalkyl acrylates etc., wherein, from the reactivity with isocyanates cross-linking agent (B) From the point of view of, it is preferably (methyl) acrylic acid 2-hydroxy methacrylate or (methyl) acrylic acid 4-hydroxyl Base butyl ester, particularly preferably (methyl) acrylic acid 2-hydroxy methacrylate.They can be used alone, Can also be used in combination of two or more.

In (methyl) acrylate copolymer (A), as the monomeric unit of this polymer of composition, Preferably comprise the hydroxyl monomer (a3) of 0.5～10 mass %, particularly preferably containing 1～5 mass %, More preferably contain 2～4 mass %.By the content of hydroxyl monomer (a3) is located at above-mentioned In the range of, it is possible to easily make the hydroxyl value of (methyl) acrylate copolymer (A) fall into described scope In, and effectively play durability, warpage inhibition and the heat-resisting inequality of excellence.

In order to make acid number in the range of described, in (methyl) acrylate copolymer (A) the most not Containing carboxyl group-containing monomer as constituting the monomeric unit of this polymer, even if containing carboxyl group-containing monomer, It is also preferred that containing the content below 0.5 mass %, particularly preferably containing containing below 0.1 mass % Amount.

In (methyl) acrylate copolymer (A), as the monomeric unit of this polymer of composition, Also can be containing other monomers beyond described monomer.As these other monomers, above-mentioned in order to not hinder The hydroxyl of hydroxyl monomer (a3) and the reaction of isocyanates cross-linking agent (B), preferably do not contain There is the monomer of the functional group of reactivity with isocyanates cross-linking agent (B).

As these other monomers, such as, can enumerate: (methyl) methoxyethyl acrylate, (methyl) Ethoxyethyl acrylate etc. (methyl) alkoxyalkyl acrylate；Acrylamide, methyl-prop The acrylamide of the non-crosslinkeds such as acrylamide；(methyl) acrylic acid N, N-dimethylamino ethyl ester, (first Base) acrylic acid N, N-dimethylamino propyl ester etc. has (methyl) propylene of non-crosslinked tertiary amino Acid esters；Vinyl acetate etc..They may be used singly or in combination of two or more use.

The polymeric species of (methyl) acrylate copolymer (A) can be random copolymer, it is possible to for Block copolymer.

In cohesiveness compositions P, (methyl) acrylate copolymer (A) can be used alone one Kind, it is also possible to it is used in combination of two or more.It addition, cohesiveness compositions P also can be containing following (first Base) acrylate polymer, should not contain containing ester ring type structure by (methyl) acrylate polymer Monomer (a1), containing aromatic rings monomer (a2) or hydroxyl monomer (a3) as constituting monomeric unit.

(2) isocyanates cross-linking agent (B)

Isocyanates cross-linking agent (B) has and is had with (methyl) acrylate copolymer (A) The reactive excellent advantage of some hydroxyls (being derived from hydroxyl monomer (a3)).

Isocyanates cross-linking agent (B) at least contains polyisocyanate compounds.As polyisocyanate Ester compounds, such as, can enumerate: toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, benzene The aromatic poly-isocyanates such as dimethylene diisocyanate；The fat such as hexamethylene diisocyanate Adoption isocyanates；The fat such as isoflurane chalcone diisocyanate, hydrogenated diphenyl methane diisocyanate Ring type polyisocyanate, in addition, also has their biuret body, isocyanuric acid ester body, with And with the low molecule such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, Oleum Ricini containing living Property hydrogen compound product i.e. add adult (be to sum up sometimes referred to as " modified body ") etc..In them, From the point of view of the durability of obtained sticker, preferably there is the compound i.e. virtue of aromatic rings Fragrant adoption isocyanates or its modified body, particularly preferably have via organic group (for example, it is preferable to can Enumerate alkylidene chain, particularly preferably can enumerate the alkylidene chain of carbon number 1～4) and fragrance ring key The polyisocyanate of the NCO closed or its modified body.Specifically, further preferred benzene two Methylene diisocyanate or its modified body, most preferably trimethylolpropane modification phenylenedimethylidyne Diisocyanate.Above-mentioned isocyanates cross-linking agent (B) can be used alone one, it is also possible to group Close two or more use.

The content of the isocyanates cross-linking agent (B) in cohesiveness compositions P is relative to (methyl) Acrylate copolymer (A) 100 mass parts, preferably 0.01～10 mass parts, particularly preferably 0.05～5 mass parts, further preferred 0.1～0.4 mass parts.By isocyanates cross-linking agent (B) Content easily enter described scope at above-mentioned scope, the gel fraction of sticker, the durability that is easy to get, Warpage inhibition and the sticker of heat-resisting inequality excellence.

(3) antistatic additive (C)

Cohesiveness compositions P contains antistatic additive (C).Be laminated in adhering agent layer stripping film or The optical thin films such as person's polaroid or composite polarizing plate are generally molded of plastic material, therefore electrical insulating property Height, as peel off stripping film time etc. be easily generated electrostatic.Under the state remaining so electrostatic of generation, When polaroid or composite polarizing plate etc. are fitted in liquid crystal cells, the orientation of liquid crystal molecule may produce Disorder, it addition, the existence of electrostatic can cause the attraction problem such as flying dust or dust and dirt.Here, by viscous The property compositions P contains antistatic additive (C), it is possible to make obtained sticker (adhering agent layer) Play antistatic behaviour, thus eliminate problem described above.

The antistatic additive (C) of present embodiment is for comprise the ionizing as anion of the fluorine sulfimide Compound.This antistatic additive (C) will not hinder by (methyl) acrylate copolymer (A) and different The durability of the sticker that cyanate cross-linking agent (B) is formed, and electrically conducting transparent erosion will not be made. Therefore, the sticker containing above-mentioned antistatic additive (C) can take into account antistatic behaviour and durability, and And for the excellent corrosion resistance of nesa coating, it is possible to maintain the outward appearance of nesa coating well. Here, the ionic compound of this specification refers to that cation and anion are mainly tied by electrostatic attraction The compound closed.

As the cation comprised in above-mentioned ionic compound, there is no particular restriction, but preferably contains Nitrogen heterocyclic cation.That is, antistatic additive (C) is preferably by nitrogen heterocyclic ring cation and fluorine sulphonyl sub- The ionic compound that amine (anion) is constituted.This ionic compound from antistatic behaviour, durability and From the point of view of the corrosion resistance of nesa coating, particularly preferably.

As the nitrogen heterocyclic ring skeleton of above-mentioned nitrogen heterocyclic ring cation, preferably pyridine ring, pyrimidine ring, Imidazole ring, triazole ring, indole ring etc., the most preferably pyridine ring.It addition, above-mentioned fluorine sulphonyl is sub- The most double (fluorine sulphonyl) imines of amine.

Above-mentioned ionic compound is the most at room temperature solid.If being at room temperature solid, even if then It is exposed to durable condition, the most easily presents stable antistatic behaviour.

As the concrete example of above-mentioned antistatic additive (C), double (the fluorine sulphur of N-decyl pyridine can be enumerated Acyl) imines, double (fluorine sulphonyl) imines of 1-ethylpyridine, 1-butyl-pyridinium be double (fluorine sulphonyl) Double (fluorine sulphonyl) imines of imines, 1-hexyl pyridine, 1-butyl-3-picoline are double (fluorine sulphonyl) Double (fluorine sulphonyl) imines of imines, 1-butyl-4-picoline, 1-hexyl-3-picoline are double (fluorine sulphonyl) imines, 1-butyl-3, double (fluorine sulphonyl) imines of 4-lutidines etc..They In, from the point of view of for the corrosion resistance of nesa coating, the double (fluorine of preferably N-decyl pyridine Sulphonyl) imines.Above antistatic additive (C) can be used alone one, it is possible to combines two or more Use.

The content of the antistatic additive (C) in the cohesiveness compositions of present embodiment is relative to (methyl) Acrylate copolymer (A) 100 mass parts, preferably 0.1～15 mass parts, particularly preferably 0.5～10 mass parts, more preferably 1～5 mass parts.By the content by antistatic additive (C) If within the above range, it is possible to effectively play antistatic behaviour, and be prevented from optical characteristics or The decline of the physical property such as durability.

(4) silane coupler (D)

In cohesiveness compositions P, in addition to mentioned component, further preferably contain silane coupler (D), From the point of view of the durability that sticker obtained by giving is excellent, particularly preferably containing containing ring TMOS coupling agent (D1) and/or (D2) Han mercaptosilane coupling agents, more preferably contain Have containing epoxy silane coupling (D1) and containing both mercaptosilane coupling agents (D2).

As containing epoxy silane coupling (D1), desirably intramolecular has at least one epoxy Base (organic group containing epoxy radicals) and at least one alkoxysilane group (alkoxysilyl group) Organo-silicon compound, and good with the compatibility of sticker composition and there is light transmission, such as Substantially transparent.

As the concrete example containing epoxy silane coupling (D1), can enumerate: 3-(+)-2,3-Epoxy-1-propanol oxygen The 3-(+)-2,3-Epoxy-1-propanols such as base propyl trimethoxy silicane, 3-glycidoxypropyl triethoxysilane Epoxide propyl trialkoxy silane；3-glycidoxypropyl diethoxy silane, 3-shrink The 3-glycidoxypropyl alkyl dialkoxy silicon such as glycerol epoxide hydroxypropyl methyl dimethoxysilane Alkane；Methyl three (glycidyl) silane；2-(3,4-expoxycyclohexyl) ethyl trimethoxy 2-(the 3,4-epoxycyclohexyethylSiOi such as silane, 2-(3,4-expoxycyclohexyl) ethyl triethoxysilane Base) ethyltrialkoxysilanes etc..Wherein, from the point of view of more improving durability, 3-shrinks Glycerol epoxide propyl trimethoxy silicane, 3-glycidoxypropyl triethoxysilane, 3-shrink Glycerol epoxide hydroxypropyl methyl diethoxy silane, 2-(3,4-expoxycyclohexyl) ethyl trimethoxy Silane is preferably, particularly preferably 3-glycidoxypropyltrimewasxysilane.They are permissible It is used alone one, it is also possible to be used in combination of two or more.

As containing mercaptosilane coupling agents (D2), desirably intramolecular has at least one sulfydryl and (contains The organic group of sulfydryl) and the organo-silicon compound of at least one alkoxysilane group, and with adhesion The compatibility of agent composition is good and has light transmission, the most substantially transparent.

As the concrete example containing mercaptosilane coupling agents (D2), can enumerate: 3-mercaptopropyi front three TMOS, 3-Mercaptopropyltriethoxysilane, 3-mercaptopropyi dimethoxymethylsilane etc. contain Sulfydryl low molecule type silane coupler；And (the such as 3-mercaptopropyi three Han mercaptosilane compound Methoxy silane, 3-Mercaptopropyltriethoxysilane, 3-mercaptopropyi dimethoxymethylsilane etc.) With containing alkyl silane cpd (such as MTES, ethyl triethoxysilane, first Base trimethoxy silane, ethyl trimethoxy silane etc.) cocondensation compound etc. containing sulfydryl oligomer type Silane coupler etc..Wherein, from the point of view of taking into account durability and operability again, preferably containing mercapto Base oligomer type silane coupler, particularly preferably containing mercaptosilane compound and containing alkyl silicon alkanisation The cocondensation compound of compound, more preferably 3-mercaptopropyi trimethoxy silane and methyl three ethoxy The cocondensation compound of base silane.They can be used alone one, it is also possible to is used in combination of two or more.

As silane coupler (D), except above-mentioned containing epoxy silane coupling (D1) and contain Outside mercaptosilane coupling agents (D2), it is also possible to as required and with such as, acryloyl one type of silane Coupling agent, hydroxy kind silane coupler, carboxyl one type of silane coupling agent, amino silane coupler, Amide groups one type of silane coupling agent, NCO one type of silane coupling agent etc..

The total content of the silane coupler (D) in cohesiveness compositions P is relative to (methyl) third Olefin(e) acid ester copolymer (A) 100 mass parts, preferably 0.01～5 mass parts, particularly preferably 0.1～2 Mass parts, more preferably 0.2～1 mass parts.

It addition, the content containing epoxy silane coupling (D1) in cohesiveness compositions P is relative In (methyl) acrylate copolymer (A) 100 mass parts, preferably 0.005～2.5 mass parts, Particularly preferably 0.05～1 mass parts, more preferably 0.1～0.5 mass parts.On the other hand, viscous The content containing mercaptosilane coupling agents (D2) in the property compositions P is relative to (methyl) propylene Acid ester copolymer (A) 100 mass parts, preferably 0.005～2.5 mass parts, particularly preferably 0.05～1 Mass parts, more preferably 0.1～0.5 mass parts.

(5) various additives

Cohesiveness compositions P can be added as needed on be typically used in acrylic compounds sticker Various additives, such as can add dispersant (such as, alkylene glycol dialkylether), viscosifier, Antioxidant, UV absorbent, light stabilizer, softening agent, filler, refractive index adjusters Deng.It addition, cohesiveness compositions P represents in adhering agent layer with former state or to have carried out reaction Removed composition in the mixture of various compositions of state residual, and drying process etc., such as Polymer solvent described later or retarder thinner are not included in cohesiveness compositions P.

