CN106164718A - Polaroid adhesive composition, adhesive phase, bonding sheet and the polaroid of band adhesive phase - Google Patents

Polaroid adhesive composition, adhesive phase, bonding sheet and the polaroid of band adhesive phase Download PDF

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Publication number
CN106164718A
CN106164718A CN201580014225.5A CN201580014225A CN106164718A CN 106164718 A CN106164718 A CN 106164718A CN 201580014225 A CN201580014225 A CN 201580014225A CN 106164718 A CN106164718 A CN 106164718A
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Prior art keywords
methyl
polaroid
adhesive phase
adhesive composition
mass
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Inventor
室井佐知
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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)

Abstract

The present invention provides a kind of warpage (bending) that can suppress liquid crystal cell and can form the polaroid adhesive composition of adhesive phase of excellent in te pins of durability.Polaroid adhesive composition is characterised by, this polaroid adhesive composition contains (A) and is obtained and utilized the degree of branching that gel permeation chromatography/multi-angle laser light scattering detector (GPC MALS) measures (methyl) acrylic copolymer below 0.55 by the copolymer composition copolymerization of (methyl) alkyl acrylate that the carbon number comprising alkyl is 4～18 and polymerism macromonomer, described compositions the gel fraction of the binding agent formed is below 30 mass %.

Description

Polaroid adhesive composition, adhesive phase, bonding sheet and band adhesive phase Polaroid
Technical field
The present invention relates to polaroid 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 polaroid is via binding agent Layer adheres to the surface of described substrate.Polaroid 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, (substrate of liquid crystal cell is such as constituted along with the slimming of liquid crystal cell Slimming) and the slimming of polaroid, the warpage of the liquid crystal cell under hot and humid thermal environment becomes all the more problem.Liquid crystal The reason of structure cell warpage can enumerate such as adhesive phase cannot catch up with the thermal contraction (change in size) of polaroid, adhesive phase should It is low that power alleviates characteristic.
It addition, under hot and humid thermal environment, be susceptible to the interface generation bubble of polaroid and substrate or bond The unfavorable conditions such as oxidant layer fracture, polaroid stripping.So, it is desirable to polaroid binding agent has high-durability.
The generally means of suppression liquid crystal cell warpage can enumerate the highly-flexible using the change in size coping with polaroid 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.
As the solution of above-mentioned problem, such as, patent document 1 discloses that one makes specifically (methyl) acrylic compounds Polymer crosslinks with the pressure-sensitive adhesive for optical films containing peroxide and isocyanate ester compound and is reacted to form bonding The method of oxidant layer.Described in patent documentation 1, by the crosslinking side by utilizing the thermal decomposition cross-linking reaction caused by peroxide Method and utilizing and is used by the cross-linking method formed of amino-formate bond produced by isocyanate ester compound in addition, it is possible to Maintain sufficient stress to alleviate characteristic the stress produced with blooming change in size, keep high-durability simultaneously.
But, in the method for patent documentation 1, the peroxide remained in the adhesive phase after cross-linking reaction can be due to Light or heat and decompose, produce free radical, the problem that therefore can produce adhesive phase deterioration.
It addition, in patent documentation 2 with heavy industry fissility (リ ワ Network), hot and humid under the conditions of durability as class Topic, discloses containing by (methyl) acrylic monomer, macromonomer and (methyl) acrylic acid with cross-linking functional group (methyl) acrylic polymer that esters monomer is polymerized and there is the sense can reacted with above-mentioned cross-linking functional group The firming agent of group and gel fraction adhesive composition of less than 80% more than 55%.
But, not about the record of suppression liquid crystal cell warpage in patent documentation 2, and the gel fraction of adhesive phase is also Higher, thus it is low to speculate that its stress alleviates characteristic.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2006-183022 publication
Patent documentation 2: Japanese Patent Laid-Open 2010-150400 publication
Summary 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 The polaroid adhesive composition of adhesive phase, described the compositions adhesive phase formed, there is described adhesive phase Polaroid bonding sheet and there is the polaroid of band adhesive phase of 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 was found that using by the carbon of alkyl Number is that (methyl) alkyl acrylate of 4～18 obtains with polymerism macromonomer copolymerization and the degree of branching is in particular range (methyl) acrylic copolymer occasion under, even if gel fraction is designed to low, the warpage that also can suppress liquid crystal cell is (curved Bent), and the adhesive phase of excellent in te pins of durability can be formed.That is, the inventors discovered that, by use, there is following specific composition Polaroid adhesive composition can solve the problem that above-mentioned technical problem, thus complete invention.
[1]～[10] that the present invention is for example, following.
[1] a kind of polaroid adhesive composition, it is characterised in that this polaroid adhesive composition contains (A) Obtained by the copolymer composition copolymerization of (methyl) alkyl acrylate that the carbon number comprising alkyl is 4～18 and polymerism macromonomer To and utilize the degree of branching that gel permeation chromatography/multi-angle laser light scattering detector (GPC-MALS) measures 0.55 with Under (methyl) acrylic copolymer, described compositions the gel fraction of the binding agent formed is below 30 mass %.
[2] the polaroid adhesive composition described in above-mentioned [1], wherein, described (methyl) acrylic copolymer (A) be by described (methyl) alkyl acrylate and polymerism macromonomer, the most also with the monomer of polar functionalities the most altogether The copolymer gathered and obtain.
[3] above-mentioned [1] or [2] described in adhesive composition, wherein, the monomer of the polar functionalities in described copolymerization Consumption in the copolymer composition of 100 mass % below 10 mass %.
[4] above-mentioned [1]～[3] any one of described in polaroid adhesive composition, 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.
