CN106104329A - Polarizer adhesive composition, adhesive phase, bonding sheet and the polarizer with adhesive phase - Google Patents

Abstract

The present invention provides a kind of warpage (bending) that can suppress liquid crystal cell and can form the polarizer adhesive composition of adhesive phase of excellent in te pins of durability.Polarizer adhesive composition is characterised by, this polarizer adhesive composition is the polarizer adhesive composition of (methyl) acrylic copolymer and (B) crosslinking agent being obtained by the monomer component copolymerization of (methyl) alkyl acrylate that the carbon number comprising alkyl is 4～18 and the monomer of polar functionalities containing (A), loss angle tangent (tan δ at 23 DEG C of the adhesive phase being formed by described composition₁) it is 0.33～0.55, and loss angle tangent (tan δ at 80 DEG C₂) it is 0.40～0.65.

Description

Polarizer adhesive composition, adhesive phase, bonding sheet and with adhesive phase Polarizer

Technical field

The present invention relates to polarizer adhesive composition.

Background technology

Liquid crystal cell has liquid crystal layer by the structure clamped by 2 pieces of substrates (such as glass plate), and polarizer is via adhesive Layer adheres to the surface of described substrate.Polarizer lacks dimensionally stable due to easy thermal contraction under hot and humid thermal environment Property, warpage can occur at liquid crystal cell.In recent years, as the slimming of liquid crystal cell (for example constitutes the substrate of liquid crystal cell Slimming) and the slimming of polarizer, the warpage of the liquid crystal cell under hot and humid thermal environment becomes all the more problem.Liquid crystal The reason that structure cell warpage can enumerate such as adhesive phase cannot catch up with the thermal contraction (change in size) of polarizer, adhesive phase should It is low that power alleviates characteristic.

In addition, under hot and humid thermal environment, the interface being susceptible to polarizer with substrate produces bubble or bonding The unfavorable conditions such as oxidant layer fracture, polarizer stripping.So, it is desirable to polarizer adhesive has high-durability.

The generally means of suppression liquid crystal cell warpage can enumerate the highly-flexible using the change in size coping with polarizer The method of property adhesive phase.But, the cohesiveness of this adhesive phase is not enough, can produce durability and deteriorate and processability deterioration Etc. problem.

For example, patent document 1 and 2 is carried out across adhesive phase with tri acetyl cellulose (TAC) base material and glass baseplate The bonding film preventing TAC base material under hot humid when stacking floats for problem from glass baseplate, discloses containing propylene Acrylic binder, isocyanates curing agent and acrylic copolymer and loss angle tangent (tan δ) viscous with particular range Mixture layer.

Prior art literature

Patent document

Patent document 1: Japanese Patent Laid-Open 2013-141801 publication

Patent document 2: Japanese Patent Laid-Open 2013-063631 publication

Content of the invention

The technical problem to be solved

The problem of the present invention is to provide and can suppress the warpage (bending) of liquid crystal cell and can form excellent in te pins of durability Adhesive phase polarizer adhesive composition, the polarizer adhesive phase being formed by described composition, have described The polarizer bonding sheet of adhesive phase and the polarizer with adhesive phase with described adhesive phase.

Solve the technical scheme that technical problem is used

The present inventor conducts in-depth research for solving above-mentioned technical problem.It is found that as containing specific (first Base) 23 DEG C of adhesive phase that is adhesive composition and that formed by described composition of acrylic copolymer and crosslinking agent With 80 DEG C at adhesive composition in particular range for the loss angle tangent can suppress the warpage (bending) of liquid crystal cell, and The adhesive phase of excellent in te pins of durability can be formed.That is, the inventors discovered that by using the polarizer with following specific composition Can solve the problem that above-mentioned technical problem with adhesive composition, thus complete invention.

For example, following [1]～[12] of the present invention.

[1] a kind of polarizer adhesive composition, it is characterised in that this polarizer adhesive composition be containing (A) by the monomer component of (methyl) alkyl acrylate that the carbon number comprising alkyl is 4～18 and the monomer of polar functionalities altogether Poly-(methyl) acrylic copolymer obtaining and the polarizer adhesive composition of (B) crosslinking agent, by described composition shape Loss angle tangent (tan δ at 23 DEG C of the adhesive phase becoming₁) it is 0.33～0.55, and loss angle tangent (tan δ at 80 DEG C₂) be 0.40～0.65.

[2] the polarizer adhesive composition described in above-mentioned [1], wherein, crosslinking agent (B) contains isocyanates chemical combination Thing (B1) and metallo-chelate (B2).

[3] the polarizer adhesive composition described in above-mentioned [2], wherein, the content of metallo-chelate (B2) is relative It is 10～1000 mass parts in the isocyanate compound (B1) of 100 mass parts.

[4] the polarizer adhesive composition described in any one of above-mentioned [1]～[3], wherein, described containing polar group The polar group of the monomer of group is carboxyl and/or hydroxyl.

[5] the polarizer adhesive composition described in any one of above-mentioned [1]～[4], wherein, described (methyl) third Olefin(e) acid analog copolymer (A) is the copolymer being obtained by described copolymerization in the presence of peroxide type polymerization initiator.

[6] the polarizer adhesive composition described in any one of above-mentioned [1]～[5], wherein, described (methyl) third The weight average molecular weight (Mw) that olefin(e) acid analog copolymer (A) utilizes gel permeation chromatography (GPC method) to measure is 200,000～1,500,000.

[7] the polarizer adhesive composition described in any one of above-mentioned [1]～[6], wherein, containing of peroxide Amount relative to (methyl) acrylic copolymers (A) of 100 mass parts below 0.1 mass parts.

[8] the polarizer adhesive composition described in any one of above-mentioned [1]～[7], wherein, by described polarizer Gel fraction with the adhesive of adhesive composition formation is 10～70 mass %.

[9] a kind of polarizer adhesive phase, it is characterised in that by the polarization described in any one of above-mentioned [1]～[8] Piece is formed by adhesive composition, loss angle tangent (tan δ at its 23 DEG C₁) it is 0.33～0.55, and loss angle tangent at 80 DEG C (tanδ₂) it is 0.40～0.65.

[10] the polarizer adhesive phase described in above-mentioned [9], wherein, gel fraction is 10～70 mass %.

[11]. a kind of polarizer bonding sheet, it is characterised in that there is the polarizer described in above-mentioned [9] or [10] and use Adhesive phase.

[12] a kind of polarizer with adhesive phase, it is characterised in that there is polarizer and be formed at described polarizer The polaroid-bindnig oxidant layer described in above-mentioned [9] or [10] on the face of at least one party.

The effect of invention

Utilize the present invention, it is possible to provide the warpage (bending) of liquid crystal cell can be suppressed and the viscous of excellent in te pins of durability can be formed The polarizer adhesive composition of mixture layer, the polarizer adhesive phase being formed by above-mentioned composition, there is above-mentioned bonding The polarizer bonding sheet of oxidant layer and the polarizer with adhesive phase with above-mentioned adhesive phase.

Detailed description of the invention

Below, to the polarizer adhesive composition of the present invention, polarizer adhesive phase, polarizer bonding sheet with And the polarizer with adhesive phase illustrates.Hereinafter, the polarizer adhesive composition of the present invention is also referred to as " viscous Mixture composite ", the polarizer adhesive phase of the present invention is also referred to as " adhesive phase ", the polarizer bonding sheet of the present invention Also referred to as " bonding sheet '.

[polarizer adhesive composition]

The polarizer adhesive composition of the present invention is characterised by, this polarizer adhesive composition be containing (methyl) acrylic copolymer (A) and the composition of crosslinking agent (B), the adhesive phase being formed by above-mentioned adhesive composition Loss angle tangent (tan δ at 23 DEG C₁) it is 0.33～0.55, and loss angle tangent (tan δ at 80 DEG C₂) it is 0.40～0.65.

The adhesive composition of the present invention also can contain selected from silane coupler (C), antistatic agent (D) and have as required At least one in machine solvent (E).

Here, " the Physica MCR300 " by using Anton Paar company (Anton Paar) to manufacture, according to based on JIS (condition is temperature range-40～180 DEG C to the Measurement of Dynamic Viscoelasticity method of K7244, programming rate 3.67 DEG C/min, frequency 1Hz) measure the viscoplasticity spectrogram according to the adhesive phase that the thickness that following condition is formed is 1.0mm, can obtain as this The loss angle tangent of bright adhesive composition characteristic.

Adhesive phase in Measurement of Dynamic Viscoelasticity is formed in the following manner.So that dried thickness reaches 20 μm Condition is at the upper coating adhesive composition of polyethylene terephthalate film (PET film) through lift-off processing, at 90 DEG C It is dried 3 minutes and removes solvent, form film.The reverse side of the sticking veneer of the above-mentioned PET film of film is fitted at stripping again The PET film of reason, stands under 23 DEG C/50%RH environment and cures for 7 days, form the adhesive phase that thickness is 20 μm.Cure PET film unilateral for obtained bonding sheet is peeled off, and is mutually carried out many to the adhesive phase that above-mentioned thickness is 20 μm by Cheng Hou Secondary laminating, forms final thickness and reaches the adhesive phase of 1.0mm, measure the above-mentioned viscoplasticity spectrogram of this adhesive phase.

In addition, the above-mentioned formation condition of adhesive phase is to measure the loss as Invention adhesive compositions characteristic Angle tangent and record, the adhesive phase being formed by the adhesive composition of the present invention is certainly not limited to be formed by above-mentioned condition Layer.