(preparation method of cohesiveness compositions)

Cohesiveness compositions P can be prepared by the following method: preparation (methyl) acrylic ester copolymer Thing (A), cross-links obtained (methyl) acrylate copolymer (A) with isocyanates Agent (B), antistatic additive (C) and the silane coupler (D) being added as needed on and additive Etc. carrying out mixing preparing.

(methyl) acrylate copolymer (A) can be by constituting with common radical polymerization Prepared by the mixture polymerization of the monomeric unit of polymer.(methyl) acrylate copolymer (A) Polymerization can use polymerization initiator as required and utilize solution polymerization process etc. to carry out.As poly- Bonding solvent, such as can enumerate ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, Hexane, butanone etc., it is possible to and with two or more.

As polymerization initiator, azo compound, organic peroxide etc. can be enumerated, it is possible to and With two or more.As azo compound, such as, can enumerate 2,2'-azobis isobutyronitrile, 2,2'- Azo double (2-methylbutyronitrile), 1,1'-azo double (hexamethylene 1-nitrile), double (the 2,4-diformazan of 2,2'-azo Base valeronitrile), 2,2'-azo double (2,4-dimethyl-4-methoxyl-valeronitrile), the double (2-of dimethyl 2,2'-azo Methylpropionate), 4,4'-azo double (4-cyanovaleric acid), 2,2'-azo double (2-hydroxymethyl propionitrile), 2,2'-azo double [2-(2-imidazoline-2-base) propane] etc..

As organic peroxide, such as can enumerate benzoyl peroxide, t-butyl perbenzoate, Cumene hydroperoxide, di-isopropyl peroxydicarbonate, peroxy dicarbonate di-n-propyl ester, two (2-ethoxyethyl group) peroxy dicarbonate, new peroxide tert-butyl caprate, peroxidating neopentanoic acid The tert-butyl ester, (3,5,5-trimethyl acetyl base) peroxide, two propiony peroxide, diacetyl Peroxide etc..

It addition, in above-mentioned polymerization process, by adding the chain-transferring agents such as 2 mercapto ethanol, it is possible to The weight average molecular weight of the polymer obtained by regulation.

After obtaining (methyl) acrylate copolymer (A), to (methyl) acrylic ester copolymer The solution of thing (A) adds isocyanates cross-linking agent (B), antistatic additive (C), Yi Jigen Add silane coupler (D), additive, retarder thinner etc. according to needs and be sufficiently mixed, thus To cohesiveness compositions P (coating solution) after solvent dilution.

As for diluting cohesiveness compositions P to form the retarder thinner of coating solution, such as may be used To use: aliphatic hydrocarbons such as hexane, heptane, hexamethylene；The aromatic hydrocarbon such as toluene, dimethylbenzene； The halogenated hydrocarbons such as dichloromethane, ethlyene dichloride；Methanol, ethanol, propanol, butanol, 1-methoxyl group-2- The alcohol such as propanol；The ketone such as acetone, butanone, 2 pentanone, isophorone, Ketohexamethylene；Ethyl acetate, The esters such as butyl acetate；The cellosolve type solvents etc. such as ethyl cellosolve.

As concentration and the viscosity of the coating solution being prepared, as long as in the range of can being coated with, then There is no particular restriction, can select the most aptly.Such as, by cohesiveness compositions P Concentration dilution become 10～40 mass %.It addition, when obtaining coating solution, add retarder thinner etc. Not necessarily condition, as long as the viscosity of cohesiveness compositions P is the viscosity etc. that can be coated, Can also be without retarder thinner.In the case of Gai, cohesiveness compositions P becomes (methyl) third The polymer solvent of olefin(e) acid ester copolymer (A) is directly as the coating solution of retarder thinner.

The sticker of present embodiment is obtained, specifically by cohesiveness compositions P described above Form for cohesiveness compositions P is carried out crosslinking.The crosslinking of cohesiveness compositions P can be by heating Process and carry out.Additionally, it is possible to by when the retarder thinner etc. of cohesiveness compositions P is volatilized Dried double as this heat treated.

When carrying out heat treated, heating-up temperature is preferably 50～150 DEG C, particularly preferably 70～120 DEG C. It addition, be preferably heat time heating time 30 seconds～10 minutes, particularly preferably 50 seconds～2 minutes.Heating After process, it is possible to set as required under room temperature (such as, 23 DEG C, 50%RH) about 1～2 week Maturation period.When needing this maturation period, after the maturation period, forming the adhesion possessing regulation physical property Oxidant layer, during without the maturation period, is then formed after heat treated terminates and possesses the viscous of regulation physical property Oxidant layer.

By above-mentioned heat treated (and ripening), (methyl) acrylate copolymer (A) is by different Cyanate cross-linking agent (B) cross-links, and forms tridimensional network.

(adhesive sheet)

The adhesive sheet of present embodiment possesses the adhering agent layer being made up of described sticker.Can glue in this The one or both sides stacking stripping film of oxidant layer.Additionally, it is possible to the one side stacking in adhering agent layer is shelled From sheet, and in the base material desired by another side stacking.It addition, when this base material is optical thin film, In this manual, this adhesive sheet is equivalent to the aftermentioned optical thin film with adhering agent layer.

The thickness of adhering agent layer suitably determines according to the application target of adhesive sheet, usually The scope of 5～100 μm, the scope of preferably 10～60 μm, such as, as the adhesion of optical thin film Oxidant layer and when using, preferably 10～50 μm, particularly preferably 15～30 μm.

As stripping film, can use such as polyethylene film, polypropylene film, polybutene thin film, Polybutadiene membrane, poly-methyl pentene film, polyvinyl chloride film, vinyl chloride copolymer thin film, Pet film, PEN thin film, poly terephthalic acid Butanediol ester thin film, polyurethane film, ethylene vinyl acetate thin film, ionomer resin Thin film, ethylene-(methyl) acrylic copolymer thin film, ethylene-(methyl) acrylate copolymer Thin film, polystyrene film, polycarbonate film, Kapton, fluorine resin film etc.. It addition, be used as their crosslinked film.It can also be their laminate film.

Preferably at least one side (release surface especially connected with adhering agent layer) of above-mentioned stripping film Implement lift-off processing.As the remover used in lift-off processing, such as, can enumerate alkyd resin Class, silicone, fluorine class, unsaturated polyester esters, TPO, the remover of wax class.It addition, The release surface of the stripping film in this specification refers to the face on stripping film with fissility, also comprises reality Execute the face after lift-off processing and be not carried out that lift-off processing also shows that in the face of fissility arbitrary Person.

When the upper stacking stripping film on the two sides of adhering agent layer, preferably using the stripping film of side as stripping From the exfoliated stripping film of the weight that power is big, and using the stripping film of opposite side as the little stripping of peeling force Type stripping film.

Thickness for stripping film is not particularly limited, but usually about 20～150 μm.

It is not particularly limited as base material, all substrate sheets as common adhesive sheet can be used And the base material used.Such as in addition to desired optical component (optical thin film), also can lift Go out: employ the fibers such as artificial silk (rayon), acrylon (acrylic), polyester spins cloth or nonwoven Cloth；Synthetic paper；The stationeries such as good quality paper, cellophane, dipping paper, coating paper；The metal such as aluminum, copper Paper tinsel；The foaming bodies such as carbamate foaming body, foam polyethylene；Polyethylene terephthalate Mylar, the polyurethane such as ester, polybutylene terephthalate (PBT), PEN Cellulose membrane, the polychlorostyrene second such as thin film, polyethylene film, polypropylene film, triacetyl cellulose Alkene thin film, polyvinylidene chloride film, polyvinyl alcohol film, vinyl-vinyl acetate copolymer are thin Film, polystyrene film, polycarbonate film, acrylic resin films, norbornene resin The plastic sheetings such as thin film, cyclic olefin resins thin film；And their two or more duplexer etc.. Plastic sheeting can be formed by uniaxial extension or twin shaft extension.

The thickness of base material can also be different according to its kind, but usually 5～500 μm, it is preferably 10～300 μm, particularly preferably 20～150 μm.

As the example of preparation method of the adhesive sheet of present embodiment, in the release surface of stripping film The coating solution of coating cohesiveness compositions P, carry out heat treated and after forming film, according to need Want, other stripping films of stacking (in the way of release surface connects with film) or base material on this film. Above-mentioned film, when need not the maturation period, directly forms adhering agent layer, and when the needs maturation period, Adhering agent layer is being formed after the maturation period.Condition about heat treated and ripening is described above.

As be coated with above-mentioned coating solution method, can use such as stick coating method, scraper for coating method, Roller rubbing method, scraper plate rubbing method, die coating methods, gravure coating process etc..

The haze value of the adhering agent layer of the adhesive sheet of present embodiment is (according to JIS K7136:2000 The value measured) it is preferably less than 2%, particularly preferably less than 1%.If haze value is less than 2%, Then the transparency is the highest, it is adaptable to optical applications.

(with the optical thin film of adhering agent layer)

The composition of the optical thin film with adhering agent layer of present embodiment is, possess optical thin film, And it is laminated in the adhering agent layer of at least one side of this optical thin film.Adhering agent layer is by above-mentioned enforcement The sticker of mode is formed, or is made up of the adhering agent layer of the adhesive sheet of above-mentioned present embodiment.Viscous The thickness transitivity oxidant layer is identical with the adhering agent layer of described adhesive sheet.

Optical thin film can be made up of monolayer, it is also possible to is made up of multilamellar.As optical thin film, example As polarizer, polaroid, polarizer, compound partially with the polaroid etc. of polarizer can be enumerated Sheet, angle compensation films, brightness enhancing films, contrast enhanced film, the liquid crystal polymer of shaking is thin Film, diffusion film, semi-penetration thin film and their duplexer etc..Wherein, from requiring Polarizer be easily shrink, change in size is big, from the point of view of durability, comprise the optics of polarizer Thin film is suitably as the optical thin film of the optical thin film with adhering agent layer of present embodiment.Especially Protective layer is through the slim polaroid of filming and employs the composite polarizing plate of this polaroid, by Weak in the power of the contraction of its protective layer suppression polarizer, easily shrink because of heat etc., therefore, optimum Optical thin film as the optical thin film with adhering agent layer of present embodiment.

Here, the face connected with adhering agent layer of optical thin film also can be made up of acrylic resin. It addition, the outermost layer connected with adhering agent layer of optical thin film also can be formed by extruded molding Acrylic resin is constituted.This acrylic resin and the attaching of known adhering agent layer Low, durability is the lowest, but according to the adhering agent layer of present embodiment even for acrylic resin Bonding force the highest, and stress relaxation is excellent.Therefore, under the high temperature conditions, wet heat condition Under, thermal shock inferior, durability is the most excellent.It addition, " extruded molding and the acrylic compounds that formed Resin bed " in also comprise extrusion molding after carry out acrylic resin that is prolonged treatment and that obtain.

1. optical thin film is the example of polaroid

With reference to Fig. 1 illustrate optical thin film be present embodiment during polaroid with adhering agent layer One example of optical thin film.As it is shown in figure 1, the optical thin film with adhering agent layer of present embodiment The composition of 10A is, possesses: polaroid 2A；And it is laminated in one side (Fig. 1 of polaroid 2A In be the face of downside) adhering agent layer 1.It addition, although not shown, it is possible to adhering agent layer 1 with Stacking stripping film on the face of polaroid 2A side opposite side, until with the optical thin film of adhering agent layer 10A is used.

Adhering agent layer 1 is formed by the sticker of above-mentioned present embodiment.

The composition of the polaroid 2A in present embodiment is to possess: polarizer 21；It has been laminated in First protective layer 22 of the one side (being the face of upside in Fig. 1) of polariscope 21；And be laminated in and be polarized Second protective layer 23 of the another side (being the face of downside in Fig. 1) of mirror 21.It addition, although not shown, Also can be between polarizer 21 and the first protective layer 22 and/or polarizer 21 and the second protective layer 23 Between be clamped with bond layer.

(1) polarizer

The polyvinyl alcohol resin thin film that polarizer 21 is adsorbed orientation by dichroic dye is configured to excellent Choosing.

The polyvinyl alcohol resin constituting polarizer 21 can be by carrying out polyvinyl acetate esters resin Saponification and obtain.As polyvinyl acetate esters resin, except the homopolymer of vinyl acetate is the most poly- Outside vinyl acetate, also exemplify vinyl acetate and can be with being total to of other monomers of its copolymerization Polymers etc..As such as can enumerating unsaturated carboxylic acid with other monomers of vinyl acetate copolymerization Class, olefines, vinyl ethers, unsaturated sulfonic acid class etc..

The saponification degree of polyvinyl alcohol resin usually 85～100 moles of %, it is preferably 98～100 and rubs In the range of you %.Polyvinyl alcohol resin also can be modified further.Such as, it is possible to use by aldehydes Modified polyvinyl formal or Pioloform, polyvinyl acetal etc..The degree of polymerization of polyvinyl alcohol resin is led to It is often 1,000～10,000, preferably 1,500～5, in the range of 000.