[5] above-mentioned [1]～[4] any one of described in polaroid adhesive composition, wherein, possibly together with (B) hand over Connection agent.
[6] the polaroid adhesive composition described in above-mentioned [5], wherein, described cross-linking agent (B) is selected from Carbimide. At least one in ester compounds (B1), metallo-chelate (B2) and epoxide (B3).
[7] above-mentioned [5] or [6] described in polaroid adhesive composition, wherein, the content of described cross-linking agent (B) Relative to (methyl) acrylic copolymer (A) described in 100 mass parts below 5 mass parts.
[8] a kind of polaroid adhesive phase, it is characterised in that by the polarization described in any one of above-mentioned [1]～[7] Sheet adhesive composition is formed, and gel fraction is below 30 mass %.
[9] a kind of polaroid bonding sheet, it is characterised in that there is the adhesive phase described in above-mentioned [8].
[10] polaroid of a kind of band adhesive phase, it is characterised in that there is polaroid and at least the one of described polaroid The adhesive phase described in above-mentioned [8] on the face of side.
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 polaroid adhesive composition of mixture layer, the above-mentioned composition adhesive phase formed, there is the inclined of above-mentioned adhesive phase Shake sheet bonding sheet and have the polaroid of band adhesive phase of above-mentioned adhesive phase.
Detailed description of the invention
Below, to the polaroid adhesive composition of the present invention, polaroid adhesive phase, polaroid bonding sheet with And the polaroid of band adhesive phase illustrates.Hereinafter, the polaroid adhesive composition of the present invention is also referred to as " viscous Mixture composite ", the polaroid adhesive phase of the present invention is also referred to as " adhesive phase ", the polaroid bonding sheet of the present invention Also referred to as " bonding sheet ".
[polaroid adhesive composition]
The polaroid adhesive composition of the present invention contains (methyl) acrylic copolymer (A).Above-mentioned binding agent group Compound, the most also can be containing selected from silane coupler (C), antistatic agent (D) and organic molten preferably possibly together with cross-linking agent (B) At least one in agent (E).
The gel fraction of the binding agent formed with adhesive composition by the polaroid of the present invention is below 30 mass %, excellent Elect 0～25 mass %, more preferably 0～20 mass % as.Even if gel fraction is within the above range, due to as described below (methyl) acrylic copolymer (A) also has a high side chain from polymerism macromonomer, thus the side chain of copolymer (A) Between can moderately be interweaved, the durability of adhesive phase or processability will not deteriorate.If gel fraction is beyond above-mentioned Scope, then adhesive phase cannot fully absorb alleviation by caused by the change in size of polaroid under hot and humid thermal environment Stress.Above-mentioned gel fraction is the number that the binding agent gathered is measured obtaining by the condition such as recorded according to embodiment Value.
[(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 copolymer composition copolymerization with polymerism macromonomer obtains.As the copolymer composition of copolymer (A), it be also possible to use The monomer of polar functionalities and at least one in other monomer in addition.
Acrylic acid and methacrylic acid are referred to as and are denoted as " (methyl) acrylic acid " by this specification.It addition, by polymer Included in the construction unit coming from certain monomer a be denoted as " monomer a unit.”
(methyl) acrylic copolymer (A) utilizes gel permeation chromatography/multi-angle laser light scattering detector (GPC- MALS) degree of branching measured below 0.55, preferably 0.10～0.54, more preferably 0.20～0.53, particularly preferably It is 0.30～0.53.The detailed content of degree of branching condition determination is recorded in embodiment.
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.It addition, in branched shaped polymer, be polymerized under the occasion that degree of branching numerical value is little The branch of thing molecule is many, is shown as having high side chain, and under the occasion that degree of branching numerical value is big, the branch of polymer molecule is few, is shown as There is low side chain.
The degree of branching (methyl) acrylic copolymer (A) within the above range has characteristics that (1) is at room temperature Because of a large amount of the generation, even if its result is polymer molecular weight and adhesive phase that interweave produced by the side chain that polymer molecule is mutual Gel fraction is designed to low, and the coherency of polymer also is able to maintain, and obtains adhesion characteristic, processes adhesive phase punching press etc. Property, the deformation of adhesive phase and the excellent adhesive phase of the keeping property such as extrusion is few；(2) polymer under high temperature (such as: 60 DEG C) The mutual above-mentioned interlaced sections of molecule relaxes, and adhesive phase presents the flexibility of excellence and in the warpage (bending) of polaroid Suppression aspect is excellent, simultaneously because the above-mentioned intertexture of part residual and present the durability of excellence.
Warpage about polaroid is suppressed this point, thus it is speculated that be due to the fact that caused.With at such as polaroid/viscous The such structure of mixture layer/clung body use glass plate illustrate as a example by the occasion of clung body.Polaroid and glass The respective percent thermal shrinkage of plate is different, and the percent thermal shrinkage (change in size) of polaroid is generally big than glass plate.Lack at adhesive phase Under the occasion of the flexibility under hot and humid thermal environment, adhesive phase cannot catch up with the change in size of polaroid, it is impossible to alleviates Stress at adhesive phase, stress concentrates on glass plate, and warpage occurs the most on a glass.And by the binding agent group of the present invention The adhesive phase that compound is formed contains high branched-chain polymer, and the part pine of above-mentioned intertexture under hot and humid thermal environment Relax, so adhesive phase can catch up with the change in size of polaroid.Therefore, will not produce stress, stress is not centered on glass plate. Shrink it addition, polaroid also is able to the most anisotropically uniform heat, the birefringence of polaroid will not be induced.As it has been described above, this In invention, adhesive phase can absorb alleviation stress along with the change in size of polaroid, applies thus without to glass plate Excessive stress (load), thus it is speculated that this is related to the suppression to glass plate warpage.