Loss modulus G of storage modulus G' with sign adhesion properties to characterize elastic property for the loss angle tangent (tan δ) " Ratio: "/G' represents G, and ratio is bigger, and the contribution of viscosity is bigger, and ratio is less, and elastic contribution is bigger.

In above-mentioned adhesive phase, loss angle tangent (tan δ at 23 DEG C₁) it is 0.33～0.55, preferably 0.35～0.52, Particularly preferably 0.40～0.49；Loss angle tangent (tan δ at 80 DEG C₂) it is 0.40～0.65, preferably 0.42～0.62, special You Xuanwei 0.47～0.56.

Loss angle tangent (tan δ at 23 DEG C₁) make it present suitable elasticity within the above range, to clung body Adaptation and workability aspect are favourable.If tan is δ₁Exceed above-mentioned scope, then the viscosity contribution of adhesive layer becomes excessive, Have the tendency of yield rate in the flow charts such as carrying punching press to reduce.If tan is δ₁Less than above-mentioned scope, then the bullet of adhesive layer Property contribution become excessive, exist the wellability to clung body reduce, adaptation be deteriorated tendency.

Loss angle tangent (tan δ at 80 DEG C₂) make its flexibility excellent within the above range, and adhesive phase can be caught up with The thermal contraction (change in size) of polarizer under high temperature.If tan is δ₂Exceed above-mentioned scope, then there is the coherency fall of adhesive phase Low, durability is difficult to the tendency obtaining.If tan is δ₂Less than above-mentioned scope, then adhesive phase cannot catch up with polarizer under high temperature Thermal contraction (change in size), exist the situation such as the warpage of polarizer or the fracture of adhesive phase occur tendency.

In above-mentioned adhesive phase, loss angle tangent (tan δ at 23 DEG C₁) with 80 DEG C at loss angle tangent (tan δ₂) ratio (tanδ₂/tanδ₁) preferably more than 1.10, more preferably 1.10～5.0, it is still more preferably 1.10～2.0.Loss The ratio of angle tangent makes flexibility under the high temperature of above-mentioned adhesive phase uprise within the above range, can catch up with the thermal contraction of polarizer (change in size).

In order to form loss angle tangent (the tan δ with above-mentioned scope₁、tanδ₂) adhesive phase, can enumerate and for example use (methyl) acrylic copolymer (A) that will be described hereinafter and isocyanate compound (B1) and metallo-chelate (B2) Deng crosslinking agent (B) as the ingredient of adhesive composition.For example, in the occasion that the total amount making (B1) and (B2) is certain Under, if making the amount minimizing of the relative isocyanate compound (B1) of metallo-chelate (B2), the then crosslinking being produced by chemical bond Ratio raises, and there is the tendency that the loss angle tangent of adhesive phase reduces.

The gel fraction of the adhesive being formed by the adhesive composition of the present invention is preferably 10～70 mass %, further It is preferably 15～65 mass %, be still more preferably 20～60 mass %.Above-mentioned gel fraction is for example to remember according to embodiment The condition carrying is measured the numerical value obtaining to the adhesive being gathered.

The adhesive composition of the present invention is applicable to constitute substrate and the polarization of liquid crystal cell owing to having above characteristic The laminating purposes of piece.Even if particularly the thickness at the glass plate of the liquid crystal cell constituting slimming is little to about 0.1～1.0mm Occasion under, be also applied for the laminating purposes of this substrate and polarizer.

[(methyl) acrylic copolymer (A)]

(methyl) acrylic copolymer (A) is by (methyl) alkyl acrylate that the carbon number comprising alkyl is 4～18 The copolymer that monomer component copolymerization with the monomer of polar functionalities obtains.As the monomer component of copolymer (A), also can enumerate Other monomers in addition.

Acrylic acid and methacrylic acid are referred to as and are denoted as " (methyl) acrylic acid " by this specification.In addition, by polymer Included in the construction unit coming from certain monomer a be denoted as " monomer a unit.”

" (methyl) alkyl acrylate "

As (methyl) alkyl acrylate, (methyl) alkyl acrylate that the carbon number of alkyl can be used to be 4～18 (CH₂=CR¹-COOR²；R¹For hydrogen atom or methyl, R²Alkyl for carbon number is 4～18), wherein, the carbon number of abovementioned alkyl enters one Step is preferably 4～12.

As (methyl) alkyl acrylate that the carbon number of alkyl is 4～18, the such as positive fourth of (methyl) acrylic acid can be enumerated Ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid nonyl ester, (methyl) decyl acrylate, (methyl) acrylic acid undecyl ester, (methyl) lauryl base Ester, (methyl) octadecyl acrylate, (methyl) acrylic acid isooctadecane base ester.These materials can be used alone a kind, it is possible to Use two or more.

In 100 mass % of the monomer component forming (methyl) acrylic copolymer (A), the carbon number of alkyl is 4～18 The total amount of (methyl) alkyl acrylate from the viewpoint of presenting good bonding force and durability, preferably 99.8～ 20 mass %, more preferably 99.5～30 mass %, be still more preferably 99～50 mass %.

Monomer component as (methyl) acrylic copolymer (A), it is possible to use the carbon number of alkyl is the (first of 1～3 Base) alkyl acrylate (CH₂=CR³-COOR⁴；R³For hydrogen atom or methyl, R⁴Alkyl for carbon number is 1～3).

As (methyl) alkyl acrylate that the carbon number of alkyl is 1～3, can enumerate such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate.These materials can be used alone a kind, It is used as two or more.

The carbon number of alkyl be the consumption of (methyl) alkyl acrylate of 1～3 from the viewpoint of stress relief characteristic, In the monomer component of 100 mass % preferably below 60 mass %, further preferably below 50 mass %, still more preferably Below 40 mass %.

" monomer of polar functionalities "

As the monomer of polar functionalities, can enumerate such as hydroxyl monomer, containing acid-based monomers, emulsion stability, contain acyl Amine-containing monomers, the monomer of nitrogenous system heterocycle, cyano-containing monomer.As the acidic group in this specification, such as carboxyl, acid anhydrides can be enumerated Base, phosphate, sulfate.It as the monomer of polar functionalities, is preferably used and there is the crosslinking can being had with crosslinking agent (B) The monomer of the polar group (cross-linking functional group) of property functional group reactions.

Wherein, from be efficiently obtained by cross-linked structure, be readily obtained good durability and further improve and polarizer From the viewpoint of the base material adaptation of blooming, monomer that polar group be carboxyl and/or hydroxyl is preferably used, i.e. preferably makes By at least one in carboxyl group-containing monomer and hydroxyl monomer.

As hydroxyl monomer, (methyl) acrylate for example containing hydroxyl can be enumerated, specifically, (first can be enumerated Base) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 3-hydroxypropyl acrylate, (methyl) acrylic acid 4-hydroxy butyl ester, (methyl) acrylic acid 6-hydroxyl (methyl) hydroxyalkyl acrylates such as own ester, (methyl) acrylic acid 8-hydroxyl monooctyl ester.The carbon of hydroxyalkyl in (methyl) hydroxyalkyl acrylate Number is usually 2～8, preferably 2～6.

The monomer of hydroxyl can be used alone a kind, it is possible to use two or more.

This hydroxyl contained in hydroxyl monomer is as the isocyanide contained with such as isocyanate compound (B1) Perester radical crosslinked cross-linking functional group play a role.The consumption of hydroxyl monomer is preferred in the monomer component of 100 mass % It is 0～15 mass %, more preferably 0.05～10 mass %, be still more preferably 0.1～7 mass %.If containing hydroxyl The consumption of base monomer is below above-mentioned higher limit, then by (methyl) acrylic copolymer (A) and isocyanate compound (B1) The crosslink density being formed will not become too high, can obtain the adhesive phase of stress relief excellent.If hydroxyl monomer Consumption more than above-mentioned lower limit, then can be effectively formed cross-linked structure, be there is suitable intensity viscous at normal temperatures Mixture layer.

As carboxyl group-containing monomer, can enumerate for example (methyl) β-acryloxypropionic acid, (methyl) acrylic acid 5-carboxylic pentyl ester, (methyl) third containing carboxyl such as succinic acid list (methyl) acryloyl-oxy ethyl ester, single (methyl) acrylic acid ω-carboxyl pla-pcl Olefin(e) acid ester；Acrylic acid, methacrylic acid, itaconic acid, butenoic acid, fumaric acid, maleic acid.As the monomer containing anhydride group, can Enumerate such as maleic anhydride, itaconic anhydride.As phosphorous acid-based monomers, (methyl) third on side chain with phosphate can be enumerated Alkene acrylic monomer, as sulfur-bearing acid-based monomers, can enumerate (methyl) acrylic monomer on side chain with sulfate.

Containing this acidic group contained in acid-based monomers as with such as isocyanate compound (B1) or metallo-chelate (B2) crosslinked cross-linking functional group plays a role.Consumption containing acid-based monomers is preferably 0 in the monomer component of 100 mass % ～15 mass %, more preferably 0.05～10 mass %, be still more preferably 0.1～5 mass %.For example, (methyl) The acid number of acrylic copolymer (A) is preferably 0～117mgKOH/g, more preferably 0.4～78mmKOH/g.

If the consumption containing acid-based monomers is below above-mentioned higher limit, then by (methyl) acrylic copolymer (A) and friendship The crosslink density that connection agent (B) is formed will not become too high, can obtain the adhesive phase of stress relief excellent.If containing acid The consumption of base monomer more than above-mentioned lower limit, then can be effectively formed cross-linked structure, is had suitably strong at normal temperatures The adhesive phase of degree.