By preferably preparing polarizer 21 described above through following operation, described operation has: Polyvinyl alcohol resin thin film is carried out uniaxial extension；With dichroic dye to polyvinyl alcohol resin Thin film carries out dyeing and make this dichroic dye to be adsorbed；And with boric acid aqueous solution to being adsorbed with two The polyvinyl alcohol resin thin film of color dyestuff processes.

Uniaxial extension can be carried out before dyeing with dichroic dye, it is possible to contaminates with dichroic dye The process of color is carried out simultaneously, also can carry out after dyeing with dichroic dye.Contaminating by dichromatic When carrying out uniaxial extension after material dyeing, this uniaxial extension can be carried out before boric acid processes, it is possible to Boric acid processing procedure is carried out.Of course it is also possible to carry out uniaxial extension in these multiple stages. When carrying out uniaxial extension, can be to uniaxial extension between the roller that peripheral speed is different, it is possible to use heat Roller is to uniaxial extension.Furthermore it is possible to extend for carrying out the dry type that extends in an atmosphere, it is possible to for The wet type carrying out extending under the state of solvent swelling extends.Extension ratio is usually about 4～8 times.

When polyvinyl alcohol resin thin film being dyeed with dichroic dye, such as, by polyethylene Alcohol based resin film impregnated in the aqueous solution containing dichroic dye.As dichroic dye, Specifically can use iodine or dichroic organic dye.

When using iodine as dichroic dye, generally use by thin film dipped for polyvinyl alcohol resin in The method carrying out dyeing in aqueous solution containing iodine and potassium iodide.The content of iodine in this aqueous solution Relative to every 100 mass parts water, usually about 0.01～0.5 mass parts, the content phase of potassium iodide For every 100 mass parts water, usually about 0.5～10 mass parts.The temperature of this aqueous solution is usual It it is about 20～40 DEG C, it addition, the dip time (dyeing time) in this aqueous solution is usually About 30～300 seconds.

Boric acid after dyeing with dichroic dye processes by by dyed polyvinyl alcohol resin Thin film dipped carry out in boric acid aqueous solution.The content of the boric acid in boric acid aqueous solution is relative to every 100 Mass parts water, usually about 2～15 mass parts, about preferably 5～12 mass parts.Use iodine During as dichroic dye, preferably containing potassium iodide in this boric acid aqueous solution.In boric acid aqueous solution The content of potassium iodide is relative to every 100 mass parts water, usually about 2～20 mass parts, is preferably 5～15 mass parts.Dip time in boric acid aqueous solution is usually 100～1, about 200 seconds, excellent Elect about 150～600 seconds as, more preferably about 200～400 seconds.The temperature of boric acid aqueous solution Degree usually more than 50 DEG C, preferably 50～85 DEG C.

Polyvinyl alcohol resin thin film after boric acid processes generally is washed with water process.Washing processes logical Cross and such as carry out thin film dipped for the polyvinyl alcohol resin processed through boric acid in water.After washing It is dried process, thus obtains polarizer 21.Water temperature during washing processes is usually 5～40 DEG C of left sides The right side, dip time is usually about 2～120 seconds.Dried followed by generally uses hot blast Drying machine or far infra-red heater are carried out.Baking temperature is usually 40～100 DEG C.It addition, it is dry The dry process time is usually about 120～600 seconds.

The thickness of polarizer 21 is preferably about 3～50 μm, when being especially required filming, preferably About 3～15 μm.

(2) protective layer

First protective layer 22 and the second protective layer 23 are (the most sometime collectively referred to as " protective layer 22,23 " Situation) be configured to preferred by transparent resin film.The transparent resin constituting protective layer 22,23 is thin Film can be without the thin film extended or any one in the thin film that single shaft or twin shaft extend.

The main constituent of transparent resin film be preferably selected from by polyester resin, polycarbonate resin, In the group that acrylic resin, amorphous polyolefins resinoid and cellulosic resin are constituted extremely Few a kind of resin.

As the amorphous polyolefins resinoid for protective layer 22,23, preferably cycloolefin resinoid. As cycloolefin resinoid, such as, can enumerate: will from cyclopentadiene and olefines by diels-Ah The norborene or derivatives thereof that Er De reaction obtains carries out ring-opening metathesis polymerization as monomer After (metathesis polymerization), then carry out hydrogenating and the resin that obtains；Will be from bicyclo- The Fourth Ring ten that pentadiene is obtained by Diels-Alder reaction with olefines or methyl acrylic ester After diene (tetracyclododecene) or derivatives thereof carries out ring-opening metathesis polymerization as monomer, Then the resin carrying out hydrogenating and obtain；Use selected from norborene, tetracyclododecen and they Derivatives class and other cyclic polyolefin hydrocarbon monomers two or more, similarly carry out open loop easy After the polymerization of position, then carry out hydrogenating and the resin that obtains；Make norborene, tetracyclododecen or he Derivant carry out addition copolymerization with the aromatic compound etc. with vinyl and the resin that obtains Deng.As the commercially available resinoid example of amorphous polyolefins, can enumerate, JSR " ARTON " of CORPORATION, " ZEONEX " of Zeon Corporation and " ZEONOR ", Mitsui Chemicals, " APO " and " APEL " of Inc etc..Amorphism is gathered Olefine kind resin is filmed and during as thin film, can suitably use solvent casting method, molten in masking Melt the known methods such as extrusion molding.

As cellulosic resin, for the hydroxyl in cellulose at least some of by acid esterification Resin, it is also possible to for a part by acid esterification and a part by other Esterification mixed esters.Fine Dimension element resinoid is preferably cellulose esters resinoid, more preferably acetylcellulose resinoid.As The resinoid concrete example of acetylcellulose, can enumerate triacetyl cellulose, diacetyl cellulose, second Acid cellulose propionate, cellulose acetate-butyrate etc..As by such acetylcellulose resinoid structure The commercially available product of the thin film become, such as, can enumerate: " Fujitac prepared by FUJIFILM Corporation TD80 ", " Fujitac TD80UF " and " Fujitac TD80UZ "；Konica Minolta Opto " KC8UX2M ", " KC2UA " and " KC8UY " prepared by Products Co., Ltd. etc..

It is used as being endowed the cellulosic resin thin film of optical compensation function.Mend as this optics Repay thin film, such as, can enumerate: containing the change with adjusting offset function in cellulosic resin The thin film of compound；The surface of cellulosic resin is coated with the change with adjusting offset function The thin film of compound；And cellulosic resin single shaft or twin shaft are extended and the thin film etc. that obtains. The example of the optical compensating film of the cellulosic resin of city's mid-sales can be enumerated: FUJIFILM " Wide view Film WV BZ 438 " and " Wide view Film WV prepared by Corporation EA ", Konica Minolta Opto Products Co., " KC4FR-1 " prepared by Ltd. and " KC4HR-1 " etc..

Protective layer 22,23 also can contain UV absorbent.This is because, by will be containing ultraviolet The protective layer of light absorbers be configured at liquid crystal cells depending on recognizing side, it is possible to protection liquid crystal cells not because of purple Outside line deteriorates.

Here, the first protective layer 22 and the second protective layer 23 can be by the transparent resins of identical type Thin film is constituted, it is possible to be made up of different types of transparent resin film.

Protective layer 22,23 before fitting in polarizer 21, can to binding face implement saponification process, The easy bonding process such as sided corona treatment, prime treatment, anchor coating process.It addition, protective layer 22,23 The surface of the binding face opposite side with polarizer 21 can have hard conating, anti-reflecting layer, anti-dazzle The various process layers such as layer.

The thickness of protective layer 22,23 is usually the scope about 5～200 μm, is preferably 10～120 μm, particularly preferably 10～85 μm, more preferably 10～30 μm.

First protective layer 22 is preferably made up of cellulosic resin, more preferably by fiber among above-mentioned Element esters resin is constituted, and is particularly preferably made up of acetylcellulose resinoid, further preferably by three Acetylcellulose is constituted.

Second protective layer 23 is preferably made up of amorphous polyolefins resinoid among above-mentioned, the most excellent Choosing is made up of described cycloolefin resinoid.In this case, adhering agent layer 1 is for the second protective layer The bonding force of 23 is the highest, therefore, with adhering agent layer optical thin film 10A under the high temperature conditions, Under wet heat condition, thermal shock inferior, durability is the most excellent.

(3) bond layer

Also it can be clamped between polarizer 21 and the first protective layer 22 and/or polarizer 21 as constituting And the bonding agent of the bond layer between the second protective layer 23, can be according to the kind of adherend and purpose And use suitable bonding agent aptly.Such as can enumerate solvent type adhesive, emulsion-type adhesive, Aqueous adhesive, pressure adhesive, remoistenable adhesive, condensation polymer type bonding agent, no-solvent type are viscous Connect agent, film like bonding agent, hot melt adhesive etc..

The preferred bonding agent constituting above-mentioned bonding agent is aqueous adhesive, and its typical example is with poly- Vinyl alcohol resin is main constituent.As the commercially available polyvinyl alcohol tree that can be aqueous adhesive Fat, such as, have " KL-318 " prepared by KURARAY CO., LTD etc..

Above-mentioned aqueous adhesive can contain cross-linking agent.As cross-linking agent, preferred amines compound, hydroformylation Compound, methylol compound, epoxide, isocyanate compound, multivalent metal salt etc., Particularly preferably epoxide.As the commercially available product of cross-linking agent, such as, there are Biformyl or Sumika " the Sumirez of the aqueous solution of the soluble epoxide compound that Chemtex Company, Limited sell Resin650 (30) " etc..

As other preferred bonding agents, can enumerate by containing being irradiated by active energy beam or adding Heat and bonding agent that the epoxylite compositions of epoxy resin that solidifies is constituted.Use this bonding agent Time, the bond layer being held between thin film is irradiated active energy beam by bonding the passing through between thin film Or heating, and the curable epoxy resin solidification contained by bonding agent is made to carry out.Based on active-energy The solidification of the epoxy resin irradiating or heating of ray, preferably by the cationic polymerization of epoxy resin Carry out.It addition, the epoxy resin in this specification refers to have two or more epoxy in intramolecular The compound of base.

From the point of view of weatherability, refractive index, cationically polymerizable, as the solidification of bonding agent Property composition epoxy resin in contained epoxy resin, the preferably intramolecular asphalt mixtures modified by epoxy resin without aromatic rings Fat.As such epoxy resin, hydrogenated epoxy resin, alicyclic epoxy resin, fat can be illustrated Fat race epoxy resin etc..

(4) preparation method of polaroid

The preparation of polaroid 2A can be carried out by usual way.Hereinafter, as an example, to use Aqueous adhesive illustrates as preparation method during above-mentioned bonding agent.

First, the binding face of polarizer 21 or the binding face of protective layer 22,23 are formed bonding Oxidant layer.The formation of bond layer may utilize such as rod coating method, scraper for coating method, roller rubbing method, Scraper plate rubbing method, die coating methods, gravure coating process etc..It addition, also be able to use so that both Binding face become the mode of inner side and supply polarizer 21 and protective layer 22,23 continuously, simultaneously in it The mode of chien shih bonding agent curtain coating.After coating adhesive, implement heat treated as required and make water Divide evaporation, thus be dried bond layer.

The thickness of bond layer arbitrarily can set according to the characteristics design of polaroid 2A, but from reduction From the point of view of adhesive material cost, smaller is preferably, the bubble or different when suppression laminating From the point of view of the defects such as thing, the greater is preferably, from the point of view of attaching property, durability, It is embodied as preferably in optimum range determined by the combination as each adherend and bonding agent.Typically It is 0.005～10 μm, is preferably 0.01～5 μm, more preferably 0.03～1 μm.

When bonding polarizer 21 is with protective layer 22,23, it is possible to be in both binding faces One or both sides formed bonding agent coating layer before, implement as Corona discharge Treatment, plasma-based process, Easy the to be bonding process that flame treatment, prime treatment, anchor coating process.

As above, after forming bond layer, across this bond layer, the first protective layer 22 is fitted In the one side of polarizer 21, and the second protective layer 23 is fitted in the another side of polarizer 21. Thus, available it is laminated by the first protective layer 22, polarizer 21 and the second protective layer 23 Polaroid 2A.

The gross thickness of polaroid 2A is usually about 15～400 μm, from reply mobile communication purposes Slimming require and maintain polarization property from the point of view of, preferably 20～100 μm, particularly preferably It is 30～80 μm.

(5) has the preparation method of the optical thin film of adhering agent layer

As an example of the preparation method of the optical thin film 10A with adhering agent layer, it is ready for adhesion The adhesive sheet of the two sides stacking stripping film of oxidant layer is used as the adhesive sheet of above-mentioned present embodiment, And peel off the stripping film (light exfoliated stripping film) of side.Then, at the adhering agent layer weight exposed Second protective layer 23 of folded polaroid 2A, pressing adhesive sheet and polaroid 2A.Thus, on obtaining State the optical thin film 10A (with stripping film) with adhering agent layer.

