CN107924009A - Polarizer adhesive phase and adhesive composition - Google Patents

Polarizer adhesive phase and adhesive composition Download PDF

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Publication number
CN107924009A
CN107924009A CN201680046837.7A CN201680046837A CN107924009A CN 107924009 A CN107924009 A CN 107924009A CN 201680046837 A CN201680046837 A CN 201680046837A CN 107924009 A CN107924009 A CN 107924009A
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China
Prior art keywords
polarizer
methyl
adhesive phase
crosslinking agent
photoelastic coefficient
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CN201680046837.7A
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CN107924009B (en
Inventor
三角忠史
室井佐知
大久保贵启
近藤惠子
黑泽翔
田中隆祐
绀野雄太
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Soken Kagaku KK
Soken Chemical and Engineering Co Ltd
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Soken Chemical and Engineering Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Abstract

The present invention provide it is a kind of can suitable for the construction that at least one party the polarizer protective film being formed on polarizer two sides is omitted in the past in and have excellent leakproof photosensitiveness and durability adhesive phase.A kind of polarizer adhesive phase, it is by being 200 × 10 containing photoelastic coefficient‑12~+200 × 10‑12(m2/ N) (methyl) acrylic copolymer and the adhesive composition of isocyanates crosslinking agent without aromatic ring formed, the photoelastic coefficient of the polarizer adhesive phase is 200 × 10‑12~+200 × 10‑12(m2/ N), and directly mutually ground connection configures with polarizer, wherein, it is 1000 × 10 that (methyl) acrylic copolymer, which has the photoelastic coefficient from homopolymer,‑12~100 × 10‑12(m2/ N) (methyl) alkyl acrylate construction unit and photoelastic coefficient from homopolymer be+500 × 10‑12~+2000 × 10‑12(m2/ N) (methyl) acrylate containing aromatic ring construction unit.

Description

Polarizer adhesive phase and adhesive composition
Technical field
The present invention relates to polarizer adhesive phase and adhesive composition.
Background technology
Liquid crystal cell have liquid crystal layer by two pieces of substrates (such as：Glass plate) clamped by construction.Form liquid crystal cell On substrate surface polarizer is pasted with via adhesive phase.Usual polarizer in order to improve its mechanical property and optical durability and Using the construction for the polarizer protective film that tri acetyl cellulose etc. is laminated on the polarizer two sides with polarization function.
In recent years, the lightweight slimming for polarizer requires, and trial, which is saved, to be formed on polarizer two sides One or both (for example, referring to patent document 1) in polarizer protective film.However, the side in polarizer protective film Or the polarizer that is omitted of both sides is directly contacted and the meeting under hot and humid thermal environment with polarizer due to adhesive phase It is subject to big stress over the binder layer with the thermal contraction of polarizer, a problem that adhesive phase is peeled off easily occurs. Become larger in addition, also there is the stress applied because of polarizer thermal contraction to adhesive phase and become easily to occur birefringent Problem.
It is therefore desirable to polarizer has excellent leakproof photosensitiveness and durability with adhesive.For leakage problem, patent text Recorded in part 2 with the adhesive phase formed by the polarizer containing a large amount of isocyanate compounds with adhesive composition Polarizing coating；The polarizer pressure-sensitive adhesive composition containing the component with positive photoelastic coefficient has been recorded in patent document 3. However, adhesive phase all on not being configured the record on polarizer directly by these documents.
Prior art literature
Patent document
Patent document 1：Japanese Patent Laid-Open 2012-128099 publications
Patent document 2：Japanese Patent Laid-Open 2010-090354 publications
Patent document 3：Japanese Patent Laid 2004-516359 publications
The content of the invention
The technical problems to be solved by the invention
It is required that in the past at least one party in the polarizer protective film that is formed on polarizer two sides be omitted it is inclined The piece that shakes has more excellent leakproof photosensitiveness and durability.The technical problems to be solved by the invention are that providing one kind can be applicable in In the structure that at least one party in the polarizer protective film being formed on polarizer two sides in the past is omitted and have Excellent leakproof photosensitiveness and the adhesive phase of durability.
Technical scheme applied to solve the technical problem
The present inventor has made intensive studies to solve above-mentioned technical problem.It turns out that using described below Under the occasion of (methyl) acrylic copolymer and crosslinking agent, the bonding of above-mentioned leakproof photosensitiveness and excellent in te pins of durability can be formed Oxidant layer.That is, the inventors discovered that, above-mentioned skill can be solved by using the polarizer adhesive phase with following specific composition Art problem, so as to complete invention.
The present invention is, for example, following [1]~[10].
[1] a kind of polarizer adhesive phase, it is by being -200 × 10 containing photoelastic coefficient-12~+200 × 10-12 (m2/ N) (methyl) acrylic copolymer (A1) and isocyanates crosslinking agent (B1) without aromatic ring adhesive combination Thing is formed, and the photoelastic coefficient of the polarizer adhesive phase is -200 × 10-12~+200 × 10-12(m2/ N), and with it is inclined Shaking, directly mutually ground connection configures element, wherein, (methyl) acrylic copolymer (A1) has the photoelasticity from homopolymer Coefficient is -1000 × 10-12~-100 × 10-12(m2/ N) (methyl) alkyl acrylate (a11) construction unit and come from The photoelastic coefficient of homopolymer is+500 × 10-12~+2000 × 10-12(m2/ N) (methyl) acrylate containing aromatic ring (a12) construction unit.
[2] the polarizer adhesive phase described in above-mentioned [1], wherein, isocyanates crosslinking agent (B1) is six methylenes Group diisocyanate class crosslinking agent.
[3] the polarizer adhesive phase described in above-mentioned [1] or [2], wherein, described adhesive composition contains relatively In the isocyanates crosslinking agent (B1) that 100 mass parts of copolymer (A1) are 0.05~10 mass parts.
[4] a kind of polarizer adhesive phase, it containing photoelastic coefficient by being less than -200 × 10-12(m2/ N) (first Base) adhesive composition of acrylic copolymer (A2) and the isocyanates crosslinking agent (B2) containing aromatic ring formed, it is described partially Shake piece adhesive phase photoelastic coefficient be -200 × 10-12~+200 × 10-12(m2/ N), and directly connect with polarizer Ground configures.
[5] the polarizer adhesive phase described in above-mentioned [4], wherein, isocyanates crosslinking agent (B2) is to be selected from first At least one of phenylene diisocyanate class crosslinking agent and sub- xylene diisocyanate class crosslinking agent.
[6] the polarizer adhesive phase described in above-mentioned [4] or [5], wherein, described adhesive composition contains relatively In 100 mass parts of copolymer (A2) be isocyanates crosslinking agents (B2) more than 2 mass parts.
[7] a kind of polarizer bonding sheet, its adhesive phase any one of with above-mentioned [1]~[6].
[8] a kind of polarizer with adhesive phase, it is layered in the polarizer with polarizer and directly extremely The adhesive phase any one of above-mentioned [1]~[6] in few one side.
[9] a kind of polarizer adhesive composition for being used to form the adhesive phase described in above-mentioned [1], it contains light Coefficient of elasticity is -200 × 10-12~+200 × 10-12(m2/ N) (methyl) acrylic copolymer (A1) and without aromatic ring Isocyanates crosslinking agent (B1), wherein, (methyl) acrylic copolymer (A1) has the photoelasticity from homopolymer Coefficient is -1000 × 10-12~-100 × 10-12(m2/ N) (methyl) alkyl acrylate (a11) construction unit and come from The photoelastic coefficient of homopolymer is+500 × 10-12~+2000 × 10-12(m2/ N) (methyl) acrylate containing aromatic ring (a12) construction unit.
[10] a kind of polarizer adhesive composition for being used to form the adhesive phase described in above-mentioned [4], it contains Photoelastic coefficient is less than -200 × 10-12(m2/ N) (methyl) acrylic copolymer (A2) and the isocyanates containing aromatic ring Crosslinking agent (B2).
The effect of invention
Protected by means of the invention it is possible to provide a kind of polarizer that can be suitable for being formed on polarizer two sides in the past In the structure that at least one party in cuticula is omitted and with excellent leakproof photosensitiveness and durability adhesive phase.
Embodiment
In the following, to the present invention polarizer adhesive composition, polarizer adhesive phase, polarizer bonding sheet with And the polarizer with adhesive phase illustrates.Hereinafter, the polarizer adhesive composition of the present invention, polarizer are used viscous Mixture layer and polarizer are also referred to as " adhesive composition ", " adhesive phase " and " bonding sheet " with bonding sheet.
[polarizer adhesive composition]
The 1st polarizer adhesive composition of the present invention is used to form the adhesive phase directly to connect with polarizer, The 1st polarizer adhesive composition contains photoelastic coefficient for -200 × 10-12~+200 × 10-12(m2/ N) (first Base) acrylic copolymer (A1) and the isocyanates crosslinking agent (B1) without aromatic ring.
The small isocyanates crosslinking agent without aromatic ring is contributed to make by using the photoelastic coefficient to adhesive phase photoelastic (methyl) acrylic copolymer crosslinking of property coefficient within the above range, can form photoelastic coefficient -200 × 10-12~ +200×10-12(m2/ N) in adhesive phase.
The 2nd polarizer adhesive composition of the present invention is used to form the adhesive phase directly to connect with polarizer, The 2nd polarizer adhesive composition contains photoelastic coefficient less than -200 × 10-12(m2/ N) (methyl) acrylic compounds Copolymer (A2) and the isocyanates crosslinking agent (B2) containing aromatic ring.