As emulsion stability, such as (methyl) acrylate, (methyl) acrylic acid diethyl can be enumerated (methyl) acrylate containing amino such as base amino ethyl ester.As amide-containing monomer, can enumerate such as (methyl) acrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-propyl group (methyl) acrylamide, N-hexyl (methyl) third Acrylamide.As the monomer of nitrogenous system heterocycle, such as pyrrolidones, acryloyl morpholine, caprolactam can be enumerated.As Cyano-containing monomer, can enumerate such as cyano group (methyl) acrylate, (methyl) acrylonitrile.

The monomer of polar functionalities can be used alone a kind, it is possible to use two or more.

" other monomers "

The monomer component forming (methyl) acrylic copolymer (A) is not damaging (methyl) acrylic copolymer (A) Physical property in the range of can be containing such as (methyl) alkyl acrylate epoxide alkyl ester, single many alkylene glycols of (methyl) alkyl acrylate epoxide Ester (ア Le U キ シ Port リ ア Le キ レ Application グ リ U Le モ ノ (メ タ) ア Network リ レ ト), contain ester ring type group or aromatic ring Other (methyl) acrylate such as (methyl) acrylate.

As (methyl) alkyl acrylate epoxide alkyl ester, such as (methyl) methoxyethyl methyl esters, (methyl) third can be enumerated Olefin(e) acid 2-methoxy acrylate, (methyl) acrylic acid 2-ethoxy ethyl ester, (methyl) acrylic acid 3-methoxyl group propyl ester, (methyl) propylene Acid 3-ethyoxyl propyl ester, (methyl) acrylic acid 4-methoxybutyl, (methyl) acrylic acid 4-Ethoxybutyl.

As list (methyl) alkyl acrylate epoxide many alkylene glycols ester, for example single (methyl) methoxyethyl two can be enumerated Glycol ester, list (methyl) methoxyethyl DPG ester, single (methyl) ethioxy triglycol ester, single (first Base) ethioxy binaryglycol ester, singly (methyl) methoxyethyl triglycol ester.

As (methyl) acrylate containing ester ring type group or aromatic ring, such as (methyl) acrylate can be enumerated Ester, (methyl) benzyl acrylate, (methyl) phenyl acrylate.

In above-mentioned copolymerization, total consumption of other (methyl) acrylate above-mentioned preferably exists in the monomer component of 100 mass % Below 60 mass %, further preferably below 40 mass %.

In addition, in the range of not damaging the physical property of (methyl) acrylic copolymer (A), it is possible to use such as benzene second Alkene, methyl styrene, dimethyl styrene, trimethyl styrene, propylstyrene, butylstyrene, hexyl benzene ethene, heptyl The ring-alkylated styrenes such as styrene and octyl styrene, fluorobenzene ethene, chlorostyrene, bromstyrol, Dowspray 9, iodobenzene second The styrene monomers such as alkene, nitrostyrolene, acetylbenzene ethene and methoxy styrene；The copolymerizable lists such as vinyl acetate Body.

In above-mentioned copolymerization, total consumption of above-mentioned co-polymerized monomer in the monomer component of 100 mass % preferably in 40 matter Amount below %, further preferably below 20 mass %.

Other monomers can be used alone a kind, it is possible to use two or more.

" manufacturing condition of (methyl) acrylic copolymer (A) "

(methyl) acrylic copolymer (A) preferably passes through above-mentioned common in the presence of peroxide type polymerization initiator Copolymer obtained by poly-.As polymerization initiator, by using peroxide type polymerization initiator, have that to obtain side chain many The tendency of polymer molecule.Therefore, (1) at room temperature because of a large amount of the sending out that interweave produced by the mutual side chain of polymer molecule Raw, even if its result is polymer molecular weight and adhesive phase gel fraction is designed to low, the coherency of polymer also can be tieed up Hold, obtain adhesion characteristic, to excellent gluing of keeping property such as the processabilities such as adhesive phase punching press, the deformation of adhesive phase and extrusion are few Mixture layer；(2) the above-mentioned interlaced sections that polymer molecule is mutual under high temperature (for example: 60 DEG C) relaxes, thus adhesive phase Adhesion properties increase degree is high to the dependence of temperature, and adhesive phase presents excellent flexibility.Therefore, the warpage at polarizer While (bending) suppression aspect is excellent, adhesive phase is made to present due to the above-mentioned intertexture of part residual excellent durable Property.

With regard to above-mentioned (1) and (2), a part of crosslinking agent (B) uses the occasion of metallo-chelate described later (B2) Under, utilize the coordinate bond between (methyl) acrylic copolymer (A)/metallo-chelate (B2) to form crosslinking (quasi-crosslink (day Literary composition: doubtful frame)).Accordingly, there exist following tendency: the described crosslinking when above-mentioned room temperature is maintained, polymer plays cohesion Property, and a part for described crosslinking releases when above-mentioned high temperature, adhesive phase presents more excellent flexibility.

Contribute to suppressing this point of warpage of polarizer with regard to the many polymer of side chain, thus it is speculated that caused by being due to the fact that. To use glass plate to carry out as a example by the occasion of clung body in such as polarizer/such structure of adhesive phase/clung body Explanation.Polarizer percent thermal shrinkage respective from glass plate is different, and the percent thermal shrinkage (change in size) of polarizer is generally than glass plate Greatly.Lacking under the occasion of the flexibility under hot and humid thermal environment at adhesive phase, adhesive phase cannot catch up with polarizer , therefore there is warpage on a glass in change in size, it is impossible to alleviating the stress at adhesive phase, stress concentrates on glass plate.And Use high branched-chain polymer and in a part for crosslinking agent, use metallo-chelate occasion under, due to high at high temperature The part releasing of the lax and above-mentioned crosslinking of a part for above-mentioned intertexture under hygrothermal environment, adhesive phase can catch up with polarizer Change in size.Therefore, will not produce stress, stress is not centered on glass plate.In addition, polarizer is also without anisotropy Ground uniform heat shrinks, and will not induce the birefringence of polarizer.As described above, adhesive phase can be with the change in size of polarizer And absorbing alleviation stress, thus without the stress (load) excessive to glass plate applying, thus it is speculated that this is related to stick up glass plate Bent suppression.

(methyl) acrylic copolymer (A) may utilize such as solution polymerization process, mass polymerization, emulsion polymerization, hangs The known so far polymerizations such as floating polymerization manufacture, wherein preferred solution polymerization process.Specifically, it is by polymer solvent and list Body becomes to be distributed in reaction vessel, adds polymerization initiator under the inert gas atmospheres such as nitrogen, and reaction starts temperature and is set as Usual 40～100 DEG C, preferably 50～80 DEG C, make reaction system maintain at a temperature of usual 50～90 DEG C, preferably 70～90 DEG C React 4～20 hours.

As peroxide type polymerization initiator, can enumerate for example:

Two (peroxidating 2-ter /-butylisopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-two (peroxidating uncle Butyl) the dialkyl group peroxidating such as hexane, tert-butyl cumyl peroxide, two tertiary hexyl peroxide, di-tert-butyl peroxide (for example: the compound representing with R-O-O-R, the R in formula is separately the substituted alkyl of alkyl or aryl to species；With R- The compound that O-O-A-O-O-R represents, the R in formula is separately the substituted alkyl of alkyl or aryl, and A is the hydrocarbon of divalent Base)；

Diisobutyl peroxide, two (3,5,5-trimethyl acetyl base) peroxide, dilauroyl peroxide, peroxidating Dibenzoyl, benzoyl (3-methyl benzoyl) peroxide, two (3-methyl benzoyl) peroxide, two (4-first Base benzoyl) diacyl peroxide class (for example: the compound representing with R-COO-OCO-R, the R in formula such as peroxide It is separately alkyl or aryl)；

Peroxy dicarbonate di-n-propyl ester, di-isopropyl peroxydicarbonate, peroxy dicarbonate two (4-t-butylcyclohexyl Base) ester, peroxy dicarbonate two (2-ethylhexyl) peroxy dicarbonate such as ester, peroxide-butyl carbonate (for example: The compound representing with R-OCO-O-O-COO-R, the R in formula is separately alkyl or cycloalkyl)；

The withered ester of peroxidating neodecanoic acid, peroxidating neodecanoic acid 1,1,3,3-tetramethyl butyl ester, the tertiary own ester of peroxidating neodecanoic acid, mistake The oxidation neodecanoic acid tert-butyl ester, the new heptanoic acid tert-butyl ester of peroxidating, the tertiary own ester of peroxidating neopentanoic acid, tert-Butyl peroxypivalate, mistake Oxidation-2 ethyl hexanoic acid 1,1,3,3-tetramethyl butyl ester, 2,5-dimethyl-2,5-two (peroxidating 2-ethyl hexyl acyl group) hexane, The tertiary own ester of peroxidating 2 ethyl hexanoic acid, the peroxidating 2 ethyl hexanoic acid tert-butyl ester, the peroxidating 3,5,5 Trimethylhexanoic acid tert-butyl ester, mistake The oxidation laurate tert-butyl ester, the tertiary own ester of perbenzoic acid, 2,5-dimethyl-2,5-two (benzoyl peroxide base) hexane, mistake The peroxyesters such as the acetic oxide tert-butyl ester, peroxidating 3-methylbenzoate, peroxidized t-butyl perbenzoate (for example: With R¹-O-O-CO-R²The compound representing, the R in formula¹For the substituted alkyl of alkyl or aryl, R²For alkyl, aryl or aryl Substituted alkyl；The compound representing with R-CO-O-O-A-O-O-CO-R, the R in formula is separately alkyl or aryl, A Alkyl for divalent)；

The tertiary own ester of isopropyl peroxide list carbonic acid, isopropyl peroxide list t-butyl carbonate, peroxidating-2-ethylhexyl list (for example: the compound representing with R-O-O-COO-R, the R in formula is separately for the peroxidating monocarbonate classes such as t-butyl carbonate For alkyl).