As other examples of the preparation method of the optical thin film 10A with adhering agent layer, at stripping film Release surface on coating containing the solution (coating solution) of described cohesiveness compositions P, carry out at heating Reason and after forming film, second protective layer 23 of overlapping polaroid 2A on this film.Above-mentioned Film, when the needs maturation period, is spaced the maturation period and forms adhering agent layer 1, and need not the maturation period Time, directly form adhering agent layer 1.Thus, the optical thin film 10A with above-mentioned adhering agent layer is obtained (with stripping film).

2. optical thin film is the example of composite polarizing plate

Illustrate when optical thin film is this enforcement during composite polarizing plate with polarizer with reference to Fig. 2 One example of the optical thin film with adhering agent layer of mode.As in figure 2 it is shown, present embodiment is attached The composition having the optical thin film 10B of adhering agent layer is to possess composite polarizing plate 2B and be laminated in The adhering agent layer 1 of the one side (being the face of downside in Fig. 2) of composite polarizing plate 2B.Though it addition, not Diagram, it is possible to stacking is peeled off on the face with composite polarizing plate 2B side opposite side of adhering agent layer 1 Sheet, until being used with the optical thin film 10B of adhering agent layer.

Adhering agent layer 1 is formed by the sticker of above-mentioned present embodiment.

The composition of the composite polarizing plate 2B in present embodiment is to possess: contact with adhering agent layer 1 First phase difference plate 24；It is positioned at the side contrary with adhering agent layer 1 side of first phase difference plate 24 Second phase difference plate 25；It is held between first phase difference plate 24 and second phase difference plate 25 The second adhering agent layer 26；Be laminated in second phase difference plate 25 with the second adhering agent layer 26 side phase The polarizer 21 of anti-side；And it is laminated in plate poor with the second phase 25 side phase of polarizer 21 The protective layer 27 of anti-side.It addition, although not shown, it is also possible at polarizer 21 and protective layer Bond layer is clamped between 27 and/or between polarizer 21 and second phase difference plate 25.This is compound partially The sheet 2B that shakes can play viewing angle compensation performance well.

(1) first phase difference plate

First phase difference plate 24 can be made up of the monolayer of performance phase contrast, it is possible to by including phase meter The multilamellar of existing layer is constituted.Being preferably configured as of this first phase difference plate 24, possesses as shown in Figure 3: Phase contrast presentation layer 242；It is laminated in the one side (for the face of downside in Fig. 3) of phase contrast presentation layer 242 The first acrylic resin 241；And it is laminated in the another side (figure of phase contrast presentation layer 242 Be the face of upside in 3) the second acrylic resin 243.Phase contrast presentation layer 242 preferably by Styrene resin is constituted.So, there is the composite polarizing plate 2B of first phase difference plate 24 at liquid Crystal display device, especially regarding in IPS (In-Place-Switching) mode liquid crystal display device Angle compensation excellent performance, the composition of described first phase difference plate 24 is to possess the first acrylic compounds tree Lipid layer 241, styrene resin the phase contrast presentation layer 242 formed and the second acrylic compounds Resin bed 243.Further, since phase contrast presentation layer 242 is present in first acrylic acid on its two sides Resinoid layer 241 and the second acrylic resin 243 are protected, so first phase difference plate The mechanical strength of 24 and resistance to chemical reagents are excellent.

And, first phase difference plate 24 postpones in being preferably endowed face by extension.Thus, visual angle Compensate performance more excellent.

The styrene resin constituting phase contrast presentation layer 242 can be the equal of styrene or derivatives thereof Polymers, it is possible to more than styrene or derivatives thereof and the binary of other co-polymerized monomers or binary Copolymer.Styrene derivative refers to that on styrene, bond has the compound of other group, such as Can enumerate, as o-methyl styrene, a methyl styrene, p-methylstyrene, 2,4-dimethyl benzene Ethylene, the ring-alkylated styrenes of adjacent ethyl styrene, p-ethyl-styrene etc. or as hydroxy styrenes, T-butoxystyrene, vinyl benzoic acid, chloro styrene, cinnamic to chlorostyrene etc. The substituted phenylethylene etc. of hydroxyl, alkoxyl, carboxyl, halogen etc. it is imported with on benzene nucleus.

It is used as special in Japanese Unexamined Patent Publication 2003-50316 publication or Japan as styrene resin Open the terpolymer disclosed in 2003-207640 publication.

The styrene resin constituting phase contrast presentation layer 242 is preferably styrene or styrene derived Thing and at least one in acrylonitrile, maleic anhydride, methyl methacrylate and butadiene The copolymer of monomer.

It addition, as the styrene resin of composition phase contrast presentation layer 242, preferably have heat-resisting The styrene resin of property.The glass transition temperature (Tg) of styrene resin generally 100 DEG C Above, but the styrene resin that preferred glass transition temperature (Tg) is more than 120 DEG C.

The thickness of phase contrast presentation layer 242 is preferably 10～100 μm.By making phase contrast presentation layer The thickness of 242 is more than 10 μm, can be showed sufficient length of delay by extending.On the other hand, phase place When the thickness of difference presentation layer 242 is below 100 μm, impact strength is high, it addition, should based on outside The delay variation of power is little, it is adaptable to during liquid crystal display, is difficult to occur heat unequal.

First acrylic resin 241 and the second acrylic resin 243 are preferably by (first Base) acrylic resin is added with (methyl) acrylic resin composition structure of rubber grain Become.By adding rubber grain, the resistance to impact of acrylic resin can be improved.

As (methyl) acrylic resin, such as, can enumerate alkyl methacrylate or propylene The copolymer etc. of the homopolymer of acid alkyl ester or alkyl methacrylate and alkyl acrylate. As alkyl methacrylate, methyl methacrylate, ethyl methacrylate, first can be enumerated Base propyl acrylate etc..It addition, as alkyl acrylate, acrylic acid methyl ester., propylene can be enumerated Acetoacetic ester, propyl acrylate etc..Such (methyl) acrylic resin, can use as extensively (methyl) acrylic resin of general use and commercially available material.It addition, (methyl) acrylic compounds Resin also comprises: be referred to as impact resistance (methyl) acrylic resin or main chain has Glutaric anhydride structure or lactonic ring structure be referred to as high heat-resisting (methyl) acrylic resin.

The rubber grain making an addition to (methyl) acrylic resin is preferably acrylic compounds.Acrylic acid Class rubber grain refers to, with such as the alkyl acrylate such as butyl acrylate or 2-EHA For main constituent, and carry out being polymerized in the presence of polyfunctional monomer and obtain there is caoutchouc elasticity Granule.

The material with caoutchouc elasticity can be made the graininess of homogenizing and form by rubber grain, it is possible to for There is the multilayer structure making of at least one of which rubber elastic layer.Acrylic rubber as multiple structure Granule, can enumerate: have the granule of caoutchouc elasticity as core using the most above-mentioned, and will be about with hard The granule that the alkyl methacrylate polymer of matter covers；By the methacrylate of hard Esters polymer is as core, and will use such as the above-mentioned acrylic with caoutchouc elasticity about The granule that thing covers；Or, by the surrounding of the core of the hard acrylic polymer with caoutchouc elasticity Compound covers, and will cover with the alkyl methacrylate polymer of hard about further Granule etc..

The average diameter of rubber grain is preferably 50～about 400nm.The average diameter of rubber grain Can be measured by laser diffraction and scattering method.

Constitute the first acrylic resin 241 and (first of the second acrylic resin 243 Base) content of above-mentioned rubber grain is preferably in every 100 mass parts in acrylic resin composition In (methyl) acrylic resin, it is about 5～50 mass parts.

As constituting the first acrylic resin 241 and the second acrylic resin 243 (methyl) acrylic resin composition, can use with (methyl) acrylic resin and propylene The commercially available material of state of acids rubber grain mixing.As being added with acrylic rubber granule The example of the commercially available product of (methyl) acrylic resin ((methyl) acrylic resin composition), Can enumerate with trade name respectively: " HT55X " that Sumitomo Chemical Co., Ltd. are peddled or " TechnolloyS001 " etc..

The glass transition temperature (Tg) of (methyl) acrylic resin composition generally 160 DEG C Hereinafter, but (methyl) acrylic resin group that glass transition temperature (Tg) is less than 120 DEG C Compound is preferably, (methyl) acrylic resin composition of particularly preferably less than 110 DEG C.That is, The preferably glass transition temperature (Tg) of phase contrast presentation layer 242 and the first acrylic resin 241 And second the glass transition temperature (Tg) of acrylic resin 243 the most overlapping, preferably phase Potential difference presentation layer 242 has than the first acrylic resin 241 and the second acrylic resin Layer 243 higher glass transition temperature (Tg).

The material of the first acrylic resin 241 and the second acrylic resin 243 can be identical, Also can be different.

The thickness of the first acrylic resin 241 and the second acrylic resin 243 is respectively It is preferably 10～100 μm.If thickness is more than 10 μm, then can easily be filmed, if thick Degree is below 100 μm, then can ignore the first acrylic resin 241 and the second acrylic acid The delay of resinoid layer 243.Additionally, it is preferred that the thickness of the first acrylic resin 241 and The thickness of diacrylate resinoid layer 243 is roughly the same.

Face in the second adhering agent layer 26 side of first phase difference plate 24, it is possible to implement sided corona treatment Process on surface.

During preparation first phase difference plate 24, such as by styrene resin and be added with rubber grain Carry out extending after (methyl) acrylic resin composition coextrusion.Can be by the most single Axle extends, the horizontal uniaxial extension of stenter, simultaneously twin shaft extend or gradually twin shaft extension etc. is prolonged Stretch, as long as extending to obtain desired length of delay.In addition to the method described above, also Can make respectively single thin film (phase contrast presentation layer the 242, first acrylic resin 241 with And second acrylic resin 243) after, after making their thermal welding by heat lamination, by this layer Stack extends.

It addition, the gross thickness of the first phase difference plate 24 after Yan Shening, from maintaining sufficient performance and answering From the point of view of slimming in mobile communication purposes is required, preferably 5～100 μm, more preferably It is 10～50 μm, particularly preferably 15～30 μm.

The face connected with adhering agent layer 1 of first phase difference plate 24 is by the first acrylic resin 241 are constituted, and in this case, adhering agent layer 1 gluing for the first acrylic resin 241 Relay is the highest, therefore, with adhering agent layer optical thin film 10B under the high temperature conditions, damp and hot Under the conditions of, thermal shock inferior, durability is the most excellent.

(2) second phase difference plate

Second phase difference plate 25 is preferably made up of olefine kind resin.Olefine kind resin refers to by from ethylene And the chain fatty race alkene such as propylene or norborene or its substituent (following, also by him Be referred to as Norbornene derivative) etc. the resin that constituted of the derivative construction unit of ester ring type alkene. Olefine kind resin alternatively uses the copolymer of two or more monomers.

Wherein, as olefine kind resin, it is preferable to use cyclic olefin resinoid, this ring-type alkene Hydrocarbon resins is the resin mainly containing the construction unit derived by ester ring type alkene.As constituting ring The typical case of the ester ring type alkene of shape olefine kind resin can enumerate Norbornene derivative etc..Norborneol Alkene refers to that a carbon-carbon bond of norbornane becomes the compound of double bond, names according to IUPAC nomenclature For dicyclo [2,2,1] hept-2-ene".As the example of the substituent of norborene, by norborene Position of double bond is set to 1, during 2-position, can enumerate 3-substituent, 4-substituent, 4,5-is di-substituted, In addition, it is possible to using bicyclopentadiene or dimethano octahydro naphthalene etc. as composition cyclic olefin resinoid Monomer.

Cyclic olefin resinoid can have norbornane ring at its construction unit, it is possible to does not has.Make For being formed in construction unit the norborneol alkenes of the cyclic olefin resinoid without norbornane ring Monomer, such as, can enumerate and become 5 Yuans rings by open loop, representational enumerate norborene, Bicyclopentadiene, 1-or 4-methyinorbornene, 4-phenyl norbornene etc..Cyclic olefin resinoid During for copolymer, the ordered state of its molecule is not particularly limited, and can be random copolymer, can be embedding Section copolymer, it is possible to for graft copolymer.

As the more specifically example of cyclic olefin resinoid, such as, can enumerate Norbornene derivative Ring-opening polymerization polymer, the ring-opening copolymer of Norbornene derivative and other monomers, they are carried out The polymer modification thing of maleic acid addition or cyclopentadiene addition etc. and by they hydrogenations The polymer become or copolymer, the addition polymer of Norbornene derivative, Norbornene derivative Addition copolymer etc. with other monomers.As other monomers during copolymer, alpha-olefin can be enumerated Class, cyclenes hydro carbons, non-conjugated diene class etc..It addition, cyclic olefin resinoid alternatively employs One or more Norbornene derivative and the copolymer of other ester ring type alkene.