By using the photoelastic coefficient for making adhesive phase shift on the occasion of the isocyanates crosslinking agent containing aromatic ring make it is photoelastic Property coefficient is crosslinked for (methyl) acrylic copolymer of negative value, can form photoelastic coefficient -200 × 10-12~+200 × 10-12(m2/ N) in adhesive phase.
In this specification, copolymer (A1) and (A2) are referred to as " copolymer (A) ", and the 1st and the 2nd polarizer of the invention is used Adhesive composition is also referred to as " the 1st adhesive composition " and " the 2nd adhesive composition " respectively, and they are referred to as " this The adhesive composition of invention ".
Acrylic acid and methacrylic acid are referred to as in this specification and are denoted as " (methyl) acrylic acid ".In addition, by polymer Included in the construction unit from certain monomer A be also denoted as " monomer A units ".In addition, certain ester (a) is also remembered for convenience For " monomer (a) ".
In this specification, unless otherwise specified, homopolymer, (methyl) acrylic copolymer formed by each monomer Unit with the photoelastic coefficient of adhesive phase is " × 10-12m2/N”.In addition, for example, -200 × 10-12~+200 × 10-12 (m2/ N) represent -200 × 10-12(m2/ N) more than ,+200 × 10-12(m2/ N) below.Other number ranges are also such.
The photoelastic coefficient of the homopolymer formed by each monomer determines in the following manner.
Homopolymer for photoelastic coefficient measure makes according to following steps.To possess mixer, reflux cooler, Add the monomer of 100 mass parts and the ethyl acetate solvent of 100 mass parts in the reaction unit of thermometer and nitrogen ingress pipe, one Side imports nitrogen while being warming up to 80 DEG C.Then, 0.1 mass parts 2,2'- azodiisobutyronitriles, in 80 in nitrogen atmosphere are added Polymerisation when progress 6 is small at DEG C.After reaction, it is diluted with ethyl acetate, it is 30 matter that solid component concentration, which is made, Measure the homopolymer solution of the above-mentioned monomer of %.
By above-mentioned lift-off processing of the leviathan solution coating in the polyethylene terephthalate film Jing Guo lift-off processing It is 3 minutes dry at 90 DEG C on face, form the film (layer of homopolymer) that dry film thickness is 20 μm.In the environment of 23 DEG C/50%RH It is lower to be mutually repeatedly bonded the layer of homopolymer that dry film thickness is 20 μm, 20 points are handled in the autoclave to 50 DEG C/5atm is adjusted Clock, is made the layer of homopolymer that thickness is 1.0mm.
The layer of homopolymer that thickness is 1.0mm is cut into the size of 15mm × 50mm, auto-wave is mounted to using fixture On long scan type ellipsometer (M220 types, Japan Spectroscopy Corporation (Japan light splitting society) manufacture), change stress while with The measure wavelength measure retardation value (retardation) of 633nm.Corresponding power as transverse axis, retardation value as the longitudinal axis figure line into Row linear fit, the photoelastic coefficient using its slope as the homopolymer formed by above-mentioned monomer.
The glass transition temperature (Tg) of the homopolymer formed by each monomer can be used for example《Polymer handbook (Polymer Handbook)》Described numerical value in fourth edition (Wiley-Interscience 2003).
In addition, it is not recorded in the monomer in above-mentioned document for Tg, such as the Tg of the homopolymer synthesized under the following conditions, Measured according to the following conditions.Added into the reaction unit for possessing mixer, reflux cooler, thermometer and nitrogen ingress pipe The ethyl acetate solvent of the monomer of 100 mass parts and 100 mass parts, imports nitrogen while being warming up to 80 DEG C.Then, add 0.1 mass parts 2,2'- azodiisobutyronitriles, polymerisation when progress 6 is small at 80 DEG C in nitrogen atmosphere.Will be obtained Homopolymer is enclosed in simple closed pot.Using differential scanning calorimeter (DSC), heated up in nitrogen stream with 10 DEG C/min, Thermal change is measured, describes " suction caloric value " to the figure line of " temperature ", using the feature abrupt change observed at this time as glass transition. In addition, Tg uses the numerical value obtained using mid-point method by DSC curve.
[(methyl) acrylic copolymer (A1)]
(methyl) acrylic copolymer (A1) has (first that the photoelastic coefficient from homopolymer is -1000~-100 Base) alkyl acrylate (a11) construction unit and photoelastic coefficient from homopolymer be+500~+2000 containing aromatic ring The construction unit of (methyl) acrylate (a12).For example, copolymer (A1) is to make the list containing monomer (a11) and monomer (a12) Copolymer obtained from the copolymerization of body component.
Above-mentioned monomer component (that is, the starting monomer component of (A1)) is preferably the monomer containing polymerism unsaturated double-bond.
The photoelastic coefficient of (methyl) acrylic copolymer (A1) is -200~+200, is preferably -100~+100, more Preferably -70~+70.
By make the photoelastic coefficient of monomer (a11) that the photoelastic coefficient of homopolymer is negative value and homopolymer be on the occasion of Monomer (a12) is copolymerized, and can obtain the copolymer (A1) of photoelastic coefficient within the above range.By using copolymer (A1), Isocyanates crosslinking agent (B1) without aromatic ring, can make in the range of the photoelastic coefficient of adhesive phase is described below, Zero is particularly close to, is taken this, the light leak of polarizer can be suppressed.
《(methyl) alkyl acrylate (a11) (monomer (a11))》
Monomer (a11) is that the photoelastic coefficient of homopolymer is -1000~-100 (methyl) alkyl acrylate.It is it is preferred that equal Above-mentioned monomer of the photoelastic coefficient of polymers in -750~-150, the above-mentioned monomer more preferably in -500~-200.
By using copolymer obtained from making monomer (a11) copolymerization of the photoelastic coefficient of homopolymer within the above range (A1), adhesive phase can be assigned with flexibility, show leakproof photosensitiveness.
Monomer (a11) is preferably (methyl) alkyl acrylates of the Tg of homopolymer below -30 DEG C, and above-mentioned Tg is more preferably For -100~-30 DEG C, more preferably -70~-30 DEG C.
As monomer (a11), can enumerate for example with CH2=CR1-COOR2The photoelasticity system of homopolymer in the compound of expression The compound of number within the above range.In formula, R1For hydrogen atom or methyl, R2The alkyl for being 1~20 for carbon number.The alkyl Carbon number is preferably 2~16, and more preferably 4~12.
As monomer (a11), such as n-butyl acrylate (- 400 can be enumerated；- 50), 2-EHA (- 700；- 70), methacrylic acid hendecane base ester (- 190；- 41), lauryl methacrylate (- 460；-65).On including Numerical value in number, left side represent the photoelastic coefficient (× 10 of the homopolymer formed by each monomer-12m2/ N), right side represents Tg (℃)。
Monomer (a11) can be used alone one kind, it is possible to use two or more.In the field using two or more monomers (a11) Under conjunction, preferably each monomer all meets photoelastic coefficient and the condition of Tg.
In the 100 mass % of starting monomer component of copolymer (A1), the dosage of monomer (a11) is preferably 50~90 matter Measure %, more preferably 55~85 mass %, more preferably 60~80 mass %.If the dosage of monomer (a11) is above-mentioned In the range of, then the photoelastic coefficient of obtained copolymer (A1) can be adjusted to above range, therefore preferably.
《(methyl) acrylate (a12) (monomer (a12)) containing aromatic ring》
Monomer (a12) is that the photoelastic coefficient of homopolymer is+500~+2000 (methyl) acrylate containing aromatic ring.It is excellent Select above-mentioned monomer of the photoelastic coefficient of homopolymer in+700~+1950, the above-mentioned list more preferably in+800~+1900 Body.
The copolymer obtained by using monomer (a12) copolymerization of the photoelastic coefficient by homopolymer within the above range (A1), adhesive phase can be assigned with appropriate durability.
Monomer (a12) is preferably (methyl) acrylate containing aromatic ring of the Tg of homopolymer more than -50 DEG C, and above-mentioned Tg is more Preferably -40~130 DEG C, more preferably -30~120 DEG C.
As monomer (a12), can enumerate for example with CH2=CR3-COOR4The photoelasticity system of homopolymer in the compound of expression The compound of number within the above range.In formula, R3For hydrogen atom or methyl, R4For the group containing aromatic ring.As the base containing aromatic ring Group, can enumerate the aryloxy alkyls such as the aralkyl such as the aryl such as phenyl, benzyl, Phenoxyethyl.R4Carbon number be preferably 6~ 12, more preferably 6~10, more preferably 7~9.
As monomer (a12), such as benzyl acrylate (1840 can be enumerated；6), benzyl methacrylate (1530；54), third Olefin(e) acid phenoxy ethyl (1830；-22).On the numerical value in bracket, left side represents the photoelastic of the homopolymer formed by each monomer Property coefficient (× 10-12m2/ N), right side represents Tg (DEG C).In addition, as monomer (a12), phenyl acrylate, methyl can be also enumerated Phenyl acrylate, phenoxyethyl methacrylate.
Monomer (a12) can be used alone one kind, it is possible to use two or more.In the field using two or more monomers (a12) Under conjunction, preferably each monomer all meets photoelastic coefficient and the condition of Tg.