In peroxide type polymerization initiator, owing to (methyl) acrylic copolymer of high side chain can be obtained, thus Preferably peroxyesters, the peroxide type polymerization initiator further preferably representing with following formula (1).

[formula 1]

In formula (1), R^A～R^FIt is separately hydrogen atom, alkyl or aryl, owing to the copolymerization of high side chain can be obtained Thing, thus alkyl, phenyl that preferred carbon number is 1～10, further preferred carbon number is the alkyl of 1～8, still more preferably carbon number Being the alkyl of 1～4, particularly preferred carbon number is the alkyl of 1～2.

With in the peroxide type polymerization initiator that formula (1) represents, preferably tert-Butyl peroxypivalate, peroxidating new penta The tertiary own ester of acid, new peroxide tert-butyl caprate, the new heptanoic acid tert-butyl ester of peroxidating, peroxide-2-ethyl hexanoic acid tert-butyl, peroxidating The withered ester of neodecanoic acid, owing to can obtain the copolymer of high side chain, thus particularly preferred tert-Butyl peroxypivalate, peroxidating are new The tertiary own ester of valeric acid, new peroxide tert-butyl caprate, the new heptanoic acid tert-butyl ester of peroxidating, peroxide-2-ethyl hexanoic acid tert-butyl.

Peroxide type polymerization initiator can be used alone a kind, it is possible to use two or more.In addition, be also not limited in polymerization In repeatedly add peroxide type polymerization initiator.

As polymerization initiator, as long as the copolymer of high side chain can be obtained, can also cause using peroxide Azo-initiator is used while agent.As azo-initiator, such as 2 can be enumerated, 2 '-azodiisobutyronitrile, 2,2 '-idol Nitrogen two (4-methoxyl group-2,4-methyl pentane nitrile), 2,2 '-azo two (2-cyclopropyl propionitrile), 2,2 '-azo two (2,4-diformazan Base valeronitrile), 2,2 '-azo two (2-methylbutyronitrile), 1,1 '-azo two (hexamethylene-1-nitrile), 2-(carbamoyl azo) different Butyronitrile, 2-phenylazo-4-methoxyl group-2,4-methyl pentane nitrile, two acidified 2,2 '-azos two (2-amidine propane), 2,2 '- Azo two (N, N '-dimethyleneisobutylamidine), 2,2 '-azo two [2-methyl-N-(2-ethoxy)-propionamide], 2,2 '-azo Two (isobutyramide) dihydrate, 4,4 '-azo two (4-cyanopentanoic acid), 2,2 '-azo two (2-cyano group propyl alcohol), dimethyl- The azo-compounds such as 2,2 '-azo two (2 Methylpropionic acid ester), 2,2 '-azo two [2-methyl-N-(2-ethoxy) propionamide]. These polymerization initiators can be used alone a kind, it is possible to use two or more.

Relative to the monomer component of formation (methyl) acrylic copolymer (A) of 100 mass parts, with usual 0.001～5 Mass parts, the amount of preferably 0.005～3 mass parts use peroxide type polymerization initiator.In addition, azo-initiator is preferably not Use, its consumption relative to the peroxide type polymerization initiator of 100 mass parts preferably below 0.5 mass parts, excellent further It is selected in below 0.2 mass parts, be still more preferably 0 mass parts.But, for the purpose of reducing the monomer reacting later half middle remaining It is then used for not limiting.In addition, in above-mentioned polymerisation, it is also possible to suitably add and add polymerization initiator, chain tra nsfer Agent, monomer component, polymer solvent.

As for the polymer solvent in polymerisation in solution, such as benzene,toluene,xylene etc. can be enumerated aromatic hydrocarbon；Just The aliphatic hydrocarbons such as pentane, n-hexane, normal heptane, normal octane；The ester ring type hydrocarbon such as pentamethylene, hexamethylene, cycloheptane, cyclooctane Class；Diethyl ether, diisopropyl ether, 1,2-dimethoxy-ethane, butyl oxide, oxolane, dioxane (dioxane), methyl phenyl ethers anisole, benzene The ethers such as ether, diphenyl ether；The halogenated hydrocarbons such as chloroform, carbon tetrachloride, 1,2-dichloroethanes, chlorobenzene；Ethyl acetate, acetic acid third The esters such as ester, butyl acetate, methyl propionate；The ketones such as acetone, MEK, diethyl ketone, methylisobutylketone, cyclohexanone；N, N-bis- The amide-types such as NMF, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE；The nitrile such as acetonitrile, benzonitrile；Diformazan is sub- The sulfoxide type such as sulfone, sulfolane.These polymer solvents can be used alone a kind, it is possible to use two or more.

In the adhesive composition of the present invention, cause as polymerization when manufacturing (methyl) acrylic copolymer (A) The available following formula of the reacted survival rate (%) of the peroxide type polymerization initiator elapsed time t that agent is preferably used is tried to achieve.

Survival rate (%)=exp (-k_dT) × 100 (%)

In formula, k_dFor thermal decomposition rate constant, with Arrhenius formula k_d=A × exp (-Δ E/RT) represents, wherein A For frequency factor, Δ E is the activation energy of polymerization initiator in pyrolysis, and R is gas constant (8.314J/ mole of K), T For absolute temperature (K)；T is the reaction time.

Can use in such as Japan Oil Co (Japan Oil Co) organic peroxide catalogue (the 10th edition) described Numerical value obtain frequency factor (A) and the activation energy (Δ E) of above-mentioned peroxide type polymerization initiator.For example, peroxidating new penta The Δ of tert-butyl acrylate E=119.1kJ/ mole, A=6.93 × 10¹⁷Hour^-1, the Δ E=of the tertiary own ester of peroxidating neopentanoic acid 118.5kJ/ mole, A=6.45 × 10¹⁷Hour^-1, Δ E=105.3kJ/ mole of the withered ester of peroxidating neodecanoic acid, A=3.94 × 10¹⁶Hour^-1。

So, owing to the k at given temperature can be calculated_d, it is thus possible to calculate at given temperature through out-of-date according to above formula Between the survival rate (%) of reacted peroxide type polymerization initiator of t.Therefore, it is possible to used in by above-mentioned copolymerization Amount × the survival rate (%) of peroxide type polymerization initiator calculates peroxide type polymerization contained in adhesive composition The remaining quantity of initiator.

" physical property of (methyl) acrylic copolymer (A) and content "

(methyl) acrylic copolymer (A) utilizes the weight average molecular weight (Mw) that gel permeation chromatography (GPC method) measures It is usually 200,000～1,500,000, preferably 400,000～1,300,000, more preferably 500,000～110 in terms of polystyrene conversion value Ten thousand.For example, if using the copolymer (A) that Mw is little, then the polymer molecular weight after crosslinking can be suppressed relatively low, thus high The mobility of the lower adhesive of temperature raises, and there is the tendency that loss angle tangent becomes big.And if using the copolymer (A) that Mw is big, then The molecular weight of crosslinked post-consumer polymer uprises, and under high temperature, the mobility of adhesive reduces, and there is the tendency that loss angle tangent diminishes.

(methyl) acrylic copolymer (A) utilizes the molecular weight distribution (Mw/Mn) that GPC method measures generally below 50, Preferably below 30, further preferably below 20.

(methyl) acrylic copolymer (A) utilizes the degree of branching that GPC-MALS method measures preferably below 0.55, enters one Step is preferably 0.10～0.54, is still more preferably 0.20～0.53, and particularly preferably 0.30～0.53.The degree of branching measures bar The detailed content of part is recorded in embodiment.It in order to adjust the loss angle tangent of adhesive phase to above-mentioned scope, is preferably used Degree of branching copolymer (A) within the above range.

The degree of branching shows the index that polymer is branched shape or linearity, is branched shape when the degree of branching is below 0.55 Polymer, is linearity polymer during more than 0.55.In addition, in branched shaped polymer, be polymerized under the little occasion of degree of branching numerical value The branch of thing molecule is many, is shown as having high side chain, and under the big occasion of degree of branching numerical value, the branch of polymer molecule is few, is shown as There is low side chain.

The glass transition temperature (Tg) of (methyl) acrylic copolymer (A) can be by the monomer for example constituting this polymer Unit and content ratio thereof utilize Fox formula to calculate.For example, it is possible to according to the glass transition temperature tried to achieve by Fox formula (Tg) condition reaching usually-70～0 DEG C, preferably-60～-30 DEG C synthesizes (methyl) acrylic copolymer (A).Logical Cross use and there is (methyl) acrylic copolymer (A) of such glass transition temperature (Tg), can obtain under normal temperature viscous The excellent adhesive composition of conjunction property.

Fox formula: 1/Tg=(W₁/Tg₁)+(W₂/Tg₂)+…+(W_m/Tg_m)

W₁+W₂+…+W_m=1

In formula, Tg is the glass transition temperature of (methyl) acrylic copolymer (A), Tg₁、Tg₂、……、Tg_mServe as reasons The glass transition temperature of the homopolymers that each monomer is constituted, W₁、W₂、……、W_mFor deriving from construction unit above-mentioned of each monomer Weight fraction in copolymer (A).

The glass transition temperature of the homopolymers being made up of each monomer in above-mentioned Fox formula can use such as " polymer hand Volume " numerical value described in (Polymer Handbook) fourth edition (Wiley-Interscience 1999).