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 sheet.Even if particularly the thickness at the glass plate of the liquid crystal cell constituting slimming is little to a 0.10～1.0mm left side Under right occasion, it is also applied for the laminating purposes of this substrate and polaroid.
" (methyl) alkyl acrylate "
As (methyl) alkyl acrylate, (methyl) alkyl acrylate that carbon number is 4～18 of alkyl can be used (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 carbon number is 4～18 of alkyl, the positive fourth of (methyl) acrylic acid can be enumerated such as Ester, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) 1-Octyl 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 copolymer composition 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 99.7～ 20 mass %, more preferably 99.4～30 mass %, the most preferably 98.7～50 mass %.
Copolymer composition 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 carbon number is 1～3 of alkyl, can enumerate such as (methyl) acrylic acid methyl ester., (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 is that the consumption of (methyl) alkyl acrylate of 1～3 is alleviated from the viewpoint of characteristic from stress, In the copolymer composition of 100 mass % preferably below 60 mass %, further preferably below 50 mass %, the most preferably Below 40 mass %.
" polymerism macromonomer "
Polymerism macromonomer is that have can be unsaturated with the polymerism of above-mentioned (methyl) alkyl acrylate copolymer The monomer that the molecular weight of group is big.
As the polymer chain (main chain) of composition polymerism macromonomer, can be with above-mentioned (methyl) third as long as have The material of the polymerism unsaturated group of olefin(e) acid Arrcostab copolymerization is just not particularly limited, but preferably since from selected from (methyl) third The constitutional repeating unit of at least one in olefin(e) acid Arrcostab, styrene and acrylonitrile is main constituent, further preferably with from The constitutional repeating unit of (methyl) alkyl acrylate is main constituent.Here, so-called main constituent, refer to relative to all repeating list Position amount, content is more than 50 mass %.
Polymer chain part is big with the polymerism as main constituent of the constitutional repeating unit from (methyl) alkyl acrylate In molecule monomer, with the constitutional repeating unit of (methyl) alkyl acrylate that the carbon number from alkyl is 1～8 it is particularly preferably The polymer chain of main constituent.Above-mentioned (methyl) alkyl acrylate can enumerate such as (methyl) acrylic acid methyl ester., (methyl) propylene Acetoacetic ester, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate.
Under the occasion that polymer chain part is made up of the constitutional repeating unit from (methyl) alkyl acrylate, polymerization In thing chain part, the carbon number of alkyl be the content of (methyl) acrylate unit of 1～8 generally more than 60 mass %, Preferably more than 80 mass %.If above-mentioned content is within the range, then can also have the weight from styrene, acrylonitrile etc. Complex structure unit.
The constitutional repeating unit constituting polymer chain (main chain) part both can be made up of a kind of constitutional repeating unit, it is possible to To be made up of two or more constitutional repeating unit.Under the occasion of the latter, polymer chain part can be random copolymer chain, embedding Any one in section copolymer chain, alternate copolymer chain.
Polymerism macromonomer reacts, in (first with above-mentioned (methyl) alkyl acrylate used as copolymer composition Base) acrylic copolymer (A) is formed the side chain from above-mentioned macromonomer.Therefore, (methyl) acrylic copolymer (A) there is the structure of highly branched chain, become high branched-chain polymer.
The polymerism unsaturated group that polymerism macromonomer is had preferably has the base of alkene unsaturated double-bond Group, can enumerate such as (methyl) acryloyl group, pi-allyl, acrylic, vinyl, inclined vinyl (PVC ニ リ デ Application base), sub-ethylene Base, preferably (methyl) acryloyl group or vinyl, particularly preferably (methyl) acryloyl group.
Polymerism unsaturated group both may be present in the end of polymer chain part, it is possible to is present on side chain, but preferably It is present in end.It addition, polymerism unsaturated group both can exist only in the end of one end of polymer chain part, it is possible to exist In the end at two ends, but from the standpoint of the stability when polymerization, preferably exist only in the end of one end of polymer chain part.
Polymerism macromonomer is preferably (methyl) acrylic compounds macromonomer.Divide greatly as (methyl) acrylic compounds Sub-monomer, can enumerate such as end and have poly-(methyl) acrylic acid methyl ester. of (methyl) acryloyl group, poly-(methyl) acrylic acid fourth Ester, poly-(methyl) Isobutyl 2-propenoate, wherein, preferably end has poly-(methyl) acrylic acid methyl ester. of (methyl) acryloyl group.
The number-average molecular weight of polymerism macromonomer generally more than 500, preferably 1000～10000, the most excellent Elect 3000～8000 as.The number-average molecular weight (Mn) of polymerism macromonomer is the polyphenyl utilizing gel permeation chromatography to measure Ethylene scaled value.
The glass transition temperature (Tg) of polymerism macromonomer closes from sufficient cohesiveness and workability or durability From the viewpoint of fitting and guaranteeing elastic performance, it is preferably-60～150 DEG C, more preferably-30～130 DEG C, the most excellent Elect 0～120 DEG C as.The glass transition temperature (Tg) of polymerism macromonomer can be by the list such as constituting this macromonomer Body unit and content ratio thereof utilize Fox formula hereinafter described to calculate.
As the commercially available product of polymerism macromonomer, such as Toagosei Co., Ltd's (synthesis (strain)) can be enumerated The commodity manufactured, i.e. functional end-group be (methyl) acryloyl group, polymer chain part be dividing greatly of polymethyl methacrylate Sub-monomer (trade name: 45%AA-6, AA-6SR, AA-6), polymer chain part is the macromole list of polybutyl methacrylate Body (trade name: AB-6), polymer chain part is the macromonomer (trade name: AW-6S) of polyisobutyl methacrylate.