In above-mentioned concrete example, as cyclic olefin resinoid, it is preferable to use and ice is dropped in use The resin that the ring-opening polymerization polymer of sheet vinyl monomer is hydrogenated.Such cyclic olefin resinoid Polarizer is made, it is possible to by extending and both will have except implementing prolonged treatment to it The shrink film determining shrinkage factor fits and implements heat shrink process, and as uniformity height and tool There is the polarizer of big phase difference value.

As employing the commercially available product of cyclic olefin resinoid of Norbornene derivative (all with commodity Name) have, " ZEONEX " and " ZEONOR ", the JSR that Zeon Corporation is sold " ARTON " that CORPORATION is sold etc..The thin film of these cyclic olefin resinoids or its Extension film all can be obtained by commercially available product, such as, have (all with trade name), Zeon Corporation " the ZEONOR thin film " that sold, JSR CORPORATION sold " ARTON is thin Film ", SEKISUI CHEMICAL CO., " ESSINA " that LTD. is sold etc..

It addition, second phase difference plate 25 is used as by the mixing containing two or more olefine kind resins Resin constitute thin film or be made up of the hybrid resin of olefine kind resin with other thermoplastic resins Thin film.Such as, as the hybrid resin containing two or more olefine kind resins, can enumerate as above The cyclic olefin resinoid stated and the mixture of chain fatty race olefine kind resin.Use olefines tree During the hybrid resin of fat and other thermoplastic resins, suitable its can be selected aptly according to purpose His thermoplastic resin.As concrete example, can enumerate: polyvinyl chloride resin, cellulose family tree Fat, polystyrene resins, acrylonitrile/butadiene/styrene copolymer resins, acrylonitrile/styrene are common Poly resin, (methyl) acrylic resin, polyvinyl acetate esters resin, polyvinylidene chloride class Resin, polyamide-based resin, polyacetal-based resins, polycarbonate resin, modified polyphenyl ethers Resin, polybutylene terephthalate (PBT) resinoid, polyethylene terephthalate resinoid, Polyphenylene sulfide resinoid, polysulfones resin, polyether sulfone resin, polyether-ether-ketone resinoid, poly-virtue Esters resin, liquid-crystalline resin, polyamideimides resin, polyimide based resin, poly-four Fluorothene resinoid etc..Thermoplastic resin can only be used alone one, or combines two or more making With.It addition, above-mentioned thermoplastic resin also can use after carrying out the most suitable polymer modification. As the example of polymer modification, can enumerate: copolymerization, crosslinking, molecular end is modified, gives vertical Structure regularity (stereoregularity) etc..

When using the hybrid resin of olefine kind resin and other thermoplastic resins, other thermoplasticities The content of resin relative to all resins, usually about 50 mass % below, about 40 mass % It is below preferred.By the content of other thermoplastic resins is set within the range, it is possible to obtain The absolute value of photoelastic coefficient is little, show good wavelength dispersion characteristics, and durability, machinery Intensity and the polarizer of transparency excellence.

Olefine kind resin can be filmed by the casting method of solution or extrusion by melting etc..Use two When the above hybrid resin of kind is filmed, its film-forming method is not particularly limited, such as, can adopt With: use and resinous principle is together stirred, with both certainty ratios and solvent, the homogeneous solution being obtained by mixing And the method preparing thin film by casting method；Resinous principle is carried out melting mixing also with both certainty ratios The method etc. of thin film is prepared by extrusion by melting.

The thin film being made up of above-mentioned olefine kind resin also can contain residual solvent, stabilizer, plasticizer, Age resister, antistatic additive and UV absorbent etc., the most also can contain other compositions. Additionally, it is possible to containing levelling agent to reduce surface roughness.

The tables such as sided corona treatment also can be implemented in the face of the second adhering agent layer 26 side of second phase difference plate 25 Face processes.

Second phase difference plate 25 has that to meet the refractive anisotrop of following condition be preferred, this Part is, in slow-axis direction, face, the refractive index of quick shaft direction and thickness direction sets respectively in by face For n_x、n_yAnd n_z, and when the thickness of thin film is set to d, by ripple defined in following formula (1) Length of delay R in face during a length of 590nm_eIt is 30～150nm,

R_e=(n_x-n_y)×d (1)

And by Nz coefficient defined in following formula (2) more than 1 and less than 2,

Nz coefficient=(n_x-n_z)/(n_x-n_y) (2)。

There is the second phase difference plate 25 such as above-mentioned refractive anisotrop, can be by by above-mentioned alkene Longitudinal uniaxial extension of thin film of hydrocarbon resins composition, the horizontal uniaxial extension of stenter, simultaneously twin shaft Extend or gradually twin shaft extension etc. and obtain, and can be by suitably adjusting extension ratio and extension Speed and select preheating temperature when extending, elongating temperature, heat setting temperature, cold aptly But the various temperature of temperature etc. and pattern thereof, obtain desired refractive anisotrop.

Second phase difference plate 25, its thickness is preferably in the range of 5～80 μm, in 10～80 μm In the range of be it is further preferred that be particularly preferred in the range of 10～30 μm.

(3) second adhering agent layers

As constituting the sticker of the second adhering agent layer 26, known sticker can be used, can be solid The property changed sticker, it is possible to for non-curable sticker, but draw from suppression due to the thermal contraction of polaroid From the point of view of the change in size risen, active energy ray-curable sticker is preferably used.

Active energy ray-curable sticker can be with the polymer of active energy ray-curable As main constituent, it is also possible to the polymer of the most active energy ray-curable is penetrated with active-energy The mixture of line curable polyfunctional monomer and/or oligomer is as main constituent.It addition, can be to have The polymer of the polymer of active energy ray-curable and the most active energy ray-curable Mixture, it is possible to for polymer and the active energy ray-curable of active energy ray-curable Property polyfunctional monomer and/or the mixture of oligomer, can be also this mixture of 3 kinds.

In above-mentioned, examine from the angle being readily obtained the sticker maintaining cohesiveness and playing cohesiveness Consider, preferably with polymer and the active energy ray-curable of the most active energy ray-curable The mixture of polyfunctional monomer and/or oligomer is as main constituent, particularly preferably with the most active The mixture of the polymer of energy ray-curable and active energy ray-curable polyfunctional monomer is made For main constituent.

As the polymer of the most active energy ray-curable, the most active energy is penetrated (methyl) acrylate polymer (hereinafter sometimes referred to " (methyl) acrylic acid of line curable base Ester polymer (X) ").The carbon that (methyl) acrylate polymer (X) preferably comprises alkyl is former Subnumber is that (methyl) alkyl acrylate of 1～20 is as the monomer constituting this polymer.Thus, Obtained sticker can show preferred cohesiveness.It addition, (methyl) acrylate polymer (X) particularly preferably, the carbon number of alkyl be 1～20 (methyl) alkyl acrylate, Have reactive functional group monomer (containing reactive functional group monomer) and with made as required The copolymer of other monomers.By making (methyl) acrylate polymer (X) containing containing anti- Answering property functional group monomer is as the monomer constituting this polymer, it is possible to improve and the glass of liquid crystal cells etc. The attaching on glass surface, additionally, it is possible to form friendship by carrying out reacting with aftermentioned cross-linking agent (Z) Connection structure.

As (methyl) alkyl acrylate that carbon number is 1～20 of alkyl, such as, can enumerate: (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) N-butyl acrylate, (methyl) acrylic acid n-pentyl ester, the most own ester of (methyl) acrylic acid, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid ester in the positive last of the ten Heavenly stems, (first Base) acrylic acid dodecyl ester, (methyl) acrylic acid myristyl ester, (methyl) acrylic acid Cetyl ester, (methyl) octadecyl acrylate etc..Wherein, from improving cohesiveness further From the point of view of, the preferably carbon number of alkyl is (methyl) acrylate of 1～8, the most excellent Choosing (methyl) n-butyl acrylate.It addition, they can be used alone, it is also possible to combine two kinds Used above.

In (methyl) acrylate polymer (X), as the monomeric unit of this polymer of composition, The carbon number of the alkyl containing 50～99 mass % is that (methyl) alkyl acrylate of 1～20 is Preferably, particularly preferably containing 60～99 mass %, 70～98 mass % are more preferably contained.

As above-mentioned containing reactive functional group monomer, it is preferable to enumerate intramolecular and there is the list of hydroxyl Body (hydroxyl monomer), intramolecular have the monomer (carboxyl group-containing monomer) of carboxyl, intramolecular has The monomer (emulsion stability) etc. of amino.These monomers Han reactive functional group can be used alone A kind of, it is also possible to be used in combination of two or more.

As hydroxyl monomer, such as, can enumerate (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) Acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxyl Butyl ester, (methyl) acrylic acid 3-hydroxybutyl, (methyl) acrylic acid 4-hydroxybutyl etc. (methyl) Hydroxyalkyl acrylates etc..

As carboxyl group-containing monomer, such as, can enumerate: acrylic acid, methacrylic acid .beta.-methylacrylic acid, horse Carry out the ethylenically unsaturated carboxylic acids such as sour, itaconic acid, citraconic acid.Wherein, from obtained (methyl) The reactivity of the carboxyl of acrylate polymer (X) and cross-linking agent (Z) and with other monomers From the point of view of copolymerizable this point, acrylic acid is preferred.They can be used alone, it is also possible to combination two Plant used above.

As emulsion stability, such as, can enumerate (methyl) acrylate, (methyl) third Olefin(e) acid n-butylamino ethyl ester etc..They may be used singly or in combination of two or more use.

In (methyl) acrylate polymer (X), as the monomeric unit of this polymer of composition, Preferably comprise 1～25 mass % containing reactive functional group monomer, particularly preferably containing 1～20 matter Amount %, more preferably contains 2～5 mass %.

The polymeric species of (methyl) acrylate polymer (X) can be random copolymer, it is possible to for Block copolymer.

The weight average molecular weight of (methyl) acrylate polymer (X) is preferably 300,000～3,000,000, Particularly preferably 1,000,000～2,500,000, more preferably 1,600,000～2,200,000.

It addition, (methyl) acrylate polymer (X) can be used alone one, it is also possible to group Close two or more use.

As the polyfunctional monomer of active energy ray-curable, preferably with (methyl) acrylate The polyfunctional acrylic ester class list of the molecular weight less than 1000 of the excellent compatibility of polymer (X) etc. Body.

As the polyfunctional acrylic ester class monomer of molecular weight less than 1000, such as, can enumerate: Isosorbide-5-Nitrae- Butanediol two (methyl) acrylate, 1,6-HD two (methyl) acrylate, neopentyl glycol Two (methyl) acrylate, Polyethylene Glycol two (methyl) acrylate, neopentyl glycol adipic acid Ester two (methyl) acrylate, hydroxyl trimethylace tonitric neopentyl glycol two (methyl) acrylate, Bicyclopentyl two (methyl) acrylate, caprolactone modification dicyclopentenyl two (methyl) propylene Acid esters, ethylene-oxide-modified di(2-ethylhexyl)phosphate (methyl) acrylate, two (acryloyl-oxyethyl) 2 functional-type such as isocyanuric acid ester, allylation cyclohexyl two (methyl) acrylate；Three hydroxyl first Base propane three (methyl) acrylate, dipentaerythritol three (methyl) acrylate, propanoic acid change Property dipentaerythritol three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, ring Ethylene Oxide modification trimethylolpropane tris (methyl) acrylate, three (acryloyl-oxyethyl) Isocyanuric acid ester, 6-caprolactone modification three-(2-(methyl) acryloyl-oxyethyl) isocyanuric acid Ester etc. 3 functional-type；Two glycerol four (methyl) acrylate, tetramethylolmethane four (methyl) propylene Acid esters etc. 4 functional-type；5 functional-type such as propanoic acid modification dipentaerythritol five (methyl) acrylate； Dipentaerythritol six (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) third Olefin(e) acid ester etc. 6 functional-type etc..They can be used alone one, it is also possible to combines two or more making With.

The content of active energy ray-curable compound (Y) gathers relative to (methyl) acrylate Compound (X) 100 mass parts, preferably 1～50 mass parts, particularly preferably 5～30 mass parts, More preferably 10～20 mass parts.

Above-mentioned active energy ray-curable sticker preferably comprises cross-linking agent (Z).Above-mentioned activity energy Amount ray-curable sticker contains as the monomeric unit constituting polymer and comprises containing reactive functional When (methyl) acrylate polymer (X) of base monomer and cross-linking agent (Z), if should Sticker carries out heating etc., then cross-linking agent (Z) and composition (methyl) acrylate polymer (X) The reactive functional group containing reactive functional group monomer react.Thus, (methyl) is formed The structure that acrylate polymer (X) is cross-linked by cross-linking agent (Z), obtained sticker Cohesiveness improves.