The content of (methyl) acrylic copolymer (A) in the adhesive composition of the present invention being somebody's turn to do in 100 mass % Composition is usually in the solid constituent in addition to organic solvent (E) 50～99.99 mass %, more preferably 60～ 99.95 mass %, particularly preferably 80～99.90 mass %.If the content of (methyl) acrylic copolymer (A) is above-mentioned In the range of, then can obtain the balance of the performance as adhesive, and adhesion characteristic is excellent.

[crosslinking agent (B)]

Crosslinking agent (B) is as long as can crosslink the composition of reaction with (methyl) acrylic copolymer (A) and just not make It is particularly limited to, such as isocyanate compound (B1), metallo-chelate (B2), epoxide (B3) can be enumerated.

Crosslinking agent (B) can be used alone a kind, it is possible to use two or more.

Isocyanate compound (B1) and metallo-chelate (B2) are preferably applied in combination by crosslinking agent (B).From by bonding The loss angle tangent of oxidant layer adjusts to above-mentioned scope, preferably by the covalency based on isocyanate compound (B1) Key to form crosslinking to (methyl) acrylic copolymer (A), and right by coming based on the coordinate bond of metallo-chelate (B2) The formation quasi-crosslink (Japanese: doubtful frame) of (methyl) acrylic copolymer (A).

In the adhesive composition of the present invention, the total content of crosslinking agent (B) is relative to (methyl) propylene of 100 mass parts Acid copolymer (A) is preferably 0.01～5 mass parts, more preferably 0.05～2.5 mass parts, is still more preferably 0.1～1 mass parts.By containing such a certain amount of crosslinking agent (B), the suitable degree of cross linking can be reached, it is achieved excellent Durability under cohesive, dimensional stability, high humid and warm environment.

" isocyanate compound (B1) "

As isocyanate compound (B1), generally use isocyanation esterification more than 2 for the isocyanates radix in 1 molecule Compound.Make (methyl) acrylic copolymer (A) crosslinked by utilizing isocyanate compound (B1), crosslinked can be formed (network polymers).

The isocyanates radix of isocyanate compound (B1) generally more than 2, preferably 2～8, more preferably 3 ～6.If isocyanates radix is within the above range, then at (methyl) acrylic copolymer (A) and isocyanate compound (B1) on this aspect of cross-linking reaction efficiency and keep adhesive this aspect of flexibility on be preferred.

As the diisocyanate cpd that isocyanates radix in 1 molecule is 2, for example aliphatic two isocyanic acids can be enumerated Ester, alicyclic diisocyanate, aromatic diisocyanates.As aliphatic vulcabond, can enumerate ethylidene diisocyanate, Tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl isophthalic acid, 5-pentane two is different Cyanate, 3-methyl isophthalic acid, the carbon number such as 5-pentane diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate is 4 The aliphatic vulcabond of～30.As alicyclic diisocyanate, IPDI, cyclopenta two can be enumerated different Cyanate, cyclohexyl diisocyanate, the sub-XDI of hydrogenation, HTDI, hydrogenation hexichol first The carbon numbers such as alkane diisocyanate, the hydrogenation sub-XDI of tetramethyl are the alicyclic diisocyanate of 7～30.As Aromatic diisocyanates, can enumerate for example phenylene vulcabond, toluene di-isocyanate(TDI), sub-XDI, The carbon numbers such as naphthalene diisocyanate, diphenyl ether diisocyanate, '-diphenylmethane diisocyanate, diphenylpropane diisocyanate are 8 The aromatic diisocyanates of～30

As isocyanate compound more than 3 for the isocyanates radix in 1 molecule, such as aromatics polyisocyanate can be enumerated Ester, aliphatic polymeric isocyanate, alicyclic polymeric isocyanate.Specifically, can enumerate 2,4,6-triisocyanate toluene, 1,3,5- Triisocyanate benzene, 4,4', 4 "-triphenylmethane triisocyanate.

In addition, as isocyanate compound (B1), can enumerate such as isocyanates radix 2 or more than 3 above-mentioned different The polymer (such as dimer or tripolymer, biuret body, isocyanuric acid ester body) of cyanate esters, derivative are (for example many The addition reaction product of diisocyanate cpd more than unit's alcohol and 2 molecules), polymer.As many in said derivative Unit's alcohol, low molecular weight polyols can enumerate the alcohol of more than the such as ternarys such as trimethylolpropane, glycerine, pentaerythrite；High score Sub-weight polyalcohol can enumerate such as PPG, PEPA, acrylic polyol, polybutadiene polyol, poly-isoamyl Diene polyol.

Such isocyanate compound can enumerate the tripolymer of such as '-diphenylmethane diisocyanate, polymethylene polyphenyl The biuret body of base PIC, hexamethylene diisocyanate or toluene di-isocyanate(TDI) or isocyanuric acid ester body, three hydroxyls Methylpropane and product (the such as toluene di-isocyanate(TDI) or Asia of toluene di-isocyanate(TDI) or sub-XDI Three molecule addition products of XDI), the product (example of trimethylolpropane and hexamethylene diisocyanate The three molecule addition products such as hexamethylene diisocyanate), polyethers PIC, polyester PIC.

In isocyanate compound (B1), can carry on good curing performance and this aspect of light leak performance, preferably trihydroxy methyl third (chemical society (is ground) by Soken Chemical & Engineering Co., Ltd. for alkane and the product of toluene di-isocyanate(TDI) or sub-XDI The L-45 manufacturing, the TD-75 etc. that Soken Chemical & Engineering Co., Ltd. manufactures), hexamethylene diisocyanate or toluene di-isocyanate(TDI) Isocyanuric acid ester body (TSE-100 that Asahi Chemical Industry Co., Ltd (Asahi Chemical Industry Gong She) manufactures, Japanese polyurethane strain formula meeting Society (Japan Port リ ウ レ タ Application society) manufacture 2050 etc.).

Isocyanate compound (B1) can be used alone a kind, it is possible to use two or more.

" metallo-chelate (B2) "

As metallo-chelate (B2), can enumerate such as alkoxide, acetylacetone,2,4-pentanedione, ethyl acetoacetate etc. to aluminium, iron, copper, The compound of the polyvalent metal coordination such as zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium.Wherein, preferably aluminium chelate compound (combines grinding Learn the M-12AT etc. that Co., Ltd. manufactures).Specifically, aluminium isopropoxide, secondary butyric acid aluminium, acetoacetate aluminium ethide two can be enumerated different Propyl ester, tri ethylacetoacetate aluminium, praseodynium aluminium.

Metallo-chelate (B2) can be used alone a kind, it is possible to use two or more.

In the adhesive composition of the present invention, in the occasion using isocyanate compound (B1) and metallo-chelate (B2) Under, the content that adds up to of above-mentioned (B1) and (B2) is preferably 0.01 relative to (methyl) acrylic copolymer (A) of 100 mass parts ～5 mass parts, more preferably 0.05～2.5 mass parts, be still more preferably 0.1～1 mass parts.If this content exists It in above-mentioned scope, then is preferred the loss angle tangent of adhesive phase being adjusted to this aspect of above-mentioned scope.If should Content exceedes above-mentioned scope, then the loss angle tangent that there is adhesive phase becomes too small tendency, if being less than above-mentioned scope, then The loss angle tangent that there is adhesive phase becomes excessive tendency.

In the adhesive composition of the present invention, the content of metallo-chelate (B2) is relative to the isocyanates of 100 mass parts Compound (B1) is preferably 10～1000 mass parts, more preferably 50～600 mass parts, be still more preferably 100～ 400 mass parts.If this content is within the above range, then the loss angle tangent of adhesive phase can adjusted to above-mentioned scope It is preferred on this aspect.Under the certain occasion of the total amount of (B1) and (B2), if the content of (B2) exceedes above-mentioned scope, then The loss angle tangent that there is adhesive phase becomes excessive tendency, if being less than above-mentioned scope, then there is the loss of adhesive phase Angle tangent becomes too small tendency.

" epoxide (B3) "

As epoxide (B3), generally use epoxide more than 2 for the 1 molecule epoxy group number.Can enumerate Such as ethylene glycol diglycidyl base ether, polyethylene glycol diglycidyl base ether, glycerine diglycidyl ether, glycerine three shrink Glyceryl ether, 1,3-double (N, N-diglycidyl amino methyl) hexamethylene, N, N, N', N'-four glycidyl group isophthalic two Methylamine, N, N, N', N'-four glycidyl group aminophenyl methane, isocyanic acid three-glycidyl ester, a N, N-diglycidyl Aminophenyl glycidyl ether, N, N-diglycidyl toluidines, N, N-diglycidylaniline.

In the adhesive composition of the present invention, under using the occasion as crosslinking agent (B) for the epoxide (B3), above-mentioned (B3) content is preferably 0～2 mass parts relative to (methyl) acrylic copolymer (A) of 100 mass parts, more preferably 0～1 mass parts, still more preferably in 0～0.5 mass parts.

[silane coupler (C)]

Preferably the polarizer adhesive composition of the present invention is possibly together with silane coupler (C).Silane coupler (C) makes to glue The clung body strong bond such as mixture layer and glass plate, contribute to preventing the stripping under high humid and warm environment.

As silane coupler (C), such as vinyltrimethoxy silane, VTES, first can be enumerated The silane coupler containing polymerism unsaturated group such as base acryloxypropyl trimethoxy silane；3-glycidoxy third Base trimethoxy silane, 3-glycidoxypropyl group triethoxysilane, 3-glycidoxypropyl dimethoxysilane, 3-glycidoxypropyl diethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane etc. contain epoxy The silane coupler of base；3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330, The silane coupler containing amino such as N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane；3-chloro propyl group three The silane coupler containing halogen such as methoxy silane.