Above-mentioned polymerism macromonomer can be used alone a kind, it is possible to use two or more.
In the copolymer composition of formation (methyl) acrylic copolymer (A) of 100 mass %, polymerism macromonomer Total amount is usually 0.3～20 mass %, preferably 0.5～12 mass %, more preferably 0.8～10 mass %.If The copolymerization amount of macromonomer within the above range, is then preferred on this aspect of coherency obtain copolymer.If divided greatly The copolymerization amount of sub-monomer exceedes above-mentioned scope, then in copolymerization, viscosity can be ramping up, if the coating fluid containing copolymer is viscous Spend height, then cannot obtain the good coating to base material.
" monomer of polar functionalities "
As the monomer of polar functionalities, can enumerate such as hydroxyl monomer, containing acid-based monomers, emulsion stability, containing acyl Amine-containing monomers, the monomer of nitrogenous system heterocycle, cyano-containing monomer.As the acidic group in this specification, such as carboxyl, anhydride can be enumerated Base, phosphate, sulfate.As the monomer of polar functionalities, it is preferably used and there is the crosslinking can being had with cross-linking agent (B) The monomer of the polar group (cross-linking functional group) of property functional group reactions.
Wherein, from the viewpoint of the base material adaptation of the bloomings such as raising and polaroid, polar group is preferably used is Carboxyl and/or the monomer of hydroxyl, be i.e. preferably used at least one in carboxyl group-containing monomer and hydroxyl monomer.
As hydroxyl monomer, (methyl) acrylate of such as hydroxyl can be enumerated, specifically, (methyl) can be enumerated Acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 3-hydroxypropyl acrylate, (methyl) acrylic acid 4-hydroxy butyl ester, (methyl) acrylic acid 6-hydroxyl are own (methyl) hydroxyalkyl acrylates such as ester, (methyl) acrylic acid 8-hydroxyl monooctyl ester.The carbon number of hydroxyalkyl in (methyl) hydroxyalkyl acrylate It 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.
As carboxyl group-containing monomer, can enumerate such as (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.
Such as, the acid number of (methyl) acrylic copolymer (A), preferably at below 117mgKOH/g, further preferably exists Below 78mmKOH/g.
As emulsion stability, (methyl) acrylate, (methyl) acrylic acid diethyl can be enumerated such as (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 ketopyrrolidine, acryloyl morpholine, caprolactam can be enumerated.As Cyano-containing monomer, can enumerate such as cyano group (methyl) acrylate, (methyl) acrylonitrile.
The consumption of the monomer of polar functionalities preferably below 10 mass %, enters one in the copolymer composition of 100 mass % Step is preferably 0.1～9 mass %, the most preferably 0.5～8 mass %.
If the consumption of the monomer of polar functionalities is below above-mentioned higher limit, then by (methyl) acrylic copolymer (A) and the crosslink density that formed of cross-linking agent (B) will not become too high, it is possible to obtain stress and alleviate the adhesive phase of excellent. In the present invention, have from the high (first of the construction unit of (methyl) acrylic compounds macromonomer and the degree of branching owing to employing Base) acrylic copolymer (A), even if therefore crosslink density is low, i.e. the gel fraction of adhesive phase be designed into 30 mass % with Under the lowest, it is also possible to obtain having high working property, keeping property and the adhesive phase of durability.
The monomer of polar functionalities can be used alone a kind, it is possible to use two or more.
" other monomer "
The copolymer composition forming (methyl) acrylic copolymer (A) is not damaging (methyl) acrylic copolymer (A) Physical property in the range of can contain 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), containing ester ring type group or aromatic ring Other (methyl) acrylate such as (methyl) acrylate.
As (methyl) alkyl acrylate epoxide alkyl ester, (methyl) methoxyethyl methyl ester, (methyl) third can be enumerated such as 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, such as 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 containing ester ring type group or aromatic ring, (methyl) acrylate can be enumerated such as Ester, (methyl) benzyl acrylate, (methyl) phenyl acrylate.
In above-mentioned copolymerization, total consumption of other (methyl) acrylate above-mentioned preferably exists in the copolymer composition of 100 mass % Below 60 mass %, further preferably below 40 mass %.
It addition, in the range of the physical property not damaging (methyl) acrylic copolymer (A), it is possible to use such as benzene second Alkene, methyl styrene, dimethyl styrene, trimethyl styrene, propylstyrene, butylstyrene, hexyl benzene ethylene, heptyl The ring-alkylated styrenes such as styrene and octyl styrene, fluorobenzene ethylene, chlorostyrene, bromstyrol, Dowspray 9, iodobenzene second The styrene monomers such as alkene, nitrostyrolene, acetylbenzene ethylene 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 copolymer composition of 100 mass % preferably in 40 matter Amount below %, further preferably below 20 mass %.
Other monomer 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) may utilize such as solution polymerization process, mass polymerization, emulsion polymerization, hangs The known polymerization so far such as floating polymerization manufactures, wherein preferred solution polymerization process.Specifically, it is by polymer solvent and to be total to Being polymerized to be distributed in reaction vessel, add polymerization initiator under the inert gas atmospheres such as nitrogen, 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.
(methyl) acrylic copolymer (A) be preferably in the presence of polymerization initiator by above-mentioned copolymerization obtained by Copolymer.As polymerization initiator, such as azo-initiator, peroxide type polymerization initiator can be enumerated.