In the 100 mass % of starting monomer component of copolymer (A1), the dosage of monomer (a12) is preferably 9~40 mass %, More preferably 12~35 mass %, more preferably 15~30 mass %.If the dosage of monomer (a12) is in above range It is interior, then the photoelastic coefficient of obtained copolymer (A1) can be adjusted to above range, therefore preferably.
《Monomer (a13) containing cross-linking functional group》
The starting monomer component of copolymer (A1), which preferably also includes, to be contained and can be reacted with isocyanates crosslinking agent (B1) Cross-linking functional group monomer, the monomer (a13) i.e. containing cross-linking functional group.That is, copolymer (A1) preferably also has From the construction unit of monomer (a13).
Monomer (a13) preferably has polymerism unsaturated double-bond.
As cross-linking functional group, such as hydroxyl, carboxyl can be enumerated.As monomer (a13), such as hydroxyl list can be enumerated Body, carboxyl group-containing monomer.
As hydroxyl monomer, (methyl) acrylate of such as hydroxyl can be enumerated, specifically, can be enumerated (methyl) Acrylic acid 2- hydroxyl ethyl esters, (methyl) acrylic acid 2- hydroxypropyl acrylates, (methyl) acrylic acid 4- hydroxy butyl esters, (methyl) acrylic acid 6- hydroxyls oneself (methyl) hydroxyalkyl acrylates such as ester, (methyl) acrylic acid 8- hydroxyl monooctyl esters.The carbon number of hydroxyalkyl in (methyl) hydroxyalkyl acrylate Usually 2~8, preferably 2~6.
As carboxyl group-containing monomer, can enumerate for example：(methyl) β-acryloxypropionic acid, (methyl) acrylic acid 5- carboxylics pentyl ester, (methyl) containing carboxyl such as succinic acid list (methyl) acryloyloxyethyl ester, list (methyl) acrylic acid ω-carboxyl pla-pcls Acrylate；Acrylic acid, methacrylic acid, itaconic acid, butenoic acid, fumaric acid, maleic acid.
Monomer (a13) can be used alone one kind, it is possible to use two or more.
In the 100 mass % of starting monomer component of copolymer (A1), the dosage of monomer (a13) be preferably greater than 0 mass % and Below 10 mass %, more preferably 0.5~7 mass %, more preferably 1~5 mass %.If the use of monomer (a13) For amount below above-mentioned upper limit value, then the crosslink density formed by copolymer (A1) and crosslinking agent (B1) will not become excessive.If The dosage of monomer (a13) can then be effectively formed cross-linked structure more than above-mentioned lower limit, obtain having the viscous of appropriate intensity Mixture layer.
《Other monomers》
As the starting monomer component of copolymer (A1), in the range of the physical property of copolymer (A1) is not damaged, can also make (methyl) alkyl acrylate, (methyl) alkyl acrylate epoxide alkyl ester, single (methyl) third beyond use-case such as above-mentioned monomer (a11) The more alkylene glycols esters of olefin(e) acid alkoxy (ア Le U キ シ Port リ ア Le キ レ Application グ リ コ ー Le モ ノ (メ タ) ア Network リ レ ー ト), (methyl) acrylate of the group containing ester ring type, amino-containing monomer, other monomers such as monomer of amide-containing.That is, copolymer (A1) can also have the construction unit from other monomers.
As (methyl) alkyl acrylate beyond above-mentioned monomer (a11), such as methyl acrylate (600 can be enumerated； 8), Tert-butyl Methacrylate (130；118), n-BMA (320；20), 2-Ethylhexyl Methacrylate (420；-10).On the numerical value in bracket, left side represents the photoelastic coefficient (× 10 of the homopolymer formed by each monomer-12m2/ N), right side represents Tg (DEG C).
As (methyl) alkyl acrylate epoxide alkyl ester, such as (methyl) methoxyethyl methyl esters, (methyl) third can be enumerated Olefin(e) acid 2- methoxy acrylates, (methyl) acrylic acid 2- ethoxy ethyl esters, (methyl) acrylic acid 3- methoxyl groups propyl ester, (methyl) propylene Sour 3- ethyoxyls propyl ester, (methyl) acrylic acid 4- methoxybutyls, (methyl) acrylic acid 4- Ethoxybutyls.
As the more alkylene glycols esters of list (methyl) alkyl acrylate epoxide, for example single (methyl) methoxyethyl two can be enumerated Glycol ester, list (methyl) methoxyethyl dipropylene glycol ester, single (methyl) ethioxy triglycol ester, single (first Base) ethioxy binaryglycol ester, singly (methyl) methoxyethyl triglycol ester.
As (methyl) acrylate of the group containing ester ring type, such as (methyl) cyclohexyl acrylate can be enumerated.
As emulsion stability, such as (methyl) acrylate, (methyl) acrylic acid diethyl can be enumerated Amino-containing (methyl) acrylate such as base amino ethyl ester.
As amide-containing monomer, such as (methyl) acrylamide, N- methyl (methyl) acrylamide, N- ethyls can be enumerated (methyl) acrylamide, N- propyl group (methyl) acrylamide, N- hexyls (methyl) acrylamide.
Other monomers can be used alone one kind, it is possible to use two or more.
In the 100 mass % of starting monomer component of copolymer (A1), as long as total dosage of above-mentioned other monomers is described (A1) Photoelastic coefficient be just not particularly limited within the above range, but preferably 0~10 mass %, more preferably 0~5 matter Measure %.
[(methyl) acrylic copolymer (A2)]
(methyl) acrylic copolymer (A2) be preferably photoelastic coefficient be less than -200, it is preferably more than -500 and small In -200, more preferably -300 less than -200 copolymer.Such copolymer is for example with the light from homopolymer The construction unit of (methyl) alkyl acrylate (a21) of coefficient of elasticity less than -200, such as can be by making containing the monomer (a21) monomer component is copolymerized to obtain.
Above-mentioned monomer component (that is, the starting monomer component of (A2)) is preferably the monomer containing polymerism unsaturated double-bond.
By using copolymer (A2), the isocyanates crosslinking agent (B2) containing aromatic ring, the photoelastic of adhesive phase can be made In the range of property coefficient is described below, zero is particularly close to, is taken this, the light leak of polarizer can be suppressed.
《(methyl) alkyl acrylate (a21) (monomer (a21))》
As monomer (a21), the photoelastic coefficient that can illustrate homopolymer in above-mentioned (methyl) alkyl acrylate (a11) is small In -200 ester.It is preferred that the photoelastic coefficient of homopolymer -750 less than -200 above-mentioned monomer, more preferably -500 Less than -200 above-mentioned monomer.
Monomer (a21) can be used alone one kind, it is possible to use two or more.In the field using two or more monomers (a21) Under conjunction, preferably each monomer all meets the condition of photoelastic coefficient.
In the 100 mass % of starting monomer component of copolymer (A2), the dosage of monomer (a21) is preferably 59~99 matter Measure %, more preferably 64~98 mass %, more preferably 69~97 mass %.If the dosage of monomer (a21) is above-mentioned In the range of, then the photoelastic coefficient of obtained copolymer (A2) can be adjusted to above range, therefore preferably.
《Monomer (a22) containing cross-linking functional group》
The starting monomer component of copolymer (A2), which preferably also includes, to be contained and can be reacted with isocyanates crosslinking agent (B2) Cross-linking functional group monomer, the monomer (a22) i.e. containing cross-linking functional group.That is, copolymer (A2) preferably also has From the construction unit of monomer (a22).
As monomer (a22), the above-mentioned monomer (a13) containing cross-linking functional group can be illustrated, preference is also identical.Monomer (a22) can be used alone one kind, it is possible to use two or more.
In the 100 mass % of starting monomer component of copolymer (A2), the dosage of monomer (a22) be preferably greater than 0 mass % and Below 10 mass %, more preferably 0.5~7 mass %, more preferably 1~5 mass %.If the use of monomer (a22) For amount below above-mentioned upper limit value, then the crosslink density formed by copolymer (A2) and crosslinking agent (B2) will not become excessive.If The dosage of monomer (a22) can then be effectively formed cross-linked structure more than above-mentioned lower limit, obtain having the viscous of appropriate intensity Mixture layer.
《Other monomers》
As the starting monomer component of copolymer (A2), in the range of the physical property of copolymer (A2) is not damaged, can also make (methyl) alkyl acrylate, (methyl) alkyl acrylate epoxide alkyl ester, single (methyl) third beyond use-case such as above-mentioned monomer (a21) The more alkylene glycols esters of olefin(e) acid alkoxy (ア Le U キ シ Port リ ア Le キ レ Application グ リ コ ー Le モ ノ (メ タ) ア Network リ レ ー ト), (methyl) acrylate, (methyl) acrylate, amino-containing monomer, the list of amide-containing containing aromatic ring of the group containing ester ring type Other monomers such as body.That is, copolymer (A2) can also have the construction unit from other monomers.
As these monomers, can illustrate described in copolymer (A1) column in《Other monomers》In each compound.As (methyl) acrylate containing aromatic ring, can enumerate such as (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) propylene Sour phenoxy ethyl.
But from the viewpoint of the photoelastic coefficient of copolymer (A2) is adjusted to above-mentioned scope, preferably to homopolymerization (methyl) alkyl acrylate and the photoelastic coefficient of homopolymer that the photoelastic coefficient of thing is+100~+1000 be+500~ The dosage of+2000 (methyl) acrylate (above-mentioned monomer (a12)) containing aromatic ring is suitably adjusted.