As cross-linking agent (Z), by anti-with what (methyl) acrylate polymer (X) was had The cross-linking agent of answering property functional group reaction, such as, can enumerate isocyanates cross-linking agent, epoxies Cross-linking agent, amine cross-linking agent, melamine class cross-linking agent, aziridines cross-linking agent, hydrazine cross-link Agent, aldehyde crosslinking agent, oxazoline class cross-linking agent, metal alkoxide class cross-linking agent, metallo-chelate Class cross-linking agent, metallic salt cross-linking agent, ammonium salt class cross-linking agent etc..As isocyanates cross-linking agent, The cross-linking agent identical with described isocyanates cross-linking agent (B) can be used.It addition, cross-linking agent (Z) Can be used alone one, it is also possible to be used in combination of two or more.

The content of cross-linking agent (Z), relative to (methyl) acrylate polymer (X) 100 matter Amount part, preferably 0.01～10 mass parts, particularly preferably 0.05～5 mass parts, further preferably It it is 0.1～1 mass parts.

Above-mentioned active energy ray-curable sticker the most also can contain various additives, example As: Photoepolymerizationinitiater initiater, silane coupler, refractive index adjusters, antistatic additive, viscosifier, Antioxidant, UV absorbent, light stabilizer, softening agent, filler etc..

Use ultraviolet as the active-energy making above-mentioned active energy ray-curable sticker solidify During ray, above-mentioned active energy ray-curable sticker preferably comprises Photoepolymerizationinitiater initiater.

As Photoepolymerizationinitiater initiater, such as, can enumerate: Benzoinum, benzoin methyl ether, Benzoinum Ether, benzoin isopropyl ether, Benzoinum n-butyl ether, benzoin isobutyl ether, 1-Phenylethanone., dimethyl Aminoacetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(first Sulfenyl) phenyl]-2-morpholinyl-propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-2-(hydroxyl-2- Propyl group) ketone, benzophenone, to phenyl benzophenone, 4,4 '-diethylamino benzophenone, two Chlorobenzophenone, 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tert-butyl group anthraquinone, 2-amino anthraquinones, 2- Methyl thiaxanthone, 2-ethyl thiaxanthone, CTX, 2,4-dimethyl thioxanthone, 2,4-diethyl Thiaxanthone, benzyl dimethyl ketal, 1-Phenylethanone. dimethyl ketal, ESCAROL 507 ester, Oligomeric [2-hydroxy-2-methyl-1 [4-(1-methyl ethylene) phenyl] acetone], 2,4,6-trimethyl Benzoyl-diphenyl-phosphineoxide etc..They may be used singly or in combination of two or more and make With.

Photoepolymerizationinitiater initiater is relative to the active-energy in above-mentioned active energy ray-curable sticker Ray-curable compound (Y) 100 mass parts, preferably makes with the amount of the scope of 0.1～20 mass parts With, particularly preferably 1～12 mass parts.

It addition, from the point of view of the attaching that the sticker obtained by improving is to thin film, above-mentioned work Property energy ray-curable sticker preferably comprises silane coupler.As silane coupler, preferably There are the organo-silicon compound of at least one alkoxysilane group in intramolecular, and with adhesion composition The compatibility is good and has light transmission.

As this silane coupler, such as, except described containing epoxy silane coupling (D1) with And containing outside mercaptosilane coupling agents (D2), also can enumerate containing polymerism unsaturated group silicon compound (such as vinyltrimethoxy silane, VTES, methacryloxy third Base trimethoxy silane etc.), containing aminosilicon compounds (such as 3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino Hydroxypropyl methyl dimethoxysilane etc.), 3-r-chloropropyl trimethoxyl silane, 3-isocyanates propyl group three Ethoxysilane or at least one in them and (such as methyl three second Han alkyl silicon compound TMOS, ethyl triethoxysilane, MTMS, ethyl trimethoxy silane Deng) condensation substance etc..They can be used alone one, it is also possible to is used in combination of two or more.

The content of silane coupler relative to (methyl) acrylate polymer (X) 100 mass parts, It is preferably 0.01～10 mass parts, particularly preferably 0.05～5 mass parts, more preferably 0.1～1 Mass parts.

It addition, the polymer with above-mentioned active energy ray-curable is preferably, side chain imports There is (the first of functional group's (active energy ray-curable base) of active energy ray-curable Base) acrylate (co) polymer.

The thickness of the second adhering agent layer 26 is usually about 1～50 μm, preferably 1～20 μm, special You Xuanwei 2～7 μm.If adhering agent layer is the thinnest, then cohesiveness can reduce, and blocked up, then hold Easily generate sticker and the undesirable condition such as stretch out.

(4) polarizer

As polarizer 21, the polarizer identical with the polarizer 21 of described polaroid 2A can be used.

(5) protective layer

Protective layer 27 is preferably made up of transparent resin film.As this protective layer 27, can use with partially The protective layer that first protective layer 22 of sheet 2A of shaking is identical.

(6) bond layer

Also it can be clamped between polarizer 21 and protective layer 27 and/or polarizer 21 is poor with second phase Bond layer between plate 25, can use identical with the bond layer of described polaroid 2A bonding Oxidant layer.

(7) preparation method of composite polarizing plate

The preparation of composite polarizing plate 2B can be carried out by usual way.Hereinafter, as an example, right Aqueous adhesive is used to illustrate as preparation method during above-mentioned bonding agent.

First, the release surface at stripping film forms the film of the sticker constituting the second adhering agent layer 26. Specifically, the coating solution of the sticker of the second adhering agent layer 26 will be constituted in the stripping of stripping film From face, and it is dried.

On the other hand, at the binding face of polarizer 21 or second phase difference plate 25 and protective layer 27 Binding face formed bond layer.The formation of this bond layer can be by with described polaroid 2A's The method that preparation method is identical is carried out.It addition, the thickness of bond layer is the most identical with easy bonding process.

After bond layer formed as above, across this bond layer protective layer 27 fitted in and be polarized The one side of mirror 21, and second phase difference plate 25 is fitted in the another side of polarizer 21, thus Obtain the duplexer (polarization being made up of protective layer 27, polarizer 21 and second phase difference plate 25 Sheet).

Then, on the face of second phase difference plate 25 side of obtained duplexer, in laminating composition State the film of the sticker of the second adhering agent layer 26 on stripping film.Then, across above-mentioned stripping film Irradiate active energy beam and make the curing of coating of above-mentioned sticker, using this film as the second adhesion Oxidant layer 26.

Wherein, active energy beam refers to electromagnetic wave or the charged particle beam with the quanta of energy, tool For body, ultraviolet or electron beam etc. can be enumerated.Among active energy beam, it is easy to the purple of operation Outside line is particularly preferred.

Ultraviolet irradiation, can pass through high voltage mercury lamp, metal halide thing lamp, Fusion H lamp, xenon Lamps etc. are carried out, and the preferred illumination of ultraviolet irradiation amount is 50～1000mW/cm²Left and right.It addition, Light quantity is preferably 50～10000mJ/cm², more preferably 80～5000mJ/cm², particularly preferably 100～1000mJ/cm².On the other hand, the irradiation of electron beam can be entered by electron-beam accelerator etc. OK, the irradiation dose of electron beam is preferably 10～about 1000krad.

Finally, from by above-mentioned the second formed adhering agent layer 26, stripping film is peeled off, by first The face of the second acrylic resin 243 side of polarizer 24 fits in the second adhesion being exposed Oxidant layer 26.Thus, obtain by protective layer 27, polarizer 21, second phase difference plate 25, second The composite polarizing plate 2B that adhering agent layer 26 and first phase difference plate 24 are laminated.

It addition, the gross thickness of composite polarizing plate 2B is preferably 20～300 μm, more preferably 30～150 μm, particularly preferably 50～100 μm.

(8) has the preparation method of the optical thin film of adhering agent layer

As an example of the preparation method of the optical thin film 10B with adhering agent layer, it is ready for adhesion The adhesive sheet of the two sides stacking stripping film of oxidant layer is used as the adhesive sheet of above-mentioned present embodiment, And peel off the stripping film (light exfoliated stripping film) of side.Then, at the adhering agent layer weight exposed The first phase difference plate 24 of folded composite polarizing plate 2B, pressing adhesive sheet and composite polarizing plate 2B.By This, obtain the above-mentioned optical thin film 10B (with stripping film) with adhering agent layer.

As other examples of the preparation method of the optical thin film 10B with adhering agent layer, at stripping film Release surface be coated with described cohesiveness compositions P coating solution, carry out heat treated and form painting After film, the first phase difference plate 24 of composite polarizing plate 2B is overlapped on this film.Above-mentioned painting Film, when the needs maturation period, is spaced the maturation period and forms adhering agent layer 1, and when need not the maturation period, Directly form adhering agent layer 1.Thus, the above-mentioned optical thin film 10B with adhering agent layer is obtained (attached There is stripping film).

3. has the physical property of the optical thin film of adhering agent layer

The table of the adhering agent layer of optical thin film 10A, 10B with adhering agent layer of present embodiment Surface resistivity is preferably 1.0 × 10¹²Ω/below sq, particularly preferably 5.0 × 10¹¹Ω/below sq, enters one Step is preferably 6.0 × 10¹⁰Ω/below sq.By making surface resistivity be below above-mentioned value, can be in display Panel plays sufficient antistatic behaviour.This surface resistivity can contain by making cohesiveness compositions P Antistatic additive (C) is had to realize.It addition, the mensuration of the surface resistivity of adhering agent layer is set to foundation JIS K6911 is carried out, the most as be described hereinafter shown in test example.It addition, under above-mentioned surface resistivity There is no particular restriction for limit value, but the angle never negatively affecting durability and heat-resisting inequality is examined Consider, be 5.0 × 10⁸About Ω/sq.

The adhesion strength with optical thin film 10A, 10B of adhering agent layer of present embodiment is, right In the adhesion strength of alkali-free glass, preferably 0.5～20N/25mm, particularly preferably 1～10N/25mm. Thus, with the optical thin film excellent in te pins of durability of adhering agent layer.And then from operability more also excellence person From the point of view of, above-mentioned adhesion strength is 2～7N/25mm to be preferred.It addition, adhesion mentioned here Power refers to substantially foundation JIS Z0237:2009 the adhesion strength measured by 180 ° of stripping methods, Be make mensuration sample for wide 25mm, long 100mm, by this mensuration sample in 0.5MPa, at 50 DEG C After pressurizeing 20 minutes and being attached at adherend, in normal pressure, 23 DEG C, place under conditions of 50%RH 24 hours, then obtain so that the peeling rate of 300mm/ minute is measured.By making adhesion Power within the above range, when attaching on liquid crystal cell, can prevent from floating or sur-face peeling etc..

It addition, optical thin film 10A, 10B with adhering agent layer of present embodiment, self-bonding in After above-mentioned adherend, further 23 DEG C, place 14 days under conditions of 50%RH after adhesion strength (adhesion strength after attaching 14 days) is preferably 1～20N/25mm, particularly preferably 3～9N/25mm. So suppress the raising of the adhesion strength of process in time, thus, present embodiment with sticker The operability again of optical thin film 10A, 10B of layer is the most excellent, after being attached at liquid crystal cells, also can Enough easily again attach.

4. has the use of the optical thin film of adhering agent layer

By using optical thin film 10A, 10B with adhering agent layer, it is possible to manufacture and such as possess liquid Brilliant unit and the liquid crystal indicator of optical thin film (polaroid or composite polarizing plate).

Specifically, by the adhering agent layer of optical thin film 10A, 10B with adhering agent layer (when When being laminated with stripping film, the adhering agent layer being exposed after peeling off this stripping film) it is overlapped in liquid crystal cells Desired face and carry out pressing.Thereby, it is possible to obtain possessing liquid crystal cells and polaroid 2A and/or the liquid crystal display of composite polarizing plate 2B.

The adhering agent layer 1 of optical thin film 10A, 10B with adhering agent layer of present embodiment Wave good antistatic behaviour, therefore, it is possible to suppression produces electrostatic when peeling off stripping film.Therefore, as Above-mentioned like that by when fitting in liquid crystal cells with optical thin film 10A, 10B of adhering agent layer, liquid Disorder is not had, it addition, be prevented from what electrostatic caused in the orientation of the liquid crystal molecule of brilliant unit Flying dust or dust and dirt enter in liquid crystal display.

The adhering agent layer 1 of optical thin film 10A, 10B with adhering agent layer of present embodiment, by In its excellent in te pins of durability, even if obtained liquid crystal indicator being positioned under hot conditions, wet Under heat condition or under thermal shock, it is also possible to the interface of suppression adhering agent layer 1 floats or surface stripping From.Such as, when by attached the glass plate of optical thin film 10A, 10B with adhering agent layer in Under the hot conditions of 85 DEG C or 60 DEG C, place 250 hours under the wet heat condition of 90%RH in the case of, Or in the case of applying the thermal shock (each 30 minutes, 200 circulations) of-35 DEG C～70 DEG C, all can Suppression floats or sur-face peeling.

It addition, the sticker of optical thin film 10A, 10B with adhering agent layer of present embodiment Layer 1, owing to its stress relaxation is the most excellent, obtained liquid crystal indicator is the most also It is difficult to warpage and then is difficult to occur heat uneven.Such as, the optics with adhering agent layer will have been attached The glass plate of thin film 10A, 10B is placed (such as, under conditions of 80～85 DEG C) under hot conditions In the case of 250 hours, it is not easy to warpage, and then is difficult to occur heat uneven.Especially, even if polarizing Sheet 2A or composite polarizing plate 2B is thin film, and liquid crystal display is not easy to warpage, even if it addition, Liquid crystal cells is fine unit, is not easy to occur heat uneven.