As azo-initiator, such as 2 can be enumerated, 2 '-azodiisobutyronitrile, 2,2 '-azo two (4-methoxyl group-2, 4-methyl pentane nitrile), 2,2 '-azo two (2-cyclopropyl propionitrile), 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo Two (2-methylbutyronitriles), 1,1 '-azo two (hexamethylene-1-nitrile), 2-(carbamoyl azo) isopropyl cyanide, 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 '-two methylene Base 2,2-Dimethylaziridine), 2,2 '-azo two [2-methyl-N-(2-ethoxy)-propionic acid amide .], 2,2 '-azo two (isobutyramide) two hydration Thing, 4,4 '-azo two (4-cyanopentanoic acid), 2,2 '-azo two (2-cyano group propanol), dimethyl-2,2 '-azo two (2-methyl Propionic ester), the azo-compound such as 2,2 '-azo two [2-methyl-N-(2-ethoxy) propionic acid amide .].
As peroxide type polymerization initiator, such as tert-butyl hydroperoxide, cumyl hydroperoxide, peroxide can be enumerated Change diisopropylbenzene (DIPB), benzoyl peroxide, lauroyl peroxide, peroxidating hexanoyl, di-isopropyl peroxydicarbonate, peroxidating two Carbonic acid two 2-Octyl Nitrite, tert-Butyl peroxypivalate, 2,2-bis-(peroxidating 4,4-di-t-butyl cyclohexyl) propane, 2,2- Two (peroxidating 4,4-bis-tert-amylcyclohexyl) propane, 2,2-bis-(peroxidating 4,4-bis-t-octyl cyclohexyl) propane, 2,2-bis- (peroxidating 4,4-bis-α-cumyl cyclohexyl) propane, 2,2-bis-(peroxidating 4,4-di-t-butyl cyclohexyl) butane, 2,2-bis-(mistake Oxidation 4,4-bis-t-octyl cyclohexyl) butane.
These polymerization initiators can be used alone a kind, it is possible to use two or more.
Relative to the copolymer composition of formation (methyl) acrylic copolymer (A) of 100 mass parts, with usual 0.001～5 The amount of mass parts, preferably 0.005～3 mass parts uses polymerization initiator.It addition, in above-mentioned polyreaction, it is also possible to suitably Add and add polymerization initiator, chain-transferring agent, copolymer composition, polymer solvent.
As 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, normal 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, butanone, diethyl ketone, methylisobutylketone, Ketohexamethylene；N, N-bis- The amide-types such as methylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone；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.
" physical property of (methyl) acrylic copolymer (A) and content "
(methyl) acrylic copolymer (A) utilizes weight average molecular weight (Mw) that GPC method measures with polystyrene conversion value Meter usually 200,000～1,500,000, preferably 400,000～1,300,000, more preferably 500,000～1,100,000.Due to copolymer (A) i.e. Mw is made the most also to have the high side chain from polymerism macromonomer, thus can between copolymer (A) side chain Moderately being interweaved, the durability of adhesive phase or processability will not deteriorate.Particularly when Mw is more than 400,000, then can Obtain the adhesive phase that coherency is high.
(methyl) acrylic copolymer (A) utilize molecular weight distribution (Mw/Mn) that GPC method measures generally below 50, Preferably below 30, further preferably below 20.
The glass transition temperature (Tg) of (methyl) acrylic copolymer (A) can be by the monomer such as 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), it is possible to obtain under room temperature viscous The adhesive composition that conjunction property is excellent.
Fox formula: 1/Tg=(W1/Tg1)+(W2/Tg2)+…+(Wm/Tgm)
W1+W2+…+Wm=1
In formula, Tg is the glass transition temperature of (methyl) acrylic copolymer (A), Tg1、Tg2、……、TgmServe as reasons The glass transition temperature of the homopolymer that each monomer is constituted, W1、W2、……、WmFor deriving from the above-mentioned of the construction unit of each monomer Weight fraction in copolymer (A).
The glass transition temperature of the homopolymer being made up of each monomer in above-mentioned Fox formula can use such as " polymer hands 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 % Usually 50～100 mass % in solid constituent in addition to organic solvent (E) in compositions, more preferably 60～ 99.999 mass %, particularly preferably 80～99.99 mass %.If the content of (methyl) acrylic copolymer (A) is upper In the range of stating, then can obtain the balance of the performance as binding agent, and adhesion characteristic is excellent.
[cross-linking agent (B)]
Preferably the polaroid adhesive composition of the present invention is possibly together with cross-linking agent (B).Cross-linking agent (B) as long as can be with The polar group from the monomer of polar functionalities included in (methyl) acrylic copolymer (A) crosslinks reaction Composition is just not particularly limited, and can enumerate such as isocyanate compound (B1), metallo-chelate (B2), epoxide (B3)。
In the present invention, common owing to employing (methyl) acrylic compounds with the high side chain from polymerism macromonomer Polymers (A), though do not use cross-linking agent (B) or the most on a small quantity use, i.e. the gel fraction of adhesive phase be designed to 30 mass % with Under the lowest, it is also possible to obtain having high working property, keeping property and the adhesive phase of durability.
Cross-linking agent (B) can be used alone a kind, it is possible to use two or more.
Isocyanate compound (B1) and/or metallo-chelate (B2) are preferably used in cross-linking agent (B).Preferably by based on The covalent bond of isocyanate compound (B1) (methyl) acrylic copolymer (A) is formed crosslinking, and/or passes through base Coordinate bond in metallo-chelate (B2) (methyl) acrylic copolymer (A) is formed quasi-crosslink (Japanese: doubtful frame).