(methyl) alkyl acrylate that photoelastic coefficient as homopolymer is+100~+1000, can enumerate such as third E pioic acid methyl ester (600), Tert-butyl Methacrylate (130), n-BMA (320), methacrylic acid 2- ethyl hexyls Ester (420).Numerical value in bracket represents the photoelastic coefficient (× 10 of the homopolymer formed by each monomer-12m2/N)。
Other monomers can be used alone one kind, it is possible to use two or more.
In the 100 mass % of starting monomer component of copolymer (A2), as long as total dosage of above-mentioned other monomers is described (A2) Photoelastic coefficient be just not particularly limited within the above range, but preferably 0~35 mass %, more preferably 0~30 matter Measure %, more preferably 0~26 mass %.
[manufacturing condition of (methyl) acrylic copolymer (A)]
The manufacturing condition of (methyl) acrylic copolymer (A) is not particularly limited, and can come for example, by solution polymerization process Manufacture.Specifically, it is to load polymer solvent and monomer component in reaction vessel, adds polymerization initiator, reaction starting temperature Degree is set as usual 40~100 DEG C, preferably 50~90 DEG C, reaction system is maintained usual 50~90 DEG C, preferably 70~90 DEG C At a temperature of reaction 2~20 it is small when.Polymerisation can carry out in the inert gas atmosphere such as nitrogen.
Copolymer (A) can be obtained for example, by being copolymerized above-mentioned monomer component, either random copolymer, can also It is block copolymer.Wherein, random copolymer is preferable.
As polymer solvent, can enumerate for example：Benzene,toluene,xylene etc. is aromatic hydrocarbon；Pentane, n-hexane, positive heptan The aliphatic hydrocarbons such as alkane, normal octane；The ester ring type hydro carbons such as pentamethylene, hexamethylene, cycloheptane, cyclooctane；Diethyl ether, diisopropyl The ethers such as ether, 1,2- dimethoxy-ethanes, butyl oxide, tetrahydrofuran, dioxanes (dioxane), methyl phenyl ethers anisole, phenetole, diphenyl ether Class；The halogenated hydrocarbons such as chloroform, carbon tetrachloride, 1,2- dichloroethanes, chlorobenzene；Ethyl acetate, propyl acetate, butyl acetate, propionic acid The esters such as methyl esters；The ketones such as acetone, methyl ethyl ketone, diethyl ketone, methylisobutylketone, cyclohexanone；N,N-dimethylformamide, N, N- bis- The amide-types such as methylacetamide, 1-methyl-2-pyrrolidinone；The nitriles such as acetonitrile, benzonitrile；The sulfoxide types such as dimethyl sulfoxide, sulfolane. These polymer solvents can be used alone one kind, it is possible to use two or more.
As polymerization initiator, such as azo-initiator, peroxide type initiators can be enumerated.Specifically, can example Lift the peroxide such as azo-compound, benzoyl peroxide, lauroyl peroxide such as 2,2'- azodiisobutyronitriles.Wherein, preferably Azo-compound.Wherein, preferred azo-compound.As azo-compound, such as 2,2'- azodiisobutyronitriles, 2 can be enumerated, 2'- azos two (4- methoxyl group -2,4- methyl pentane nitriles), 2,2'- azos two (2- cyclopropyl propionitrile), two (2,4- of 2,2'- azos Methyl pentane nitrile), 2,2'- azos two (2- methylbutyronitriles), 1,1'- azos two (hexamethylene -1- nitriles), 2- (carbamoyl azo) Isobutyronitrile, 2- phenylazo -4- methoxyl group -2,4- methyl pentane nitriles, two acidified 2,2'- azos two (2- amidine propanes), 2, 2'- azos two (N, N'- dimethyleneisobutylamidine), 2,2'- azos two (isobutyramide) dihydrate, (the 4- cyanogen of 4,4'- azos two Base valeric acid), 2,2'- azos two (2- cyano group propyl alcohol), dimethyl -2,2'- azos two (2 Methylpropionic acid ester), 2,2'- azos two [2- methyl-N- (2- ethoxys) propionamide].These polymerization initiators can be used alone one kind, it is possible to use two or more.
Relative to 100 mass parts of starting monomer component of (methyl) acrylic copolymer (A), polymerization initiator is with usual 0.01~5 mass parts, the amount preferably in the range of 0.1~3 mass parts use.In addition, in above-mentioned polymerisation, can also be appropriate Additional addition polymerization initiator, chain-transferring agent, monomer component, polymer solvent.
[physical property and content of (methyl) acrylic copolymer (A)]
The photoelastic coefficient of (methyl) acrylic copolymer (A) is as described above.
The weight average molecular weight (Mw) that (methyl) acrylic copolymer (A) is measured by gel permeation chromatography (GPC method) It is usually 300,000~2,000,000 in terms of polystyrene scaled value, is preferably 400,000~1,800,000, more preferably 500,000~1,500,000.It is logical Cross and use Mw within the above range and there is the copolymer (A) of above-mentioned monomeric unit, easily obtain the balance of bonding force, formed and had There is the adhesive composition of the viscosity suitable for coating.In addition, the copolymer (A) by using Mw more than 500,000, can obtain The adhesive phase of durability higher.
The molecular weight distribution (Mw/Mn) that (methyl) acrylic copolymer (A) is measured by GPC method usually below 20, Preferably 2~15, more preferably 2~9.
The glass transition temperature (Tg) of (methyl) acrylic copolymer (A) can be by for example forming the monomer of the copolymer Unit and its content ratio are calculated according to Fox formula.For example, it is preferable to according to the glass transition temperature tried to achieve by Fox formula (Tg) reach usually -70~-10 DEG C, preferably -60~-20 DEG C of condition synthesize (methyl) acrylic copolymer (A).Pass through Using (methyl) acrylic copolymer (A) with such glass transition temperature (Tg), stress can be obtained and relax spy The excellent adhesive composition of adhesiveness under property and excellent in te pins of durability and room temperature.
Fox formula：1/Tg=(W1/Tg1)+(W2/Tg2)+……+(Wm/Tgm)
W1+W2+……+Wm=1
In formula, Tg be (methyl) acrylic copolymer (A) glass transition temperature (K), Tg1、Tg2、……、TgmFor The glass transition temperature (K) for the homopolymer being made of each monomer, W1、W2、……、WmFor the construction unit from each monomer Weight fraction in above-mentioned copolymer (A).As the weight fraction of the construction unit from each monomer, copolymer synthesis can be used When each single phase for whole monomers ingredient proportion.
The glass transition temperature for the homopolymer being made of in above-mentioned Fox formula each monomer can be used for example《Polymer hand Volume (Polymer Handbook)》Described numerical value in fourth edition (Wiley-Interscience 2003).In addition, for Tg is not recorded in the monomer in above-mentioned document, and the numerical value for example obtained using the above method can be used.
In 1st adhesive composition, the content of (methyl) acrylic copolymer (A1) removes organic solvent in the composition It is usually 60~99.95 mass % in 100 mass % of solid constituent in addition, is preferably 70~99.5 mass %, particularly preferably For 80~99.0 mass %.If the content of (methyl) acrylic copolymer (A1) is within the above range, work can be obtained For the balance of the performance of adhesive, and adhesion characteristic is excellent.
In 2nd adhesive composition, the content of (methyl) acrylic copolymer (A2) removes organic solvent in the composition It is usually 60~98.0 mass % in 100 mass % of solid constituent in addition, is preferably 70~96.2 mass %, particularly preferably 80~92.6 mass %.If the content of (methyl) acrylic copolymer (A2) is within the above range, conduct can be obtained The balance of the performance of adhesive, and adhesion characteristic is excellent.
[crosslinking agent (B)]
1st adhesive composition also contains the isocyanates crosslinking agent (B1) without aromatic ring.2nd adhesive composition is also Contain the isocyanates crosslinking agent (B2) containing aromatic ring.
《Isocyanates crosslinking agent (B1)》
As isocyanates crosslinking agent (B1), aromatic ring is free of more than 2 usually using isocyanates radix in 1 molecule Isocyanate compound.(methyl) acrylic copolymer (A1) is crosslinked by using crosslinking agent (B1), can be formed durable The excellent crosslinked (network polymers) of property.In addition, pass through the copolymer with photoelastic coefficient in the range of -200~+200 (A1) crosslinking agent (B1) without aromatic ring is used together, adhesive of the photoelastic coefficient in the range of -200~+200 can be formed Layer.
The isocyanates radix of crosslinking agent (B1) is preferably 2~8 usually more than 2, and more preferably 3~6.If isocyanide Acid esters radix within the above range, then (methyl) acrylic copolymer (A1) and crosslinking agent (B1) cross-linking reaction efficiency this It is preferable on point and on this aspect of the flexibility of adhesive phase is kept.
As the diisocyanate cpd that isocyanates radix in 1 molecule is 2, for example aliphatic diisocyanate can be enumerated Ester, alicyclic diisocyanate.As aliphatic vulcabond, such as ethylidene diisocyanate, tetramethylene two can be enumerated Isocyanates, pentamethylene diisocyanate, hexamethylene diisocyanate, 2- methyl isophthalic acids, 5- pentane diisocyanates, 3- first The carbon numbers such as base -1,5- pentane diisocyanates, 2,2,4- trimethyl -1,6- hexamethylene diisocyanates are 4~30 aliphatic series Diisocyanate.As alicyclic diisocyanate, such as isophorone diisocyanate, cyclopenta diisocyanate can be enumerated Ester, cyclohexyl diisocyanate, the sub- xylene diisocyanate of hydrogenation, hydrogenated toluene diisocyanate, hydrogenated methylene diphenyld two The alicyclic diisocyanate that the carbon numbers such as isocyanates, hydrogenation tetramethyl Asia xylene diisocyanate are 7~30.