Here, there is nesa coating sometimes in the binding face with adhering agent layer 1 of liquid crystal cells, In this case, it is also possible to suppression electrically conducting transparent erosion or the resistance change of nesa coating. Especially, in present embodiment, by (methyl) propylene using acid number to be below 5mgKOH/g Acid ester copolymer (A), and use specific antistatic additive (C), the effect above can be given full play to.

As above-mentioned nesa coating, such as can enumerate by the metals such as platinum, gold, silver, copper, aluminum, Oxide, the tin-doped indium oxides such as stannum oxide, Indium sesquioxide., Aska-Rid., zinc oxide, zinc oxide (ITO), Zinc oxide doped Indium sesquioxide., Fluorin doped Indium sesquioxide., antimony-doped tin oxide, Fluorin doped oxygen Change the composite oxides such as stannum, aluminium-doped zinc oxide, chalcogenide, lanthanum hexaboride, titanium nitride, carbon Change the non-oxidized compound such as titanium etc. to constitute.

The implementation described above is for ease of understanding that the present invention records, not for limiting this Bright and record.Therefore, purport also includes belonging in being each key element disclosed in above-mentioned embodiment All design variant of the technical scope of the present invention and equivalent.

Embodiment

Hereinafter, further the present invention is specifically described by embodiment etc., but the model of the present invention Enclose and be not limited to these embodiments etc..

(embodiment 1)

1. the preparation of the first optical thin film (polaroid)

(1) making of polarizer

By be made up of the polyvinyl alcohol of average degree of polymerization about 2,400,99.9 moles of more than % of saponification degree Thickness is the polyvinyl alcohol film of 75 μm, extends about 5 times in dry type uniaxial extension mode, further Keep tension, impregnate 1 minute in the pure water of 60 DEG C.Afterwards, in the matter of iodine/potassium iodide/water Measure in the aqueous solution that ratio is 0.05/5/100 and impregnate 60 seconds with 28 DEG C.Then, in potassium iodide/boric acid/ The mass ratio of water be 8.5/8.5/100 aqueous solution in 72 DEG C impregnate 300 seconds.Then, with 26 DEG C Pure water after 20 seconds, obtain iodine gas absorption quantity in polyvinyl alcohol so that 65 DEG C are dried Polarizer.

(2) making of polaroid

Prepare by the carboxy-modified polyvinyl alcohol of 3 mass parts (prepared by KURARAY CO., LTD, Trade name " KL-318 ") it is dissolved in the water of 100 mass parts, and with the addition of 1.5 in this aqueous solution Mass of water-soluble epoxy resin i.e. daiamid epoxy class additive (Taoka Chemical Co., Ltd. Preparation, trade name " Sumirez Resin 650 (30) ", solid component concentration 30 mass % water-soluble Liquid) and the epoxies bonding agent that obtains.This epoxies bonding agent is coated by above-mentioned and obtain The one side of polarizer.

On the coating layer of above-mentioned epoxies bonding agent, coating surface implements the thickness that saponification processes The triacetylcellulose film of 25 μm (prepared by Konica Minolta Opto Products Co., Ltd., Trade name " KC2UA ") as the first protective layer.

Then, the another side at above-mentioned polarizer is coated with epoxies bonding agent as described above, right Zero phase difference thin film (the Japan that the laminating of this coating layer is made up of the cyclic olefin resinoid of thickness 23 μm Zeon Corporation system, trade name " ZEONOR ") it is used as the second protective layer.Afterwards, exist It is dried 5 minutes at 80 DEG C, thus above-mentioned first protective layer and the second protective layer is adhered to polarizer. After bonding, ripening 168 hours at 40 DEG C, obtained stacking the first protective layer (thickness 25 μm), Polarizer (extension ratio 5 times, thickness 15 μm) and the second protective layer (thickness 23 μm) form The polaroid (the first optical thin film) of gross thickness 63 μm.

2. the preparation of the second optical thin film (composite polarizing plate)

(1) formation of the film of active energy ray-curable bonding agent

Co-polypropylene acid N-butyl 95 mass parts and acrylic acid 5 mass parts and prepare (methyl) third Olefine acid ester polymer (X).Being measured by aftermentioned method should (methyl) acrylate polymer (X) Molecular weight, result weight average molecular weight (Mw) is 2,000,000.

By using above-mentioned (methyl) acrylate polymer (X) 100 mass parts, as activity energy Three (acryloyl-oxyethyl) isocyanide of amount ray-curable compound (Y) (polyfunctional monomer) Urea acid esters (prepared by TOAGOSEI CO., LTD., trade name " ARONIXM-315 ") 15 mass Part, as the trimethylolpropane modified toluene diisocyanate (Nippon of cross-linking agent (Z) Prepared by Polyurethane Industry Co., Ltd., trade name " CORONATEL ") 0.3 mass parts, As polymerization initiator by benzophenone and 1-hydroxycyclohexylphenylketone with the mass ratio of 1:1 (prepared by Chiba Specialty Chemicals company, trade name for the mixture that carries out mixing " IRGACURE500 ") 1.5 mass parts and the 3-glycidoxypropyl as silane coupler Propyl trimethoxy silicane (prepared by Shin-Etsu Chemical Co., Ltd., trade name " KBM403 ") 0.2 mass parts mixes, and is sufficiently stirred for and is diluted by ethyl acetate, obtains active-energy and penetrates The coating solution of line curable sticker.

One side in pet film has been carried out at stripping by silicone remover The stripping film (prepared by LINTEC Corporation, SP-PET3811, thickness: 38 μm) managed and obtain Lift-off processing face, with blade coating machine be coated with obtained by active energy ray-curable sticker Coating solution after, with 90 DEG C of heat treated 1 minute, thus form active energy ray-curable The film of property sticker.

(2) making of first phase difference plate

The acrylic compounds rubber of mean diameter 200nm constituting the first acrylic resin will be added with Methacrylic resin (Sumitomo Chemical Co., the Ltd. system of glue granule about 20 mass % Standby, trade name " TechnolloyS001 "), constitute the phenylethylene-maleic anhydride class of phase contrast presentation layer Copolymer resins (NOVA Chemicals Corporation., trade name " DYLARK D332 "), with And it is added with the acrylic rubber of mean diameter 200nm constituting the second acrylic resin The methacrylic resin of grain about 20 mass % (prepared by Sumitomo Chemical Co., Ltd., Trade name " TechnolloyS001 "), carry out 3 layers of coextrusion in the order, obtain 3-tier architecture Laminate film.Make obtained laminate film extend, thus in obtaining face, phase difference value is 60nm, thickness 25 μm first phase difference plate (the first acrylic resin/phase contrast presentation layer/ Second acrylic resin).

(3) making of composite polarizing plate

First, described first optical thin film (polaroid) is prepared.First protective layer of this polaroid with And second protective layer be respectively equivalent to the protective layer of composite polarizing plate and the second phase that make at this Difference plate.That is, stacking protective layer, polarizer and the polaroid of second phase difference plate are prepared.

On the face of the second phase difference plate side of above-mentioned polaroid, fit and obtained by above-mentioned operation (1) The film of the active energy ray-curable sticker arrived, across above-mentioned stripping film under the following conditions Irradiation ultraviolet radiation, makes the curing of coating of above-mentioned sticker become the second adhering agent layer.Afterwards, from After stripping film is peeled off by the second obtained adhering agent layer, in the table of the second adhering agent layer exposed Face, the second acrylic resin of the first phase difference plate that laminating is obtained by above-mentioned operation (2) The face of side.So, obtain by stacked guard layer, polarizer, second phase difference plate, second glue (second is optically thin the composite polarizing plate of gross thickness 93 μm of oxidant layer and first phase difference plate Film).It addition, the thickness of the second adhering agent layer formed is 5 μm.

＜ ultraviolet irradiates condition ＞

Use high voltage mercury lamp

Illumination 300mW/cm², light quantity 300mJ/cm²

EYE GRAPHICS CO., LTD. is used to prepare the UV illumination/quantometer of " UVPF-A1 "

3. has the preparation of the optical thin film of adhering agent layer

(1) preparation of (methyl) acrylate copolymer

By n-butyl acrylate 87 mass parts, isobornyl acrylate 5 mass parts, acrylic acid 2- Phenyl chlorocarbonate 5 mass parts and acrylic acid 2-hydroxy methacrylate 3 mass parts carry out copolymerization and prepare (first Base) acrylate copolymer (A).Measuring by aftermentioned method should (methyl) acrylate copolymer (A) molecular weight, result weight average molecular weight (Mw) is 1,600,000.It addition, join according to above-mentioned It is 14.49mgKOH/g that ratio can calculate the hydroxyl value of this (methyl) acrylate copolymer (A), Acid number is 0mgKOH/g.

(2) preparation of cohesiveness compositions

Mix (methyl) acrylate copolymer (A) 100 matter obtained in above-mentioned operation (1) Amount part, different as the trimethylolpropane modification phenylenedimethylidyne two of isocyanates cross-linking agent (B) Cyanate (Mitsui Chemicals, Incorporated system, trade name " TAKENATE D110N ") 0.2 mass parts, as antistatic additive (C) double (fluorine sulphonyl) imines of N-decyl pyridine ( Be the ionic compound of solid under room temperature) 1.5 mass parts, as containing epoxy silane coupling (D1) 3-glycidoxypropyltrimewasxysilane (Shin-Etsu Chemical Co., Ltd. system, Trade name " KBM403 ") 0.2 mass parts, as the 3-sulfydryl containing mercaptosilane coupling agents (D2) Propyl trimethoxy silicane and cocondensation compound (the Shin-Etsu Chemical of MTES Co., Ltd.'s system, trade name " X-41-1810 ", mercapto equivalents: 450g/ mole) 0.2 mass parts, fill Divide stirring, and with diluted ethyl acetate, resulting in the coating solution of cohesiveness compositions.

Wherein, (methyl) acrylate copolymer (A) is set to 100 mass parts (solid constituents Scaled value) time each proportioning (solid constituent scaled value) of cohesiveness compositions be shown in table 1.It addition, The detailed contents such as the abbreviation described in table 1 are as described below.

[(methyl) acrylate copolymer]

BA: n-butyl acrylate

HEA: acrylic acid 2-hydroxy methacrylate

IBXA: isobornyl acrylate

PhEA: acrylic acid 2-phenyl chlorocarbonate

CHA: cyclohexyl acrylate

[isocyanates cross-linking agent]

XDI: trimethylolpropane modification XDI (Mitsui Chemicals, Incorporated system, trade name " TAKENATE D110N ")

HDI: trimethylolpropane modification hexamethylene diisocyanate (Nippon Polyurethane Industry Co., Ltd. system, trade name " CORONATE HL ")

[antistatic additive]

Double (fluorine sulphonyl) imines of Pry+FSI-:N-decyl pyridine (is at room temperature the ion of solid Compound)

K+PF6-: Potassium Hexafluorophosphate (being at room temperature the ionic compound of solid)

(3) has the making of the optical thin film of adhering agent layer

One side in pet film has been carried out at stripping by silicone remover The stripping film (prepared by LINTEC Corporation, SP-PET3811, thickness: 38 μm) of reason Lift-off processing face, after the coating solution of the cohesiveness compositions obtained by being coated with blade coating machine, With 90 DEG C of heat treated 1 minute, thus form the film of cohesiveness compositions.

Then, the polaroid as the first optical thin film that will obtain in above-mentioned, with its second protection The mode that connects with the exposed surface of above-mentioned film of surface of layer, fits with above-mentioned film, 23 DEG C, Ripening 7 days under 50%RH, resulting in and be formed with the first of adhering agent layer on polaroid and have The optical thin film of adhering agent layer.It addition, the thickness of this adhering agent layer formed is 20 μm.

Further, the composite polarizing plate as the second optical thin film that will obtain in above-mentioned, with its first The side that the surface of the first acrylic resin of polarizer connects with the exposed surface of above-mentioned film Formula, fits with above-mentioned film, 23 DEG C, ripening 7 days under 50%RH, resulting in compound It is formed with the second of adhering agent layer on polaroid and has the optical thin film of adhering agent layer.It addition, this institute The thickness of the adhering agent layer formed is 20 μm.

(embodiment 2～12, comparative example 1～7)

Kind and the ratio, (first of each monomer of (methyl) acrylate copolymer (A) will be constituted Base) weight average molecular weight of acrylate copolymer (A), the kind of isocyanates cross-linking agent (B) Class and addition and the kind of antistatic additive (C) and addition are changed to beyond as shown in table 1, It is prepared for the optical thin film with adhering agent layer same as in Example 1ly.

Here, described weight average molecular weight (Mw) is for using gel permeation chromatography (GPC) following Under conditions of measure the weight average molecular weight of polystyrene conversion of (GPC mensuration).