In the adhesive composition of the present invention, the total content of cross-linking agent (B) is relative to (methyl) propylene of 100 mass parts Acid copolymer (A) is preferably below 5 mass parts, further preferably below 2.5 mass parts, and the most preferably 0.001 ～1 mass parts, particularly preferably 0.01～0.5 mass parts.Even this small amount of use or do not use the body of cross-linking agent (B) System, it is also possible to realize the adhesive phase with the durability under the cohesive of excellence, dimensional stability, high humid and warm environment.
[isocyanate compound (B1)]
As isocyanate compound (B1), generally use isocyanates radix isocyanation esterification more than 2 in 1 molecule Compound.By utilizing isocyanate compound (B1) to make (methyl) acrylic copolymer (A) cross-link, it is possible to form crosslinked (net Shaped polymer).
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 binding agent this aspect of flexibility on be preferred.
It is the diisocyanate cpd of 2 as isocyanates radix in 1 molecule, the most aliphatic two Carbimide .s 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, isophorone diisocyanate, cyclopenta two can be enumerated different Cyanate, cyclohexyl diisocyanate, hydrogenation Asia XDI, hydrogenated tolylene diisocyanate, hydrogenation hexichol first The alicyclic diisocyanates that carbon number is 7～30 such as alkane diisocyanate, hydrogenation tetramethyl Asia XDI.As Aromatic diisocyanates, can enumerate such as 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 isocyanates radix isocyanate compound more than 3 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.
It 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 trimer, biuret body, isocyanuric acid ester body) of cyanate esters, derivant are (the most The additive 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 ternarys such as such as trimethylolpropane, glycerol, tetramethylolmethane；High score Sub-weight polyalcohol can enumerate such as polyether polyol, PEPA, acrylic polyol, polybutadiene polyol, poly-isoamyl Diene polyol.
Such isocyanate compound can enumerate the trimer of such as '-diphenylmethane diisocyanate, polymethylene polyphenyl The biuret body of base polyisocyanate, hexamethylene diisocyanate or toluene di-isocyanate(TDI) or isocyanuric acid ester body, three hydroxyls Methylpropane and toluene di-isocyanate(TDI) or product (the such as toluene di-isocyanate(TDI) or Asia of 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 polyisocyanate, polyester polyisocyanate.
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 manufactured, 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.
In the adhesive composition of the present invention, the content of isocyanate compound (B1) is relative to (the first of 100 mass parts Base) acrylic copolymer (A) is preferably below 5 mass parts, further preferably below 2.5 mass parts, the most preferably Below 1 mass parts, particularly preferably below 0.5 mass parts.If this content is within the above range, the most easily obtain durability With the balance that stress alleviates characteristic, thus preferably.Use lower limit for example, 0.001 mass parts time above-mentioned (B1), be preferably 0.01 mass parts.
[metallo-chelate (B2)]
As metallo-chelate (B2), can enumerate such as alkoxide, acetylacetone,2,4-pentanedione, ethyl acetoacetate etc. to aluminum, ferrum, copper, The compound of the polyvalent metal coordination such as zinc, stannum, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium.Wherein, preferably aluminium chelate compound (combines grinding Learn the M-12AT etc. that Co., Ltd. manufactures).Specifically, aluminum isopropylate., secondary butanoic acid aluminum, acetoacetic acid aluminium ethide two can be enumerated different Propyl ester, tri ethylacetoacetate aluminum, praseodynium aluminum.
Metallo-chelate (B2) can be used alone a kind, it is possible to use two or more.
Metallo-chelate (B2) makes (methyl) acrylic copolymer (A) cross-link (quasi-crosslink) by coordinate bond.Using Under the metallo-chelate (B2) occasion as cross-linking agent (B), when room temperature, described crosslinking is maintained, and polymer plays cohesion Property, and the part releasing of described crosslinking when high temperature, adhesive phase presents more excellent flexibility.
In the adhesive composition of the present invention, the content of metallo-chelate (B2) is relative to (methyl) third of 100 mass parts Olefin(e) acid analog copolymer (A) is preferably below 5 mass parts, further preferably below 2.5 mass parts, the most preferably in 1 matter Below amount part, particularly preferably below 0.5 mass parts.If this content is within the above range, the most easily obtains durability and answer The balance of power alleviation characteristic, thus preferably.Use lower limit for example, 0.001 mass parts time above-mentioned (B2), preferably 0.01 Mass parts.
In the adhesive composition of the present invention, using isocyanate compound (B1) and metallo-chelate (B2) as handing over Connection agent (B) occasion under, the content of above-mentioned (B2) relative to 100 mass parts above-mentioned (B1) be usually more than 0 mass parts and Below 1000 mass parts, further preferably more than 0 mass parts and below 600 mass parts, the most preferably greater than 0 mass parts And below 400 mass parts.If this content is within the above range, then at suppression amount of bow and the optics such as raising and polaroid It is preferred on this aspect of the base material adaptation of film.
" epoxide (B3) "
As epoxide (B3), generally use 1 molecule epoxy group number epoxide more than 2.Can enumerate Such as Ethylene glycol diglycidyl ether, polyethyleneglycol diglycidylether, glycerin diglycidyl ether, glycerol three-glycidyl Ether, 1,3-double (N, N-diglycidyl amino methyl) hexamethylene, N, N, N', N'-four glycidyl group m-xylene diamine, N, N, N', N'-four glycidyl group aminophenyl methane, Carbimide. three-glycidyl ester, a N, N-diglycidyl aminobenzene Base glycidyl ether, N, N-diglycidyl toluidines, N, N-diglycidylaniline.
In the adhesive composition of the present invention, the content of epoxide (B3) is relative to (methyl) third of 100 mass parts Olefin(e) acid analog copolymer (A) is preferably below 2 mass parts, further preferably below 1 mass parts, the most preferably in 0.5 matter Below amount part.Use lower limit for example, 0.001 mass parts time above-mentioned (B3), preferably 0.01 mass parts.