As isocyanate compound of the isocyanates radix more than 3 in 1 molecule, for example aliphatic polyisocyanate can be enumerated Ester, alicyclic polymeric isocyanate.
In addition, as crosslinking agent (B1), above-mentioned isocyanation esterification of such as isocyanates radix 2 or more than 3 can be enumerated The polymer (such as dimer or tripolymer, biuret body, isocyanuric acid ester body) of compound, derivative (such as polyalcohol and 2 points The addition reaction product of above-mentioned diisocyanate cpd more than sub), polymer.As the polyalcohol in the derivative, Low molecular weight polyols can enumerate the alcohol more than ternary such as trimethylolpropane, glycerine, pentaerythrite；High molecular weight is more It is more that first alcohol can enumerate such as polyether polyol, polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene First alcohol.
As such isocyanate compound, the biuret body or isocyanide of such as hexamethylene diisocyanate can be enumerated Reaction product (such as the hexamethylene diisocyanate of urea acid esters body, trimethylolpropane and hexamethylene diisocyanate Three molecule addition products), polyethers polyisocyanate, polyester polyisocyanate.
In crosslinking agent (B1), on good curing performance and leakproof photosensitiveness this aspect is carried, preferably hexamethylene diisocyanate class is handed over Join agent.As hexamethylene diisocyanate class crosslinking agent, such as hexamethylene diisocyanate and its derivative, contracting can be enumerated Two urea bodies or isocyanuric acid ester body.In addition, as commercial product, such as Soken Chemical ＆ Engineering Co., Ltd. (Integrated can be enumerated and grind chemistry (strain)) manufacture " D-94 ".
Crosslinking agent (B1) can be used alone one kind, it is possible to use two or more.
In 1st adhesive composition, the content of crosslinking agent (B1) is relative to 100 matter of (methyl) acrylic copolymer (A1) It is usually 0.05~10 mass parts to measure part, is preferably 0.5~8 mass parts, more preferably 1~5 mass parts.If crosslinking agent (B1) Content within the above range, then easily obtain the balance of durability and leakproof photosensitiveness, thus preferably.
《Isocyanates crosslinking agent (B2)》
As isocyanates crosslinking agent (B2), usually using isocyanates radix in 1 molecule more than 2 containing aromatic ring Isocyanate compound.(methyl) acrylic copolymer (A2) is crosslinked by using crosslinking agent (B2), durability can be formed Excellent crosslinked (network polymers).In addition, contained by being used together with copolymer (A2) of the photoelastic coefficient less than -200 The crosslinking agent (B2) of aromatic ring, can form adhesive phase of the photoelastic coefficient in the range of -200~+200.
The isocyanates radix of crosslinking agent (B2) is preferably 2~8 usually more than 2, and more preferably 3~6.If isocyanide Acid esters radix within the above range, then (methyl) acrylic copolymer (A2) and crosslinking agent (B2) cross-linking reaction efficiency this It is preferable on point and on this aspect of the flexibility of adhesive phase is kept.
As the diisocyanate cpd that isocyanates radix in 1 molecule is 2, such as aromatics diisocyanate can be enumerated Ester.As aromatic diisocyanates, it is different that such as phenylene vulcabond, toluene di-isocyanate(TDI), sub- dimethylbenzene two can be enumerated Cyanate, naphthalene diisocyanate, diphenyl ether diisocyanate, '-diphenylmethane diisocyanate, diphenylpropane diisocyanate etc. Carbon number is 8~30 aromatic diisocyanates.
As isocyanate compound of the isocyanates radix more than 3 in 1 molecule, such as aromatics polyisocyanate can be enumerated Ester.Specifically, 2,4,6- triisocyanate toluene, 1,3,5- triisocyanate benzene, 4,4', 4 "-triphenylmenthane three can be enumerated Isocyanates.
In addition, as crosslinking agent (B2), above-mentioned isocyanation esterification of such as isocyanates radix 2 or more than 3 can be enumerated The polymer (such as dimer or tripolymer, biuret body, isocyanuric acid ester body) of compound, derivative (such as polyalcohol and 2 points The addition reaction product of above-mentioned diisocyanate cpd more than sub), polymer.As the polyalcohol in the derivative, Low molecular weight polyols can enumerate the alcohol more than ternary such as trimethylolpropane, glycerine, pentaerythrite；High molecular weight is more It is more that first alcohol can enumerate such as polyether polyol, polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene First alcohol.
Such isocyanate compound can enumerate the tripolymer of such as '-diphenylmethane diisocyanate, polymethylene polyphenyl Base polyisocyanate, the biuret body or isocyanuric acid ester body of toluene di-isocyanate(TDI), trimethylolpropane and toluene diisocyanate The reaction product of acid esters or sub- xylene diisocyanate (such as the three of toluene di-isocyanate(TDI) or sub- xylene diisocyanate Molecule addition product), polyethers polyisocyanate, polyester polyisocyanate.
In crosslinking agent (B2), on good curing performance and leakproof photosensitiveness this aspect is carried, the friendship of toluene di-isocyanate(TDI) class is preferably selected from Join at least one of agent and sub- xylene diisocyanate class crosslinking agent, more preferably toluene di-isocyanate(TDI) class crosslinking agent.Make For toluene di-isocyanate(TDI) class crosslinking agent, such as toluene di-isocyanate(TDI) and its derivative, biuret body or isocyanide urea can be enumerated Acid esters body.As sub- xylene diisocyanate class crosslinking agent, can enumerate for example sub- xylene diisocyanate and its derivative, Biuret body or isocyanuric acid ester body.In addition, as commercial product, " the L- that for example Soken Chemical ＆ Engineering Co., Ltd. manufactures can be enumerated 45”。
Crosslinking agent (B2) can be used alone one kind, it is possible to use two or more.
In 2nd adhesive composition, the content of crosslinking agent (B2) is relative to 100 matter of (methyl) acrylic copolymer (A2) Amount part is usually more than 2 mass parts, is preferably 4~30 mass parts, more preferably 8~15 mass parts.If crosslinking agent (B2) Content within the above range, even then containing photoelastic coefficient for negative value copolymer (A2) composition, can also be formed Layer of the photoelastic coefficient close to zero, it is therefore, preferred on durability and the balance of leakproof photosensitiveness this aspect is easily obtained.
《Other crosslinking agents》
As long as the photoelastic coefficient of obtained adhesive phase is within the above range, the 1st, the 2nd adhesive composition each Also containing other crosslinking agents beyond above-mentioned crosslinking agent (B1) or above-mentioned crosslinking agent (B2).For example, by the way that bonding will not be made The crosslinking agent that the photoelastic coefficient of oxidant layer significantly shifts on the occasion of side is combined with above-mentioned crosslinking agent, can be tieed up by photoelastic coefficient While holding in the range of being described below, durability is further improved.
As other crosslinking agents, as long as it can occur with the cross-linking functional group for the monomer for carrying out self-contained cross-linking functional group The component of cross-linking reaction is just not particularly limited, and can enumerate such as metallo-chelate (B3), epoxide (B4).
The content of the crosslinking agent is relative to (methyl) propylene when using other crosslinking agents in the 1st, the 2nd adhesive composition Acid copolymer (A) 100 mass parts are preferably below mass part 2, more preferably 0.01~1.5 mass parts, more preferably 0.03~1 mass parts.
<Metallo-chelate (B3)>
As metallo-chelate (B3), can enumerate such as alkoxide, acetylacetone,2,4-pentanedione, ethyl acetoacetate to aluminium, iron, copper, The compound that the polyvalent metal coordinations such as zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium form.
Wherein, particularly preferred aluminium chelate compound.Specifically, aluminium isopropoxide, secondary butyric acid aluminium, acetoacetate aluminium ethide can be enumerated Diisopropyl ester, tri ethylacetoacetate aluminium, praseodynium aluminium.In addition, as commercial product, it can enumerate and for example comprehensive grind chemical strain " M-12AT " of formula commercial firm manufacture.
Metallo-chelate (B3) can be used alone one kind, it is possible to use two or more.
Metallo-chelate (B3) makes (methyl) acrylic copolymer (A) be crosslinked (quasi-crosslink) by coordinate bond.Into one Step uses metallo-chelate (B3), and as under the occasion of crosslinking agent, in room temperature, described be crosslinked is maintained, and polymer plays solidifying Poly- property, and the crosslinked part releases at high temperature, adhesive phase shows more excellent flexibility.
《Epoxide (B4)》
As epoxide (B4), usually using epoxide of the 1 molecule epoxy group number more than 2.It can enumerate Such as ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, glycerin diglycidyl ether, glycerine three-glycidyl Ether, 1,3- couples of (N, N- diglycidyl amino methyl) hexamethylenes, N, N, N', N'- four glycidyl groups m-xylene diamine, N, N, N', N'- four glycidyl group aminophenyl methane, triglycidyl isocyanurate, a N, N- diglycidyl amino Phenyl glycidyl ether, N, N- diglycidyls toluidines, N, N- diglycidylanilines.In addition, as commercial product, " E-5C " of such as Soken Chemical ＆ Engineering Co., Ltd.'s manufacture can be enumerated.