The content of the silane coupler (C) in the polarizer adhesive composition of the present invention is relative to 100 mass parts (methyl) acrylic copolymer (A) generally below 1 mass parts, preferably 0.01～1 mass parts, more preferably 0.05 ～0.5 mass parts.If content is within the above range, then has and prevent polarizer under high humid and warm environment from peeling off or hot environment The tendency that lower silane coupler (C) is oozed out.

[antistatic agent (D)]

Antistatic agent can be used to for example reduce the sheet resistance value of polarizer adhesive composition of the present invention (D).Antistatic agent (D) can enumerate such as surfactant, ionic compound, electric conductive polymer.

As surfactant, can enumerate such as quaternary ammonium salt, amidoquat salt, pyridine salt, have primary amino radical～ The cationic surface active agent of the cationic groups such as tertiary amino；There are sulphonate-base, sulfuric ester alkali, phosphate alkali etc. The anionic surfactant of anionic group；Alkyl betaines bases, alkyl imidazole betaines, alkyl amine The amphoteric surfactantes such as class, amino acid sulfuric acid ester；Fatty acid glycerine esters, sorbitan fatty acid ester class, polyoxy second Allylic alkylation amine, polyoxyethylene alkyl amine fatty acid ester, N-ethoxy-N-2-hydroxyalkyl amine, alkyl diethanolamide class Deng nonionic surface active agent.

In addition, surfactant also can enumerate the reactive emulsifier with polymerizable group, it be also possible to use and make containing upper State the polymer types of surfactants obtained by the monomer component molecular weight of surfactant or reactive emulsifier.

Ionic compound is made up of cationic moiety and anionicsite, and at room temperature (23 DEG C/50%RH) are in solid-state Or any one in liquid.

The cationic moiety constituting ionic compound both can be appointing in mineral-type cation or organic cation One, it is also possible to be both.Mineral-type cation preferred as alkali ion and alkaline-earth metal ion, further preferred antistatic The excellent Li of property⁺、Na⁺And K⁺.As organic cation, such as pyridylium, piperidines cation, pyrrolidones can be enumerated Cationoid, pyrrolin cation, pyrroles's cation, glyoxaline cation, tetrahydropyrimidine cation, dihydro-pyrimidin cation, pyrrole Azoles cation, pyrazine cation (ピ ラ ゾ リ ニ ウ system カ チ オ Application), tetraalkylammonium cation, trialkylsulfonium cation, four alkane Base phosphine cation and their derivative.

As long as constitute ionic compound anionicsite can with cationic moiety ionic bonding and form ion The material of type compound is then not specially limited.Specifically, F can be enumerated^-、Cl^-、Br^-、I^-、AlCl₄ ^-、Al₂Cl₇ ^-、BF₄ ^-、 PF₆ ^-、SCN^-、ClO₄ ^-、NO₃ ^-、CH₃COO^-、CF₃COO^-、CH₃SO₃ ^-、CF₃SO₃ ^-、(CF₃SO₂)₂N^-、(F₂SO₂)₂N^-、(CF₃SO₂)₃C^-、AsF₆ ^-、SbF₆ ^-、NbF₆ ^-、TaF₆ ^-、F(HF)_n ^-、(CN)₂N^-、C₄F₉SO₃ ^-、(C₂F₅SO₂)₂N^-、C₃F₇COO^-(CF₃SO₂) (CF₃CO)N^-.Wherein, the anion containing fluorine atom is preferred because providing the ionic compound of low melting point, particularly preferably (F₂SO₂)₂N^-(CF₃SO₂)₂N^-。

Ionic compound preferred bis-trifluoromethylsulfoandimide lithium, double difluoro sulfimide lithium, three (trifyls) Methane lithium, bis-trifluoromethylsulfoandimide potassium, double difluoro sulfimide potassium, hexafluorophosphoric acid 1-ethylpyridine, hexafluorophosphoric acid 1-butyl Pyridine, hexafluorophosphoric acid 1-hexyl-4-picoline, hexafluorophosphoric acid 1-octyl group-4-picoline, 1-octyl group-4-picoline two Fluorine sulfimide, 1-octyl group-4-picoline bis-trifluoromethylsulfoandimide, tetrafluoro boric acid (N, N-diethyl-N-methyl-N-(2- Methoxy ethyl) ammonium, N, N-diethyl-N-methyl-N-(2-methoxy ethyl) ammonium bis-trifluoromethylsulfoandimide, 1-octylpyridinium Fluorine thionyl imide (1-オ Network チ Le ピ リ ジ ニ ウ system Off Le オ ロ ス ホ ニ ウ system イ ミ De), 1-octyl group-3-picoline, three Fluorine thionyl imide (ト リ Off Le オ ロ ス Le ホ ニ ウ system イ ミ De).

As electric conductive polymer, such as polythiophene, polyaniline, polypyrrole and their derivative can be enumerated.

The content of the antistatic agent (D) in the polarizer adhesive composition of the present invention is relative to (the first of 100 mass parts Base) acrylic copolymer (A) generally below 3 mass parts, preferably 0.01～3 mass parts, more preferably 0.05～ 2.5 mass parts.

[organic solvent (E)]

The adhesive composition of the present invention preferably comprises organic solvent (E) to regulate its coating.Organic solvent can Enumerate the polymer solvent of explanation in (methyl) acrylic copolymer (A) hurdle.For example, can be by containing of obtaining in above-mentioned copolymerization The polymer solution having (methyl) acrylic copolymer (A) and polymer solvent mixes to come modulating adhesive group with crosslinking agent (B) Compound.In the adhesive composition of the present invention, the content of organic solvent is usually 50～90 mass %, preferably 60～85 matter Amount %.

In addition, " solid constituent " in this specification refers to have except above-mentioned in composition contained in adhesive composition Whole compositions beyond machine solvent (E), " solid component concentration " refers to the adhesive relative to 100 mass % for the above-mentioned solid constituent The ratio of composition.

[peroxide]

(peroxide is crosslinked preferably not to blend the peroxide as crosslinking agent in the adhesive composition of the present invention Agent).The content of peroxide includes that the peroxide type polymerization being used during the synthesis of (methyl) acrylic copolymer (A) draws Send out including the remaining quantity of agent, relative to (methyl) acrylic copolymers (A) of 100 mass parts preferably below 0.1 mass parts, Further preferably below 0.05 mass parts, still more preferably below 0.01 mass parts.By using isocyanates chemical combination Thing (B1), metallo-chelate (B2), epoxy crosslinking agent (B3) etc. do not use peroxide crosslinking agent as crosslinking agent (B), The deterioration of the adhesive phase causing because of the peroxide of residual can be suppressed.

[additive]

The adhesive composition of the present invention is in addition to mentioned component, in the range of not damaging effect of the present invention, also may be used Containing beyond antioxidant, light stabilizer, preventing metal corrosion agent, tackifier, plasticizer, crosslinking accelerator, above-mentioned (A) One kind or two or more in (methyl) acrylic polymer and heavy industry remover (Japanese: リ ワ Network).

[modulation of polarizer adhesive composition]

The polarizer adhesive composition of the present invention can be by utilizing known so far method to (methyl) acrylic compounds Copolymer (A) carries out mixing modulating with crosslinking agent (B) and other compositions using as desired.Can enumerate for example to conjunction The polymer solution containing this polymer obtained when becoming (methyl) acrylic copolymer (A) blends crosslinking agent (B) Other compositions using as desired.

[polarizer adhesive phase]

The adhesive phase of the present invention can be obtained by for example carrying out the cross-linking reaction in above-mentioned adhesive composition, specifically It is can be by making (methyl) acrylic polymer (A) crosslinking obtain with crosslinking agent (B).

In the adhesive phase of the present invention, loss angle tangent (tan δ at 23 DEG C₁) it is 0.33～0.55, preferably 0.35～ 0.52, particularly preferably 0.40～0.49；And loss angle tangent (tan δ at 80 DEG C₂) it is 0.40～0.65, preferably 0.42～ 0.62, particularly preferably 0.47～0.56.

In above-mentioned adhesive phase, loss angle tangent (tan δ at 23 DEG C₁) with 80 DEG C at loss angle tangent (tan δ₂) ratio (tanδ₂/tanδ₁) preferably more than 1.10, more preferably 1.10～5.0, it is still more preferably 1.10～2.0.

Above-mentioned loss angle tangent is by for example repeatedly fitting between above-mentioned adhesive phase, making thickness and be about The duplexer of 1.0mm, the value being calculated by the dynamic viscoelastic spectrogram that this duplexer is recorded.

The formation condition of adhesive phase is for example as described below.It is coated on the adhesive composition of the present invention on supporting mass, Temperature is different because of solvent species, but generally 50～150 DEG C, preferably carry out at 60～100 DEG C usually 1～10 minute, excellent Elect the drying of 2～7 minutes as to remove solvent, form film.The thickness of dry coating is usually 5～75 μm, preferably 10～ 50μm。

Adhesive phase is preferably formed under the following conditions.It is coated on the adhesive composition of the present invention on supporting mass, After pasting cover layer on the film that formed under these conditions, usual 5～60 DEG C, preferably 15～40 DEG C and usual 30～ Maintenance usual more than 3 days, preferably 7～10 days in the environment of 70%RH, preferably 40～70%RH.If in curing as described above Under the conditions of carry out crosslinking, then can be efficiently formed crosslinked (network polymers).