[silane coupler (C)]
Preferably the polaroid 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. are containing 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 polaroid 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 polaroid 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 such as reduce the sheet resistance value of the polaroid 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 ester alkali etc. The anionic surfactant of anionic group；Alkyl betaines bases, alkyl imidazole betaines, alkyl amine The amphoteric surfactantes such as class, aminoacid 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 surfactant.
It 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 macromolecule quantization 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 Property excellent Li+、Na+And K+.As organic cation, such as pyridylium, piperidines cation, ketopyrrolidine 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 derivant.
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, particularly preferably because providing the ionic compound of low melting point (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, Tetrafluoroboric 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 derivant can be enumerated.
The content of the antistatic agent (D) in the polaroid 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.Such as, 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 cross-linking 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 %.
It 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 above-mentioned solid constituent binding agent relative to 100 mass % The ratio of compositions.
[additive]
The adhesive composition of the present invention, in addition to mentioned component, is not damaging in the range of effect of the present invention, also may be used Containing beyond antioxidant, light stabilizer, preventing metal corrosion agent, viscosifier, 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 polaroid adhesive composition]
The polaroid adhesive composition of the present invention can be by utilization known method so far to (methyl) acrylic compounds Copolymer (A) and other composition used as desired carry out mixing to modulate.Can enumerate such as to synthesis (methyl) propylene When acid copolymer (A) obtained by the polymer solution containing this polymer in blend as required cross-linking agent (B) and its Its composition.
[adhesive phase]
The adhesive phase of the present invention can obtain by such as being coated being dried to above-mentioned adhesive composition；Or Obtain by carrying out the cross-linking reaction in above-mentioned adhesive composition, specifically can be by making (methyl) third with cross-linking agent (B) Olefin(e) acid analog copolymer (A) crosslinking obtains.
The formation condition of adhesive phase is the most as described below.The adhesive composition of the present invention is coated 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 as 2～7 minutes be dried to remove solvent, formation film.The thickness of dry coating is usually 5～75 μm, preferably 10～ 50μm。
Adhesive phase is formed the most under the following conditions.The adhesive composition of the present invention is coated on supporting mass, After coverlay is pasted 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 ripening as described above Under the conditions of cross-link, then can be efficiently formed crosslinked (network polymers).
As the coating process of adhesive composition, known method can be used, such as by 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 coverlay, the polyester films such as 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 formed by the adhesive composition of the present invention is from suppression polaroid distortion, cohesiveness, bonding force, again From the viewpoint of fissility, gel fraction below 30 mass %, preferably 0～25 mass %, more preferably 0～20 matter Amount %.Even if dividing greatly from polymerism owing to gel fraction (methyl) acrylic copolymer (A) within the above range also has The high side chain of sub-monomer, thus can moderately be interweaved between the side chain of copolymer (A), the durability of adhesive phase or add Work will not deteriorate.If gel fraction exceeds above-mentioned scope, then adhesive phase cannot fully absorb alleviation by hot and humid heat Stress caused by the change in size of polaroid under environment.
[polaroid bonding sheet]
The polaroid bonding sheet of the present invention has the adhesive phase formed by above-mentioned polaroid adhesive composition.Make For bonding sheet, can enumerate and the most 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 above-mentioned adhesive phase being formed on the face of base material one side Bonding sheet and these bonding sheets are pasted with the coverlay through lift-off processing with base material on the face not contacted of adhesive phase Bonding sheet.
As base material and coverlay, the polyester films such as such as polyethylene terephthalate (PET) can be enumerated；Polyethylene, The plastic foil of the polyolefin film such as polypropylene, vinyl-vinyl acetate copolymer etc..
Formation condition or the gel fraction of adhesive phase are identical with condition described in [adhesive phase] hurdle.
The thickness of adhesive phase is usually 5～75 μm, preferably 10～50 μm from the viewpoint of maintaining bond properties.Base The thickness of material and coverlay is not particularly limited, but usually 10～125 μm, preferably 25～75 μm.
[polaroid of band adhesive phase]
The polaroid of the band adhesive phase of the present invention be characterized by polaroid and at above-mentioned polaroid at least one The adhesive phase formed by polaroid adhesive composition of the present invention on the face of side.It addition, in this specification, " polaroid " Use with the implication comprising " polarizing coating ".
Polaroid can use known polarizing coating so far.Can enumerate such as to have and be made up of polyvinyl alcohol resin by making Film in the stretched film that obtains containing carrying out stretching after polarized component and the multilamellar of protecting film being configured in above-mentioned stretched film Film.As polyvinyl alcohol resin, such as polyvinyl alcohol, polyvinyl formal, Pioloform, polyvinyl acetal, ethylene second can be enumerated Vinyl acetate copolymer saponified.Polarized component can enumerate such as iodine or dichroic dye.As protecting film, can enumerate such as The cellulose membranes such as tri acetyl cellulose, polycarbonate membrane, poly (ether sulfone) film.
The thickness of polaroid is usually 30～250 μm, preferably 50～200 μm.
The method forming adhesive phase on polaroid surface is not particularly limited, and can enumerate use direct stick coating method etc. partially Shake and make its method being dried after being coated with above-mentioned adhesive composition on sheet surface, the polaroid bonding sheet of the present invention is had Adhesive phase be transferred to polaroid surface after make the method for its ripening.Be dried and cooking conditions or gel fraction scope etc. with Condition described in [adhesive phase] hurdle is identical.
The thickness of the adhesive phase being formed on polaroid is usually 5～75 μm, preferably 10～50 μ in terms of dry film thickness m.As long as it addition, on the face of the adhesive phase at least one party that is formed at polaroid, adhesive phase can be enumerated and is only formed at partially The shake form on sheet one side, adhesive phase is formed at the form on polaroid two sides.