[silane coupling agent (C)]
The adhesive composition of the present invention preferably also contains silane coupling agent (C).Silane coupling agent (C) make adhesive phase with The clung body strong bond such as glass plate, helps to prevent the stripping of polarizer under high humid and warm environment.
As silane coupling agent (C), can enumerate for example：Vinyltrimethoxysilane, vinyltriethoxysilane, first The silane coupling agents containing polymerism unsaturated group such as base acryloxypropyl trimethoxy silane；3- glycidoxies third Base trimethoxy silane, 3- glycidoxypropyl groups triethoxysilane, 3- glycidoxypropyls dimethoxysilane, 3- glycidoxypropyls diethoxy silane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane etc. contain epoxy The silane coupling agent of base；3- TSL 8330s, N- (2- amino-ethyls) -3- TSL 8330s, The silane coupling agents containing amino such as N- (2- amino-ethyls) -3- amino propyl methyl dimethoxysilanes；3- chloros propyl group three The silane coupling agent containing halogen such as methoxy silane, 3- ketobutyric acids -3- (trimethoxy silicon substrate) propyl ester.In addition, as city Product is sold, can be enumerated " A-50 " of such as Soken Chemical ＆ Engineering Co., Ltd.'s manufacture.
In the adhesive composition of the present invention, the content of silane coupling agent (C) is relative to (methyl) acrylic copolymer (A) 100 mass parts are usually below mass part 1, are preferably 0.01~1 mass parts, more preferably 0.05~0.5 mass Part.If content is within the above range, have prevent under high humid and warm environment polarizer peel off or hot environment under it is silane coupled The tendency of agent (C) exudation.
[antistatic agent (D)]
It can be used to for example reduce the sheet resistance value of the adhesive phase formed by the adhesive composition of the present invention Antistatic agent (D).As antistatic agent (D), such as surfactant, ionic compound, electric conductive polymer can be enumerated.
As surfactant, can enumerate for example：Quaternary ammonium salt, amidoquat salt, pyridine salt, have primary amino radical~ The cationic surface active agent of the cationic groups such as tertiary amino；With 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- hydroxyalkyls amine, alkyl diethanolamide class Deng nonionic surface active agent.
In addition, surfactant can also enumerate the reactive emulsifier with polymerizable group, also make containing upper Polymer types of surfactants obtained from stating the monomer component molecular weight of surfactant or reactive emulsifier.
Ionic compound is made of cationic moiety and anionicsite, and (23 DEG C/50%RH) can be in solid-state at room temperature Any of with liquid.
The cationic moiety of ionic compound is formed either any in inorganic cationoid or organic cationoid Person or both.Inorganic cationoid preferred as alkali ion and alkaline-earth metal ion, more preferably excellent electrostatic prevention property Li+、Na+And K+.As organic cationoid, can enumerate for example pyridylium, piperidines cation, pyrrolidonium cation, Pyrroles's cation moiety, pyrroles's cation, glyoxaline cation, tetrahydropyrimidine cation, dihydro-pyrimidin cation, pyrazoles cation, Dihydropyazolo cation (ピ ラ ゾ リ ニ ウ system カ チ オ Application), tetraalkylammonium cation, trialkylsulfonium cation, tetraalkyl Phosphine cation and their derivative.
As form ionic compound anionicsite, as long as can with cationic moiety ionic bonding and formed from The material of sub- compound is not particularly limited.Specifically, F-, Cl-, Br-, I-, AlCl can be enumerated4 -、Al2Cl7 -、BF4 -、 PF6 -、SCN-、ClO4 -、NO3 -、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO2)2N-、(F2SO2)2N-、(CF3SO2)3C-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、(CN)2N-、C4F9SO3 -、(C2F5SO2)2N-、C3F7COO-(CF3SO2)(CF3CO)N-。 Wherein, the anion containing fluorine atom because be capable of providing the ionic compound of low melting point and it is preferred that, particularly preferred (F2SO2)2N-With (CF3SO2)2N-。
The preferred bis-trifluoromethylsulfoandimide lithium of ionic compound, double difluoro sulfimide lithiums, three (trifyl) first Alkane lithium, bis-trifluoromethylsulfoandimide potassium, double difluoro sulfimide potassium, 1- ethylpyridines hexafluorophosphate, 1- butyl-pyridinium hexafluoros Phosphate, 1- hexyl -4- picolines hexafluorophosphate, 1- octyl group -4- picolines hexafluorophosphate, 1- octyl group -4- methyl The double fluorine sulfimides of pyridine, 1- octyl group -4- picolines bis-trifluoromethylsulfoandimide, the double fluorine sulfimides of tributyl first ammonium, three Butyl first ammonium bis-trifluoromethylsulfoandimide, (N, N- diethyl-N- methyl-N- (2- methoxy ethyls) ammonium tetrafluoroborate, N, N- Diethyl-N- methyl-N- (2- methoxy ethyls) 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- picolines, trifluoro thionyl imide (ト リ Off Le オロスルホニウムイミド)。
As electric conductive polymer, such as polythiophene, polyaniline, polypyrrole and their derivative can be enumerated.
In the adhesive composition of the present invention, the content of antistatic agent (D) is relative to (methyl) acrylic copolymer (A) 100 mass parts are usually below mass part 3, are 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 adjust its coating.As organic molten Agent, can enumerate and be illustrated in as polymer solvent《The manufacturing condition of (methyl) acrylic copolymer (A)》Solvent in one column.Example Such as, polymer solution and the friendship containing (methyl) acrylic copolymer (A) and polymer solvent that will can be obtained in above-mentioned copolymerization Join agent (B) mixing and carry out modulating adhesive composition.In the adhesive composition of the present invention, the content of organic solvent (E) is usually 50~90 mass %, are preferably 60~85 mass %.
In addition, " solid constituent " in this specification refers to have in component contained in adhesive composition except above-mentioned Whole components beyond solvent (E), " solid component concentration " refer to adhesive of the above-mentioned solid constituent relative to 100 mass % The ratio of composition.
[additive]
The adhesive composition of the present invention within the scope of the effect of the invention, may be used also in addition to mentioned component Containing beyond antioxidant, light stabilizer, preventing metal corrosion agent, tackifier, plasticizer, crosslinking accelerator, above-mentioned (A) (methyl) acrylic polymer and agent (リ ワ ー Network drug of doing over again) one or both of more than.
[modulation of polarizer adhesive composition]
The present invention adhesive composition can by using known method so far to (methyl) acrylic copolymer (A) with Crosslinking agent (B) and other components that are as needed and using are mixed to modulate.It can enumerate for example to synthesis (methyl) third Crosslinking agent (B) and as needed is blended when olefin(e) acid analog copolymer (A) in the obtained polymer solution containing the polymer And the other components used.
By using the adhesive composition of the present invention, even only on polarizer single side there is polarizer to protect The polarizer of cuticula and on the two sides of polarizer without polarizer protective film polarizer on form adhesive During layer, it can also suppress light leakage phenomena.In addition, in the present invention, even the construction that adhesive phase directly connects with polarizer, Also the fracture of adhesive phase, stripping of polarizer etc. can be suppressed under hot and humid thermal environment.
What above-mentioned adhesive composition was suitable for forming substrate and the polarizer of liquid crystal cell is bonded purposes.
[polarizer adhesive phase]
The 1st polarizer of the present invention is formed with adhesive phase by above-mentioned 1st adhesive composition.The 2nd polarization of the present invention Piece is formed with adhesive phase by above-mentioned 2nd adhesive composition.1st and the 2nd adhesive phase is also collectively referred to as " bonding of the invention Oxidant layer ".
By using the adhesive composition of the present invention, the adhesive phase with following photoelasticity characteristic can be formed.This The photoelastic coefficient of the adhesive phase of invention is -200~+200, is preferably -150~+150, more preferably -100~+100, into One step is preferably -70~+70.The unit of photoelastic coefficient is " × 10-12m2/N”。
Above-mentioned photoelastic coefficient is that it is about 1.0mm to make thickness for example, by above-mentioned adhesive phase is mutually repeatedly bonded Layered product, obtained from being measured with the measure wavelength of 633nm to the layered product.Detailed determination condition is recorded in implementation In example.
The adhesive phase of the present invention is due to excellent on the leakproof photosensitiveness with above characteristic and under hot and humid thermal environment It is different.Further, since the adhesive phase of the present invention is excellent on durability, it is not easy to fracture, the adhesive phase of adhesive phase occurs Situation about being peeled off from polarizer.
The adhesive phase of the present invention from the viewpoint of the warpage of polarizer, cohesiveness, bonding force, releasable is suppressed, Gel fraction is preferably more than 40 mass %, more preferably 50~97 mass %, more preferably 60~95 mass %.If Within the above range, then adhesive phase shows excellent durability to gel fraction.Detailed determination condition is recorded in embodiment In.
The adhesive phase of the present invention can be obtained for example, by carrying out the cross-linking reaction in above-mentioned adhesive composition, specifically It is to obtain by using crosslinking agent (B) (methyl) acrylic polymer (A) crosslinking.
The formation condition of adhesive phase is for example as described below.The adhesive composition of the present invention is coated on supporting mass, Temperature is different according to solvent species, but usually 50~150 DEG C, preferably carried out at 60~100 DEG C usually 1~10 minute, The drying of preferably 2~7 minutes and remove solvent, formed film.The thickness of dried film is usually 5~75 μm, preferably For 10~50 μm, the thickness of the adhesive phase finally obtained is preferably also within the above range.Thickness is using such as turntable thickness (ダ イ ヤ Le シ ッ Network ネ ス ゲ ー ジ) is counted to measure.