＜ condition determination ＞

GPC determinator: prepared by Tosoh Corporation, HLC-8020

GPC post (passes through) in the following order: Tosoh Corporation system

TSK guard column HXL-H

TSK gel GMHXL(×2)

TSK gel G2000HXL

Mensuration solvent: oxolane

Mensuration temperature: 40 DEG C

Following test example is to have the light of adhering agent layer in embodiment and comparative example the second of preparation Learn thin film and carry out.

(test example 1) (mensuration of gel fraction)

Replace the optics used when making the optical thin film with adhering agent layer in embodiment or comparative example Thin film, uses the one side of pet film to be shelled by silicone remover From the stripping film (prepared by LINTEC Corporation, SP-PET3801, thickness: 38 μm) processed Make adhesive sheet.Specifically, the stripping obtained in by the preparation process of embodiment or comparative example On the film exposed of the structure of the film composition of sheet/cohesiveness compositions, above-mentioned stripping film Stacking in the way of side, lift-off processing face connects, 23 DEG C, ripening seven days under conditions of 50%RH. Thus, make by stripping film (SP-PET3801)/adhering agent layer (thickness: 20 μm)/stripping The adhesive sheet that the structure of sheet (SP-PET3811) is constituted.

Obtained adhesive sheet is cut with the size of 80mm × 80mm, by its adhering agent layer It is coated on polyester net (mesh) (net size 200), weighs its quality with precision balance, deduct State the single quality of net, thus calculate the quality of only sticker.Quality now is set to M1.

Then, will be coated on the sticker of above-mentioned polyester net, at room temperature (23 DEG C) are in acetic acid Ethyl ester impregnates 24 hours.Then take out sticker, at temperature 23 DEG C, the ring of relative humidity 50% Under border, air-dry 24 hours, be dried 12 hours in the baking oven of 80 DEG C further.After drying, use Precision balance weighs its quality, deducts the single quality of above-mentioned net, thus calculates only sticker Quality.Quality now is set to M2.Gel fraction (%) represents with (M2/M1) × 100. Result is shown in table 2.

(test example 2) (durability evaluation)

Cut the optical thin film with adhering agent layer obtained in embodiment and comparative example, make The sample of 150mm × 200mm size.Stripping film is peeled off and via the adhesion exposed from this sample After oxidant layer is attached at alkali-free glass (prepared by Corning Incorporated, Eagle XG), use Autoclave prepared by KURIHARA is in 0.5MPa, pressurize 20 minutes at 50 DEG C.

Thereafter, in the environment of putting into condition as durable in following three, put with 10 times after 250 hours Big mirror confirms with or without floating or sur-face peeling.Evaluation criterion is as follows.Result is shown in table 2.

◎: unconfirmed to floating or sur-face peeling.

Zero: confirm floating or sur-face peeling of below 0.5mm size.

△: confirm floating or sur-face peeling more than 0.5mm and below 1.0mm size.

×: confirm floating or sur-face peeling more than 1.0mm size.

Durable condition ＞ of ＜

Heat-resisting: 85 DEG C are dried

Damp and hot: 60 DEG C, relative humidity 90%RH

H.S.:Under the thermal shock test of each 30 minutes, 200 circulations

(test example 3) (resistance to warpage evaluation)

The optical thin film with adhering agent layer obtained in embodiment and comparative example is cut growth 200mm, wide 150mm.Peel stripping film from this off with the optical thin film of adhering agent layer, will be revealed The adhering agent layer gone out fits in long 250mm, wide 175mm, the alkali-free glass (Corning of thick 0.5mm Prepared by Incorporated, trade name " Eagle-XG ") central part, using this as sample.Should Sample in 85 DEG C, be dried under atmosphere and place 250 hours.Thereafter, taking-up is placed in 25 DEG C, 50%RH In the environment of, polaroid side is positioned on horizontal stand upward, measures each angle (4 point) of sample The amount of warpage (angle and the distance of platform) of distance platform, adds up to the amount of warpage at each angle.Tie according to it Fruit is following evaluates resistance to warpage.Result is shown in table 2.

◎: amount of warpage add up to below 10mm

Zero: the total of amount of warpage is more than 10mm and below 15mm

The total of △: amount of warpage is more than 15mm and below 20mm

×: the total of amount of warpage is more than 20mm

(test example 4) (evaluation of heat-resisting inequality)

The optical thin film with adhering agent layer that will obtain in embodiment and comparative example, with cutting dress Put (Ogino Seisakusho Co., Super Cutter PN1-600 prepared by Ltd.) to be adjusted to 200mm × 150mm size.Peel stripping film off and be attached at alkali-free via the adhering agent layer exposed After glass (prepared by Corning Incorporated, Eagle XG), prepare with KURIHARA Autoclave is in 0.5MPa, pressurize 20 minutes at 50 DEG C.Fit at alkali-free glass it addition, above-mentioned Surface so that being orthogonal Niccol (cross with the polarization axle of optical thin film of adhering agent layer Nicol) mode (polarization axle: ∠ 45 °, ∠ 135 °) of state is carried out.With this state, at 80 DEG C Be dried after placing 250 hours under (dry) environment, in 23 DEG C, place 2 in the environment of 50%RH Hour, using this as sample, by method shown below, heat-resisting inequality is evaluated.Result It is shown in table 2.

＜ evaluation methodology ＞

Above-mentioned sample is arranged at planar lighting device (FLAT ILLUMINATOR) (Raytronics Corp., preparation, HF-SL-A312LC, illumination: 26,000Lux, brightness: 10,000cd) on, with two-dimensional color luminance meter (prepared by KONICA MINOLTA, INC., CA-2000) shoot, and with analyze software (prepared by KONICA MINOLTA, INC., CA-S20w) Luminance Distribution image it is converted into.Luminance Distribution image to obtained sample, base It is evaluated in Fig. 4 and evaluation criterion shown below.

◎: Luminance Distribution is generally uniform.

The Luminance Distribution on zero: four limit has some distortions.

The Luminance Distribution on △: four limits has obvious distortion.

×: the Luminance Distribution on four limits has serious distortion.

(test example 5) (corrosion resistance evaluation)

The making ＞ of ＜ metallic diaphragm laminated glass substrate

By use aluminum as sputtering target and use argon as the sputtering method of sputter gas, accurate in advance One surface of standby alkali-free glass forms the metallic aluminum of thickness 500nm.

Then, in the way of solid constituent conversion becomes 2 mass %, at acrylic compounds hard varnish (JSR CORPORATION system, Opstar (registered trade mark) Z7535) in mixing comprise the first of phosphate Base acrylic acid derivative (KYOEISHA CHEMICAL Co., LTDorporation system, LIGHT ESTER P-2M), use butanone to be diluted to solid component concentration 7.5 matter as retarder thinner Amount %, resulting in hard varnish coating fluid.

By obtained hard varnish coating solution in the exposed surface side of above-mentioned metallic aluminum, at 80 DEG C Under be dried 3 minutes after, irradiation ultraviolet radiation (use mercury lamp, 1200mJ/cm²), make film cross-link, Thus form the hardcoat surface layer of thickness 2.0 μm.Thus, at glass substrate has been made The metallic diaphragm laminated glass substrate of metallic aluminum, hardcoat surface layer it is sequentially formed with on surface.

The evaluation ＞ of ＜ corrosion resistance

The optical thin film with adhering agent layer obtained in embodiment and comparative example is cut to The test film of 20mm × 50mm size.Stripping film, the adhesion that will be exposed is peeled off from this test film Oxidant layer attaches exposing of the hardcoat surface layer of the metallic diaphragm laminated glass substrate obtained in above-mentioned operation Side, face.By its temperature 60 C, relative humidity 90% baking box in keeping 750 hours after, take Go out to put at room temperature.Then, the above-mentioned test film that is fitted with of metallic diaphragm laminated glass substrate is observed The state of metallic aluminum of part, and the corrosion resistance with following standard evaluation.Show the result in table 2.

: metallic aluminum does not produces spot corrosion, white opacity.

×: metallic aluminum creates spot corrosion, white opacity.

(test example 6) (mensuration of the surface resistivity of adhering agent layer)

The optical thin film with adhering agent layer obtained in embodiment and comparative example is cut into The size of 50mm × 50mm, by obtained sample under the temperature of 23 DEG C, the humidity of 50%RH Place 24 hours.Thereafter, peel stripping film off, in the adhering agent layer surface exposed, use resistance (prepared by Mitsubishi Chemical Analytech Co., Ltd., Hiresta UP MCP-HT450 for rate meter Type) and measure surface resistivity (Ω/sq) according to JIS K6911.Result is shown in table 2.

(test example 7) (adhesion strength mensuration-operability evaluation again)

The optical thin film with adhering agent layer obtained from embodiment and comparative example cuts out 25mm Wide, the sample of 100mm length, peels stripping film off and is attached at alkali-free via the adhering agent layer exposed After glass (prepared by Corning Incorporated, Eagle XG), prepare with KURIHARA Autoclave is in 0.5MPa, pressurize 20 minutes at 50 DEG C.Thereafter, 23 DEG C, the condition of 50%RH Lower placement 24 hours, and use cupping machine (prepared by ORIENTEC Co., Ltd., TENSILON), measure under conditions of peeling rate 300mm/ minute, glass angle 180 degree Adhesion strength (the adhesion strength after attaching a day；N/25mm).The condition outside this that is recorded in is in accordance with JIS Z 0237:2009 and be measured.Result is shown in table 2.

23 DEG C, place 14 days under conditions of 50%RH after, measure the most in the same manner as described above Adhesion strength (the adhesion strength after attaching 14 days；N/25mm).Result is shown in table 2.

Based on the adhesion strength after above-mentioned attaching fortnight, carry out again the evaluation of operability in order to lower standard. Result is shown in table 2.

◎: attaching the adhesion strength after fortnight is below 8.8N/25mm

Zero: attach the adhesion strength after fortnight more than 8.8N/25mm and less than 10N/25mm

△: attaching the adhesion strength after fortnight is that 10N/25mm is less than 20N/25mm

×: attaching the adhesion strength after fortnight is more than 20N/25mm

(test example 8) (mensuration of haze value)

Make identically with test example 1 and there is the sticker corresponding with each embodiment or each comparative example Layer and by stripping film (SP-PET3801)/adhering agent layer (thickness: 20 μm)/stripping film (SP-PET3811) adhesive sheet (ripening 7 days) that structure is constituted.Adhesion to this adhesive sheet Oxidant layer, utilize haze meter (NIPPON DENSHOKU INDUSTRIES Co., LTD system, NDH2000), haze value (%) (being sometimes abbreviated as Hz (%)) is measured according to JIS K7136:2000. Show the result in table 2.

[table 1]

[table 2]

As known from Table 2, the durability with the optical thin film of adhering agent layer obtained in embodiment is excellent Different, and at high temperature it is not easy to warpage, it is not easy to occur heat uneven.Further, embodiment obtains The optical thin film with adhering agent layer arrived is for the excellent corrosion resistance of nesa coating, and glues The surface resistivity oxidant layer is low, shows good antistatic behaviour.And, embodiment obtains Operability again with the optical thin film of adhering agent layer is excellent, and the adhering agent layer of embodiment is transparent Property is the highest.

Industrial applicibility

The sticker of the present invention, adhesive sheet and the optical thin film with adhering agent layer are suitable to polaroid of fitting Or composite polarizing plate and liquid crystal cells, especially there is at binding face the liquid crystal cells of nesa coating.

Claims (7)

1. a sticker, it is obtained by cohesiveness compositions, it is characterised in that described cohesiveness Compositions contains:

(methyl) acrylate copolymer (A), its contain containing ester ring type structures alone (a1), Containing aromatic rings monomer (a2) and hydroxyl monomer (a3) as constituting the monomeric unit of polymer, Hydroxyl value is 5～20mgKOH/g, and acid number is below 5mgKOH/g, and weight average molecular weight is 1,300,000～300 Ten thousand；

Isocyanates cross-linking agent (B)；And

Antistatic additive (C),

The gel fraction of described sticker is 62～90%, and described antistatic additive (C) is for comprising fluorine sulphur Acid imide is as the ionic compound of anion.

Sticker the most according to claim 1, it is characterised in that described containing ester ring type structure Ester ring type structure in monomer (a1) is multi-ring ester ring type structure.

Sticker the most according to claim 1, it is characterised in that described cohesiveness compositions Possibly together with containing epoxy silane coupling (D1).

Sticker the most according to claim 1, it is characterised in that described cohesiveness compositions Possibly together with containing mercaptosilane coupling agents (D2).

Sticker the most according to claim 1, it is characterised in that described isocyanates is handed over Connection agent (B) is the compound with aromatic rings.

6. an adhesive sheet, it is characterised in that possess gluing according to any one of Claims 1 to 5 The adhering agent layer that agent is constituted.

7. the optical thin film with adhering agent layer, it is characterised in that possess:

Optical thin film；And

Adhering agent layer, in its Claims 1 to 5 by least one side being laminated in described optical thin film Sticker described in any one is constituted.