As the coating process of adhesive composition, known method can be used, for example, pass through spin-coating method, cutter coating, roller Coating, stick coating method, scraper coating, die coating method, gravure coating method etc. form the coating drying means of specific thickness.

As supporting mass and cover layer, the such as polyester films such as polyethylene terephthalate (PET) can be enumerated；Poly-second The plastic foil of the polyolefin films etc. such as alkene, polypropylene, vinyl-vinyl acetate copolymer.

The adhesive phase being formed by the adhesive composition of the present invention is from suppression polarizer distortion, cohesiveness, bonding force, again From the viewpoint of fissility, gel fraction is preferably 10～70 mass %, more preferably 15～65 mass %, further It is preferably 20～60 mass %.Even if owing to gel fraction (methyl) acrylic copolymer (A) within the above range also has High side chain, thus can moderately be interweaved between the side chain of copolymer (A), durability or the processability of adhesive phase will not Deteriorate.Particularly when gel fraction is more than 20 mass %, then can obtain the high adhesive phase of coherency.If gel divides Number exceeds above-mentioned scope, then adhesive phase cannot fully absorb and alleviate by the change in size of polarizer under hot and humid thermal environment Caused stress.

[polarizer bonding sheet]

The polarizer bonding sheet of the present invention has the adhesive phase being formed by above-mentioned polarizer adhesive composition.Make For bonding sheet, can enumerate and for example only there is the double-sided adhesive sheet of above-mentioned adhesive phase, there is base material and be formed on base material two sides Above-mentioned adhesive phase double-sided adhesive sheet, there is base material and the one side of the above-mentioned adhesive phase being formed on the face of base material one side Bonding sheet and these bonding sheets are pasted with the cover layer through lift-off processing with base material on the face not contacted of adhesive phase Bonding sheet.

As base material and cover layer, the such as polyester films such as polyethylene terephthalate (PET) can be enumerated；Polyethylene, The plastic foil of the polyolefin film such as polypropylene, vinyl-vinyl acetate copolymer etc..

The formation condition of adhesive phase or loss angle tangent, gel fraction are remembered in [polarizer adhesive phase] hurdle The condition carrying is identical.

The thickness of adhesive phase is usually 5～75 μm from the viewpoint of maintaining bond properties, preferably 10～50 μm.Base The thickness of material and cover layer is not particularly limited, but usually 10～125 μm, preferably 25～75 μm.

[with the polarizer of adhesive phase]

The polarizer with adhesive phase of the present invention is characterized by polarizer and at above-mentioned polarizer at least The adhesive phase being formed by polarizer adhesive composition of the present invention on the face of side.In addition, in this specification, " polarizer " Use with the implication comprising " polarizing coating ".

Polarizer can use known so far polarizing coating.Can enumerate and for example have by making to be made up of polyvinyl alcohol resin Film in multilayer containing stretched film and the diaphragm being configured in above-mentioned stretched film obtained from stretching after polarized component Film.As polyvinyl alcohol resin, such as polyvinyl alcohol, polyvinyl formal, Pioloform, polyvinyl acetal, ethene second can be enumerated Vinyl acetate copolymer saponified.Polarized component can enumerate such as iodine or dichroic dye.As diaphragm, can enumerate for example The cellulose membranes such as tri acetyl cellulose, polycarbonate membrane, poly (ether sulfone) film.

The thickness of polarizer is usually 30～250 μm, preferably 50～200 μm.

The method forming adhesive phase on polarizer surface is not particularly limited, and can enumerate use direct stick coating method etc. partially Shaking makes its method being dried, is had the polarizer bonding sheet of the present invention after being coated with above-mentioned adhesive composition on piece surface Adhesive phase be transferred to polarizer surface after make its method curing.It is dried and cooking conditions or loss angle tangent, gel divide The condition described with [polarizer adhesive phase] hurdle such as the scope of number is identical.

The thickness of the adhesive phase being formed on polarizer is usually 5～75 μm in terms of dry film thickness, preferably 10～50 μ m.As long as in addition, on the face of the adhesive phase at least one party that is formed at polarizer, adhesive phase can be enumerated and is only formed at partially The shake form on piece one side, adhesive phase is formed at the form on polarizer two sides.

Furthermore it is also possible to be laminated such as protective layer, antiglare layer, phase separation layer, angle of visibility on above-mentioned polarizer to improve layer Etc. the layer with other functions.

By the polarizer with adhesive phase of the present invention obtaining in the manner described above is arranged on the base of liquid crystal cell Plate manufactures liquid crystal cell on surface.Here liquid crystal cell has liquid crystal layer by the construction clamped by 2 pieces of substrates.

The substrate with liquid crystal cell can enumerate such as glass plate.The thickness of substrate is usually 0.1～1mm, is preferably 0.15～0.8mm.Especially in the present invention, sticking up of polarizer and substrate can be suppressed by using above-mentioned adhesive composition Bent.Therefore, though above-mentioned adhesive composition under the little occasion of substrate thickness (for example: below 0.8mm, preferably 0.15～ 0.7mm), it is also possible to be suitably used for the laminating of polarizer and substrate.

Embodiment

Carry out more specific description to the present invention below based on embodiment, but the present invention is not limited to these embodiments.With In the record of lower embodiment etc., if no special instructions, " part " expression " mass parts ".

[GPC and GPC-MALS]

Gel permeation chromatography (GPC method) is used to utilize gel permeation chromatography/multi-angle laser light according to following condition Weight average molecular weight (Mw) and number-average molecular weight (Mn) to (methyl) acrylic copolymer for the scatter detector (GPC-MALS) is entered Row measures, and obtains the degree of branching according to following condition.

Determinator: HLC-8320GPC (TOSOH Co., Ltd's (ソ (strain)) production)

The composition of GPC post: following 4 pedestals (all being produced by TOSOH Co., Ltd)

(1) TSKgel HxL-H (guard column)

(2)TSKgel GMHxL

(3)TSKgel GMHxL

(4)TSKgel G2500HxL

Flow velocity: 1.0mL/ minute

Column temperature: 40 DEG C

Sample solution concentration: 1.5% (w/v) (diluting with oxolane)

Mobile phase solvent: oxolane

Detector: DAWN HELEOS (MALS detector)+Optilab rEX (RI detector)

Polystyrene standard conversion (measures the occasion of Mw and Mn)

[synthesis example 1]

98.8 parts of propylene are added in the reaction unit possessing mixer, reflux cooler, thermometer and nitrogen ingress pipe Acid N-butyl, 1 part of acrylic acid 4-hydroxy butyl ester, 0.2 part of acrylic acid and 100 parts of ethyl acetate solvents, import nitrogen and rise Temperature is to 80 DEG C.Then, add the tert-Butyl peroxypivalate of 0.1 part, carry out the polymerization of 6 hours in a nitrogen atmosphere in 80 DEG C Reaction.After reaction terminates, being diluted with ethyl acetate, prepared solid component concentration is the polymer solution of 30 mass %.Institute The weight average molecular weight (Mw) of (methyl) the acrylic copolymer A obtaining is 700,000, and molecular weight distribution (Mw/Mn) is 7.1, acid number For 1.6mgKOH/g.

[synthesis example 2～13]

Except the monomer component used in polymerisation and polymerization initiator are changed to content described in table 1 with Outward, synthesizing according to the mode identical with synthesis example 1, prepared solid component concentration is the polymer solution of 30 mass %.Knot Fruit is shown in table 1.

[table 1]

[embodiment 1]

(1) modulation of adhesive composition

By (methyl) acrylic polymer solution (solid component concentration is 30 mass %) being obtained by synthesis example 1 and (methyl) acrylic polymer contained relative in this solution of 100 parts (solid constituent amounts) is 0.05 part, and (solid becomes Component) as isocyanate compound Soken Chemical & Engineering Co., Ltd. manufacture " TD-75 " (solid constituent is 75 mass %, Ethyl acetate solution), 0.14 part (solid constituent amount) as metallo-chelate Soken Chemical & Engineering Co., Ltd. manufacture " M- 12AT " (solid constituent is 10 mass %, toluene, acetylacetone,2,4-pentanedione solution), the SHIN-ETSU HANTOTAI's chemistry work as silane coupler of 0.2 part " KBM-403 " (solid constituent is 100%) and the conduct of 1 part that industry Co., Ltd. (SHIN-ETSU HANTOTAI's chemistry work (strain)) manufactures are prevented " AS-804 " (solid constituent is 100%) that Di-ichi Kogyo Seiyaku Co., Ltd.'s (the first work (strain)) of electrostatic agent manufactures Mix, obtain adhesive composition.

(2) making of bonding sheet

After froth breaking, with scraper in the upper coating of polyethylene terephthalate film (PET film) through lift-off processing by upper State the adhesive composition that (1) obtains, be dried 3 minutes at 90 DEG C, form the film that desciccator diaphragm thickness is 20 μm.At film Fit through the PET film of lift-off processing on the reverse side of the sticking veneer of above-mentioned PET film further, quiet under 23 DEG C/50%RH environment Put 7 days after curing, obtain having by the bonding sheet of the adhesive phase that the thickness clamped by 2 pieces of PET film is 20 μm.

(3) making of the polarizer with adhesive phase

After froth breaking, with scraper in the upper coating of polyethylene terephthalate film (PET film) through lift-off processing by upper State the adhesive composition that (1) obtains, be dried 3 minutes at 90 DEG C, form the piece with the film that desciccator diaphragm thickness is 20 μm. Make sheet above and polarizer (thickness: 110 μm, Rotating fields: tri acetyl cellulose film/polyvinyl alcohol film/tri acetyl cellulose Film) fit in the way of making above-mentioned film connect with polarizer, stand after within 7 days, curing under conditions of 23 DEG C/50%RH, Obtain having the polarizer with adhesive phase of PET film and adhesive phase that thickness is 20 μm and polarizer.