Adhesive phase is preferably formed under the following conditions.The adhesive composition of the present invention is coated on supporting mass, Film is formed under above-mentioned condition, as needed on above-mentioned film paste cover layer after, usual 5~60 DEG C, preferably 15~ Conserved in the environment of 40 DEG C and usual 30~70%RH, preferably 40~70%RH usual more than 3 days, preferably 7~10 days.If It is crosslinked under cooking conditions as described above, then crosslinked (network polymers) can be efficiently formed.
As the coating method of adhesive composition, known method can be used, such as pass through spin-coating method, cutter painting method, roller Coating, stick coating method, scraper coating, die coating method, gravure coating method etc. form the coating method of specific thickness.
As supporting mass and cover layer, can enumerate for example：The polyester films such as polyethylene terephthalate (PET)；Poly- second The plastic foil of the polyolefin films such as alkene, polypropylene, vinyl-vinyl acetate copolymer etc..
[polarizer bonding sheet]
The polarizer of present invention bonding sheet has the adhesive phase that the adhesive composition by the present invention is formed.As viscous Piece is closed, the double-sided adhesive sheet for example only with above-mentioned adhesive phase can be enumerated, with base material and be formed at upper on base material two sides The double-sided adhesive sheet of stating adhesive phase, the single side bonding sheet with base material and the above-mentioned adhesive phase being formed in base material one side, And these bonding sheets are pasted with the bonding of the cover layer by lift-off processing on the face not contacted with base material of adhesive phase Piece.
As base material and cover layer, can enumerate for example：The polyester films such as polyethylene terephthalate (PET)；Polyethylene, The plastic foil of the polyolefin films such as polypropylene, vinyl-vinyl acetate copolymer etc..
The formation condition of adhesive phase is identical with condition described in [polarizer adhesive phase] column.
The thickness of adhesive phase is usually 5~75 μm from the viewpoint of bond properties is maintained, and is preferably 10~50 μm.Base The thickness of material and cover layer is not particularly limited, but usually 10~125 μm, it is preferably 25~75 μm.
[polarizer with adhesive phase]
The polarizer with adhesive phase of the present invention has polarizer and is directly layered in the polarizer at least The adhesive phase formed by the adhesive composition of the present invention on simultaneously.In addition, in this specification, " polarizer " with comprising The implication of " polarizing coating " uses.
As polarizer, polarizing coating known so far can be used.Can enumerate for example polarizer in itself, there is polarizer With the multilayer film of polarizer protective film of the configuration on polarizer.In the present invention, due to above-mentioned adhesive phase with polarization The mode that element directly connects configures, thus can enumerate for example only on the single side of polarizer configure polarizer protective film and Do not configure the construction of polarizer protective film on another side, do not configure the structure of polarizer protective film on polarizer two sides Make.
As polarizer, it can enumerate and contain it in the film for for example making to be made of polyvinyl alcohol resin after polarized component Stretched film obtained from stretching.As polyvinyl alcohol resin, such as polyvinyl alcohol, polyvinyl formal, poly- second can be enumerated Ketene acetal, vinyl-vinyl acetate copolymer it is saponified.As polarized component, such as iodine or dichroic dye can be enumerated.
As polarizer protective film, the film being for example made of thermoplastic resin can be enumerated., can example as thermoplastic resin Citing such as tri acetyl cellulose celluosic resin, polyester resin, polyethersulfone resin, polysulfone resin, polycarbonate resin, gather Amide resin, polyimide resin, vistanex, (methyl) acrylic resin, cyclic polyolefin resin (borneol alkenes tree Fat), polyarylate resin, polystyrene resin, polyvinyl alcohol resin and the two or more mixing in these resins Thing.
The thickness of polarizer is usually 10~200 μm, is preferably 30~100 μm.In the present invention, it can save and be formed in partially The polarizer protective film to shake on element, it is thus possible to be thinned polarizer.
In the present invention, above-mentioned adhesive phase is formed in a manner of directly connecting with polarizer.Band as the present invention glues The polarizer of mixture layer, can enumerate for example with lower structure：Polarizer protective film, polarizer and above-mentioned adhesive phase layer successively The folded structure formed；What above-mentioned adhesive phase, polarizer protective film, polarizer and above-mentioned adhesive phase stacked gradually Structure；The structure that above-mentioned adhesive phase, polarizer and above-mentioned adhesive phase stack gradually.In these structures, bond Above-mentioned cover layer be can also configure in oxidant layer as outermost layer.
It is not particularly limited, can be enumerated on polarizer surface for the method that adhesive phase is formed on polarizer surface Make the method for its drying and curing after the upper above-mentioned adhesive composition of coating, by possessed by the polarizer bonding sheet of the present invention Adhesive phase attaches or is transferred to the method for curing it behind polarizer surface.The model of dry and cooking conditions or gel fraction Enclose etc. identical with condition described in [polarizer adhesive phase] column.
The thickness of adhesive phase is usually 5~75 μm, is preferably 10~50 μm.In addition, adhesive phase is in polarizer Connect at least one side with polarizer and formed, the shape that adhesive phase is only formed on polarizer single side can be enumerated State, adhesive phase are formed at the form on polarizer two sides.
Furthermore it is also possible to such as protective layer, antiglare layer, phase separation layer, angle of visibility are laminated on above-mentioned polarizer improves layer Deng having the function of other layers.
By the base that the polarizer of the invention with adhesive phase obtained in the manner described above is arranged on to liquid crystal cell Liquid crystal cell is manufactured in plate surface.Here liquid crystal cell has liquid crystal layer by the construction clamped by two pieces of substrates.With liquid The substrate of Jingjing born of the same parents can enumerate such as glass plate.The thickness of substrate is usually 0.05~3 millimeter, is preferably 0.2~1 millimeter.
Embodiment
In the following, the present invention will be more specifically described based on examples, but the present invention is not limited to these Examples.Below In the record of embodiment etc., unless otherwise instructed, " part " expression " mass parts ".
[GPC]
For (methyl) acrylic copolymer, it is equal to obtain weight using gel permeation chromatography (GPC method), with following conditions Molecular weight (Mw) and number-average molecular weight (Mn).
Measurement device：HLC-8320GPC (TOSOH Co., Ltd (East ソ ー (strain)) is produced)
The composition of GPC columns：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：1.0 ml/min
Column temperature：40℃
Sample solution concentration：1.5% (w/v) (being diluted with tetrahydrofuran)
Mobile phase solvent：Tetrahydrofuran
It is converted into polystyrene standard
[photoelastic coefficient]
For (methyl) acrylic copolymer, photoelastic coefficient measures in the following way.
By the equal leviathan solution coating containing (methyl) acrylic copolymer obtained in synthesis example by peeling off It is 3 minutes dry at 90 DEG C on the lift-off processing face of the polyethylene terephthalate film of processing, dry film thickness is formed as 20 μm film (polymeric layer).The polymeric layer that dry film thickness is 20 μm is mutually repeatedly pasted in the environment of 23 DEG C/50%RH Close, handled 20 minutes in the autoclave to 50 DEG C/5atm is adjusted, the polymeric layer that thickness is 1.0mm is made.It is by thickness The polymeric layer of 1.0mm is cut into the size of 15mm × 50mm, and automatic length scanning type ellipsometer is mounted to using fixture In (M220 types, Japan Spectroscopy Corporation's manufacture), change stress while measuring retardation value with the measure wavelength of 633nm. Photoelasticity system by straight slope when being the longitudinal axis using stress as transverse axis, retardation value as above-mentioned (methyl) acrylic copolymer Number.
[synthesis example 1]
76.5 parts of propylene are added into the reaction unit for possessing mixer, reflux cooler, thermometer and nitrogen ingress pipe Sour N-butyl, 19.0 parts of acrylates, 1.5 parts of acrylic acid, 3.0 parts of acrylamides and 100 parts of ethyl acetate solvents, Nitrogen is imported while being warming up to 80 DEG C.Then, 0.1 part of 2,2'- azodiisobutyronitrile is added, in 80 DEG C in nitrogen atmosphere It is lower carry out 6 it is small when polymerisation.After reaction, it is diluted with ethyl acetate, it is 30 matter that solid component concentration, which is made, Measure the polymer solution of %.The weight average molecular weight (Mw) of obtained (methyl) acrylic copolymer 1 is 800,000, molecular weight point Cloth (Mw/Mn) is 7.5, and photoelastic coefficient is -58 × 10-12(m2/N)。
[synthesis example 2~3]
In addition to monomer component used in by polymerisation is changed to content described in table 1, according to conjunction The mode identical into example 1 is synthesized, and the polymer solution that solid component concentration is 30 mass % is made.The results are shown in table 1.
[table 1]
Table 1
[embodiment A1]
(1) modulation of adhesive composition
By the polymer solution obtained in synthesis example 1 (solid component concentration is 30 mass %), relative to institute in the solution 1100 parts of (methyl) acrylic copolymer (solid content) contained is used as isocyanates for 2.0 parts (solid content) " D-94's " and 0.2 part (solid content) of Soken Chemical ＆ Engineering Co., Ltd.'s manufacture of compound grinds as the comprehensive of metallo-chelate " the A- that " M-12AT " of Chemical Co., Ltd. manufacture, 0.2 part Soken Chemical ＆ Engineering Co., Ltd. as silane coupling agent manufacture 50 " (solid constituent is 100 mass %) are mixed, and obtain adhesive composition.
(2) making of bonding sheet
In the polyethylene terephthalate film (PET film) Jing Guo lift-off processing, adhesive that above-mentioned (1) is obtained Scraper for coating is used after composition defoaming, it is 3 minutes dry at 90 DEG C, form the film that dry film thickness is 20 μm.In the upper of film State the PET film being bonded again on the reverse side of the adhesive surface of PET film by lift-off processing, stand 7 days under 23 DEG C/50%RH environment and After curing it, obtain with the bonding sheet by the thickness clamped by 2 pieces of PET films for 20 μm of adhesive phase.
(3) making of the polarizer with adhesive phase
In the polyethylene terephthalate film (PET film) Jing Guo lift-off processing, adhesive that above-mentioned (1) is obtained Scraper for coating is used after composition defoaming, it is 3 minutes dry at 90 DEG C, form the sheet material with the film that dry film thickness is 20 μm. So that the coated surface of the sheet material with by the polyvinyl alcohol film as polarizer and the triacetyl as polarizer protective film The mode that the polyvinyl alcohol film one side of the polarizer for the double-decker (thickness is 60 μm) that cellulose membrane is formed connects is bonded, After standing 7 days under conditions of 23 DEG C/50%RH and being cured, the adhesive phase that obtains there is PET film, thickness is 20 μm, partially Shake the polarizer with adhesive phase of element and polarizer protective film.
[embodiment B1~B2,1~A2 of Comparative examples A, B1~B3]
Except by the polymer solution in embodiment A1 be changed to the polymer solution that is obtained by each synthesis example and/or Person is changed to composition is blended beyond content described in table 2, and adhesive group is obtained according to the mode identical with embodiment A1 Compound, bonding sheet and the polarizer with adhesive phase.
[evaluation]
[gel fraction]
The adhesive for gathering about 0.1g in the adhesive phase of obtained bonding sheet from embodiment comparative example is placed in examination In sample bottle, when adding that concussion 4 is small after the ethyl acetate of 30mL, then with the stainless steel metal mesh of 200 purposes to the sample bottle Content is filtered, and dry weight is measured after drying when small to the residue progress 2 on metal mesh at 100 DEG C.According to Following formula obtains the gel fraction of adhesive.
Gel fraction (%)=(dry weight/adhesive collection weight) × 100 (%)
[photoelastic coefficient]
PET film is peeled off to the bonding sheet that is obtained in embodiment comparative example, by adhesive phase that thickness is 20 μm 23 DEG C/ Mutually repeatedly fitting, is handled 20 minutes, thickness, which is made, is in the autoclave to 50 DEG C/5atm is adjusted in the environment of 50%RH The adhesive phase of 1.0mm.The adhesive phase that thickness is 1.0mm is cut into the size of 15mm × 50mm, is installed using fixture To automatic length scanning type ellipsometer (M-220 types, Japan Spectroscopy Corporation manufacture), change stress while with The measure wavelength measure retardation value of 633nm.It regard straight slope when being the longitudinal axis using stress as transverse axis, retardation value as adhesive phase Photoelastic coefficient.
[light leak experiment]
By obtained 2 pieces in the embodiment comparative example polarizers with adhesive (by PET film/adhesive phase/polarization member The layered product that part/polarizer protective film is formed) cut into 310 millimeters × 385 millimeters of size, test piece.By PET film Peeled off from test film, with laminating roll by the layered product being made of adhesive phase/polarizer/polarizer protective film so that partially The mode that the axis that shakes is mutually orthogonal and adhesive phase connects with glass plate is conformed on the both sides for the glass plate that thickness is 0.5 millimeter. Obtained layered product is kept for 20 minutes in the autoclave to 50 DEG C/5atm is adjusted, test piece.The test film is existed Temperature for 80 DEG C/it is dry under conditions of place 500 it is small when, light leak is observed according to following benchmark.
AA：Not it was observed that light leak
BB：It was observed that a small amount of light leak
CC：It was observed that obvious light leak
[endurancing (experiment of heat resistance humidity resistance)]
By the obtained polarizer with adhesive phase in embodiment comparative example (by PET film/adhesive phase/polarization member The layered product that part/polarizer protective film is formed) cut into 150 millimeters × 250 millimeters of size, test piece.By PET film Peeled off from test film, with laminating roll by the layered product being made of adhesive phase/polarizer/polarizer protective film so that viscous The mode that mixture layer connects with glass plate is conformed on the single side for the glass plate that thickness is 0.5 millimeter.By obtained layered product Kept for 20 minutes in the autoclave to 50 DEG C/5atm is adjusted, test piece.2 pieces of identical test films are made.By above-mentioned examination It is (wet-heat resisting under conditions of 60 DEG C/humidity is 90%RH to test plate (heat resistance) or temperature under conditions of temperature is 80 DEG C/drying Property) place 500 it is small when, defect (foaming, tilt and peel off) is observed and evaluated according to following benchmark.
AA：Zero defect
BB：Defect area does not influence to actually use below 5%
CC：Defect area influences to actually use more than 5%
[table 2]
·D-94：Hexamethylene diisocyanate class crosslinking agent
(Soken Chemical ＆ Engineering Co., Ltd. manufactures, 90 mass % of solid constituent)
·L-45：Toluene di-isocyanate(TDI) class crosslinking agent
(Soken Chemical ＆ Engineering Co., Ltd. manufactures, 45 mass % of solid constituent, ethyl acetate/toluene solution)
·E-5C：Epoxy resin crosslinking agent
(Soken Chemical ＆ Engineering Co., Ltd. manufactures, 5 mass % of solid constituent)
·M-12AT：Aluminium chelate compound class crosslinking agent (Soken Chemical ＆ Engineering Co., Ltd. manufactures, 10 mass % of solid constituent, and toluene/ Acetylacetone,2,4-pentanedione solution)
·A-50：Silane coupling agent
(Soken Chemical ＆ Engineering Co., Ltd. manufactures, 50 mass % of solid constituent, toluene solution)

Claims (10)

1. a kind of polarizer adhesive phase, it is by being -200 × 10 containing photoelastic coefficient-12~+200 × 10-12(m2/ N) The adhesive composition of (methyl) acrylic copolymer (A1) and isocyanates crosslinking agent (B1) without aromatic ring is formed, institute The photoelastic coefficient for stating polarizer adhesive phase is -200 × 10-12~+200 × 10-12(m2/ N), and it is direct with polarizer Mutually ground connection configuration, wherein, it is -1000 that (methyl) acrylic copolymer (A1), which has the photoelastic coefficient from homopolymer, ×10-12~-100 × 10-12(m2/ N) (methyl) alkyl acrylate (a11) construction unit and from the photoelastic of homopolymer Property coefficient is+500 × 10-12~+2000 × 10-12(m2/ N) (methyl) acrylate (a12) containing aromatic ring structure list Member.
2. polarizer adhesive phase as claimed in claim 1, it is characterised in that isocyanates crosslinking agent (B1) is sub- for six Methyl diisocyanate class crosslinking agent.
3. polarizer adhesive phase as claimed in claim 1 or 2, it is characterised in that described adhesive composition contains phase For the isocyanates crosslinking agent (B1) that 100 mass parts of copolymer (A1) are 0.05~10 mass parts.
4. a kind of polarizer adhesive phase, it containing photoelastic coefficient by being less than -200 × 10-12(m2/ N) (methyl) propylene The adhesive composition of acid copolymer (A2) and isocyanates crosslinking agent (B2) containing aromatic ring is formed, and the polarizer is with viscous The photoelastic coefficient of mixture layer is -200 × 10-12~+200 × 10-12(m2/ N), and directly mutually ground connection configures with polarizer.
5. polarizer adhesive phase as claimed in claim 4, it is characterised in that isocyanates crosslinking agent (B2) is to be selected from At least one of toluene di-isocyanate(TDI) class crosslinking agent and sub- xylene diisocyanate class crosslinking agent.
6. polarizer adhesive phase as described in claim 4 or 5, it is characterised in that described adhesive composition contains phase It is isocyanates crosslinking agents (B2) more than 2 mass parts for 100 mass parts of copolymer (A2).
7. a kind of polarizer bonding sheet, it is with adhesive phase according to any one of claims 1 to 6.
8. a kind of polarizer with adhesive phase, it is layered at least one side of the polarizer with polarizer and directly On adhesive phase according to any one of claims 1 to 6.
9. a kind of polarizer adhesive composition for being used to form the adhesive phase described in claim 1, it contains photoelasticity Coefficient is -200 × 10-12~+200 × 10-12(m2/ N) (methyl) acrylic copolymer (A1) and the isocyanide without aromatic ring Esters of gallic acid crosslinking agent (B1), wherein, (methyl) acrylic copolymer (A1) has the photoelastic coefficient from homopolymer For -1000 × 10-12~-100 × 10-12(m2/ N) (methyl) alkyl acrylate (a11) construction unit and from homopolymerization The photoelastic coefficient of thing is+500 × 10-12~+2000 × 10-12(m2/ N) (methyl) acrylate (a12) containing aromatic ring Construction unit.
10. a kind of polarizer adhesive composition for being used to form the adhesive phase described in claim 4, it contains photoelasticity Coefficient is less than -200 × 10-12(m2/ N) (methyl) acrylic copolymer (A2) and isocyanates crosslinking agent containing aromatic ring (B2)。
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