[embodiment 2～14, comparative example 1]

Except (methyl) acrylic polymer solution in embodiment 1 being changed to by gathering that synthesis example 2～13 obtains Polymer solution and/or by blend composition be changed to content described in table 2 beyond, according to side same as in Example 1 Formula obtains the polarizer of adhesive composition, bonding sheet and band adhesive phase.

[evaluation]

[loss angle tangent]

It on the bonding sheet obtaining in embodiment comparative example, in the environment of 23 DEG C/50%RH, to thickness is 20 μm Repeatedly fitting between adhesive phase, processing 20 minutes in the autoclave of 50 DEG C/5 atmospheric pressure, making thickness is 1.0mm Adhesive phase.By " PhysicaMCR300 " that use Anton Paar company to manufacture, glue according to based on the dynamic of JIS K7244 Elasticity measurement method (condition is temperature range-40～180 DEG C, programming rate 3.67 DEG C/min, frequency 1Hz) measures this thickness The viscoplasticity spectrogram of the adhesive phase that degree is 1.0mm, determines the loss angle tangent (tan δ) that temperature is at 23 DEG C and 80 DEG C.

[gel fraction]

The adhesive gathering about 0.1g from the bonding sheet being obtained by embodiment comparative example is placed in sample bottle, adds The ethyl acetate of 30mL after shaking 4 hours, was carried out by the content to this sample bottle for the 200 stainless steel wire nettings of purpose Filter, measures dry weight carry out the drying of 2 hours to the residue on wire netting after at 100 DEG C.Following formula is utilized to obtain bonding The gel fraction of agent.

Gel fraction (%)=(dry weight/adhesive gathers weight) × 100 (%)

[creep value]

By the polarizer with adhesive phase that obtained by embodiment comparative example (by PET film/adhesive phase/polarizer The duplexer constituting) cut into the size of wide 10mm × long 100mm, peel off the above-mentioned PET film through lift-off processing, through alkali So that above-mentioned adhesive phase connects with above-mentioned glass plate and fitting area reaches the mode of 10mm × 10mm on the glass plate processing Fit, obtain evaluation bonding processing polarizer test film.

To evaluation bonding processing polarizer test film carry out autoclave process (50 DEG C, 5 atmospheric pressure), 23 DEG C/ 24 hours are stood under 50%RH atmosphere.Then above-mentioned test film is set to fixing card in the chamber BOX of micro-creep analyzer The a length of 15mm of disc portion.With tensile load, the stretching time of 1000 seconds of 800g, along be parallel to this polarizer with above-mentioned Above-mentioned evaluation in above-mentioned test film is used viscous by the composition surface between glass plate and the direction for the length direction of above-mentioned polarizer Close processing polarizer to pull, measure the deviation distance (μ of the above-mentioned glass plate of above-mentioned test film and the fitting part of polarizer M) as creep value.

[mensuration of bonding force]

By the polarizer with adhesive phase that obtained by embodiment comparative example (by PET film/adhesive phase/polarizer structure The duplexer becoming) cut into the size of 70mm × 25mm, prepare test film.PET film is peeled off from test film, will with laminating roll The duplexer being made up of adhesive phase/polarizer is bonded to the glass plate of 2mm with glass plate in the way of making adhesive phase connect One side on.Obtained duplexer is being adjusted to the autoclave of 50 DEG C/5 atmospheric pressure holding 20 minutes.Then, 23 DEG C/50%RH environment under place after 1 hour, along relative to the direction that glass pane surface is 90 DEG C with the speed of 300mm/ minute Polarizer end is pullled by degree, measures bonding force (peel strength).

[bending (warpage)]

By the polarizer with adhesive phase that obtained by embodiment comparative example (by PET film/adhesive phase/polarizer structure The duplexer becoming) cut into the size in 35mm × 400mm (tensile axis direction), prepare test film.PET film is shelled from test film From the duplexer being made up of adhesive phase/polarizer being bonded in the way of making adhesive phase connect with glass plate with laminating roll To the one side of the glass plate of 0.7mm, 40mm × 410mm.Obtained duplexer is being placed under 23 DEG C/50%RH environment After 24 hours, keep 72 hours in the stove of 60 DEG C.It is fixed on unilateral end on metope perpendicular to the ground, use ruler The amount tilting opposite side extremities is measured.Implement to measure after just taking out from stove and after 24 hours.

[endurancing]

By the polarizer with adhesive phase that obtained by embodiment comparative example (by PET film/adhesive phase/polarizer structure The duplexer becoming) cut into the size of 150mm × 250mm, prepare test film.PET film is peeled off from test film, uses laminating roll The duplexer being made up of adhesive phase/polarizer is bonded in the way of making adhesive phase connect with glass plate the glass of 2mm On the one side of plate.Obtained duplexer is adjusted to the autoclave of 50 DEG C/5 atmospheric pressure holding 20 minutes, prepares examination Test plate.Make 2 pieces of identical breadboards.By above-mentioned breadboard, under conditions of temperature is 80 DEG C, (heat resistance) or temperature are 60 DEG C/humidity under conditions of be 90%RH (humidity resistance) place 500 hours, according to following benchmark, foaming and fracture are entered Row is observed and evaluates.Foaming occurs under the hypodynamic occasion of cohesion, breaks at and occurs under the not enough occasion of stress relief.

(foaming)

AA: have no foaming completely.

BB: foaming area is less than overall 1%.

CC: foaming area overall more than 1% less than 5%.

DD: foaming area is overall more than 5%.

(fracture)

AA: have no fracture completely.

BB: area of fracture is less than overall 1%.

CC: area of fracture overall more than 1% less than 5%.

DD: area of fracture is overall more than 5%.

[table 2]

As shown in table 2, if the tan δ of adhesive phase₁(23 DEG C) are more than 0.33, and tan δ₂(80 DEG C) more than 0.40, Then bendability and durability (resistance to foaming, resistance to fracture) can make people satisfied.And if the tan δ of adhesive phase₁(23 DEG C) are less than 0.33, or tan δ₂(80 DEG C) are less than 0.40, then bendability and durability (resistance to fracture) are low.

In table 2, the amount of peroxide type polymerization initiator calculates by the following method.By above-mentioned survival rate formula: exp (- k_dT) × 100 (%) calculate, for example in embodiment 1, and k_d=A × exp (-Δ E/RT), A=6.93 × 10¹⁷Hour^-1, Δ E= 119.1kJ/ mole, R=8.314J/ mole of K, T=353K, reaction time t=6 hour, used in above-mentioned copolymerization The amount × survival rate (%) of peroxide type polymerization initiator calculate 5 × 10^-3Mass parts.

Claims (12)

1. a polarizer adhesive composition, this polarizer adhesive be containing (A) by the carbon number comprising alkyl be 4～ (methyl) acrylic compounds that the monomer component copolymerization of (methyl) alkyl acrylate of 18 and the monomer of polar functionalities obtains is common Polymers and the polarizer adhesive composition of (B) crosslinking agent,

Loss angle tangent (tan δ at 23 DEG C of the adhesive phase being formed by described composition₁) it is 0.33～0.55, and

Loss angle tangent (tan δ at 80 DEG C₂) it is 0.40～0.65.

2. polarizer adhesive composition as claimed in claim 1, it is characterised in that crosslinking agent (B) contains isocyanates Compound (B1) and metallo-chelate (B2).

3. polarizer adhesive composition as claimed in claim 2, it is characterised in that the content phase of metallo-chelate (B2) Isocyanate compound (B1) for 100 mass parts is 10～1000 mass parts.

4. the polarizer adhesive composition as according to any one of claims 1 to 3, it is characterised in that described containing polarity The polar group of the monomer of group is carboxyl and/or hydroxyl.

5. the polarizer adhesive composition as according to any one of Claims 1 to 4, it is characterised in that described (methyl) Acrylic copolymer (A) is the copolymer being obtained by described copolymerization in the presence of peroxide type polymerization initiator.

6. the polarizer adhesive composition as according to any one of Claims 1 to 5, it is characterised in that described (methyl) The weight average molecular weight (Mw) that acrylic copolymer (A) utilizes gel permeation chromatography (GPC method) to measure is 200,000～1,500,000.

7. the polarizer adhesive composition as according to any one of claim 1～6, it is characterised in that peroxide Content relative to (methyl) acrylic copolymers (A) of 100 mass parts below 0.1 mass parts.

8. the polarizer adhesive composition as according to any one of claim 1～7, it is characterised in that by described polarization The gel fraction of the adhesive that piece adhesive composition is formed is 10～70 mass %.

9. a polarizer adhesive phase, it is characterised in that used viscous by the polarizer according to any one of claim 1～8 Mixture composite is formed,

Loss angle tangent (tan δ at its 23 DEG C₁) it is 0.33～0.55, and

Loss angle tangent (tan δ at 80 DEG C₂) it is 0.40～0.65.

10. polarizer adhesive phase as claimed in claim 9, it is characterised in that gel fraction is 10～70 mass %.

11. 1 kinds of polarizer bonding sheets, it is characterised in that there is the polarizer adhesive phase described in claim 9 or 10.

12. 1 kinds of polarizers with adhesive phase, it is characterised in that there is polarizer and be formed at described polarizer at least Polaroid-bindnig oxidant layer described in claim 9 or 10 on the face of one side.