Furthermore it is also possible to stacking such as protective layer, antiglare layer, phase separation layer, angle of visibility improve layer on above-mentioned polaroid Etc. the layer with other function.
By the polaroid of the band adhesive phase of the present invention obtained in the manner described above being 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 structure 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 the most in the present invention, by using above-mentioned adhesive composition can suppress sticking up of polaroid and substrate Bent.Therefore, though above-mentioned adhesive composition under the occasion that substrate thickness is little (such as: below 0.8mm, preferably 0.15～ 0.7mm), it is also possible to be suitably used for the laminating of polaroid and substrate.
Embodiment
Below based on embodiment, the present invention carried out more specific description, 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 the number-average molecular weight (Mn) of (methyl) acrylic copolymer are entered by scatter detector (GPC-MALS) 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 parts of acrylic acid are added in the reaction unit possessing blender, reflux cooler, thermometer and nitrogen ingress pipe N-butyl, 1 part of end have Polymethyl Methacrylate Macromonomer (trade name: AA-6, the East Asia synthesis of methylacryloyl Co., Ltd. manufactures, Tg:105 DEG C, Mn:6000), 1 part of acrylic acid 4-hydroxy butyl ester and 100 parts of ethyl acetate solvents, importing Nitrogen is while being warming up to 80 DEG C.Then, add the 2 of 0.1 part, 2 '-azodiisobutyronitrile, carry out 6 in 80 DEG C in a nitrogen atmosphere Hour polyreaction.After reaction terminates, being diluted by ethyl acetate, prepared solid component concentration is the polymerization of 30 mass % Thing solution.The weight average molecular weight (Mw) of obtained (methyl) acrylic copolymer A is 700,000, molecular weight distribution (Mw/Mn) Being 7.2, the degree of branching is 0.54, and acid number is 0mgKOH/g.
[synthesis example 2～14]
Except the copolymer composition used in polyreaction and polymerization initiator are changed in table 1 described content 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.
In table 1, MMA macromonomer represents that end has the Polymethyl Methacrylate Macromonomer of methylacryloyl (trade name: AA-6, Toagosei Co., Ltd manufactures, Tg:105 DEG C, Mn:6000), BA macromonomer represents that end has The butyl acrylate macromonomer of acryloyl group (trade name: AB-6, Toagosei Co., Ltd manufactures, Tg:-50 DEG C, Mn: 6000)。
[table 1]
[embodiment 1]
(1) modulation of adhesive composition
By (methyl) acrylic polymer solution (solid component concentration is 30 mass %) obtained by synthesis example 1 and (solid becomes to be 0.08 part relative to (methyl) acrylic polymer contained in this solution of 100 parts (solid constituent amounts) Component) as isocyanate compound Soken Chemical & Engineering Co., Ltd. manufacture " TD-75 " (solid constituent is 75 mass %, Ethyl acetate solution) and the Shin-Etsu Chemial Co., Ltd as silane coupler (SHIN-ETSU HANTOTAI's chemistry work (strain)) of 0.2 part " KBM-403 " (solid constituent is 100%) and the Di-ichi Kogyo Seiyaku Co., Ltd. as antistatic agent of 1 part manufactured " AS-804 " (solid constituent is 100%) that (the first work (strain)) manufactures mixes, and obtains 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 On the reverse side of the sticking veneer of above-mentioned PET film, laminating is through the PET film of lift-off processing further, quiet under 23 DEG C/50%RH environment Put 7 days after carrying out ripening, obtain having by the bonding sheet of the adhesive phase that thickness is 20 μm clamped by 2 pieces of PET film.
(3) making of the polaroid of band 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 sheet with the film that desciccator diaphragm thickness is 20 μm. Make sheet above and polaroid (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 polaroid, stand after within 7 days, carrying out ripening under conditions of 23 DEG C/50%RH, Obtain having the polaroid of the band adhesive phase of PET film and adhesive phase that thickness is 20 μm and polaroid.
[embodiment 2～14, comparative example 1～3]
Except (methyl) acrylic polymer solution in embodiment 1 being changed to by gathering that synthesis example 2～14 obtains Polymer solution and/or be changed in table 2 beyond described content by blending composition, according to side same as in Example 1 Formula obtains adhesive composition, bonding sheet and the polaroid of band adhesive phase.In table 2, M-12AT represents that metallo-chelate is the most comprehensive Grind " M-12AT " (solid constituent is 10 mass %, toluene, acetylacetone,2,4-pentanedione solution) that KCC manufactures.
[evaluation]
[gel fraction]
The binding agent gathering about 0.1g from the bonding sheet obtained by embodiment comparative example is placed in sample bottle, adds The ethyl acetate of 30mL after shaking 4 hours, was carried out the content of this sample bottle with 200 purpose stainless steel wire netting Filter, at 100 DEG C, the residue on wire netting is carried out 2 hours measure dry weight after drying.Following formula is utilized to obtain bonding The gel fraction of agent.
Gel fraction (%)=(dry weight/binding agent gathers weight) × 100 (%)
[creep value]
By the polaroid of band adhesive phase that obtained by embodiment comparative example (by PET film/adhesive phase/polaroid The duplexer constituted) 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 processed Fit, obtain evaluation bonding processing polaroid test film.
To evaluation bonding processing polaroid 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 being parallel to this polaroid with above-mentioned Composition surface between glass plate and be the direction of length direction of above-mentioned polaroid to the above-mentioned evaluation in above-mentioned test film with viscous Close processing polaroid to pull, measure the deviation distance (μ of the above-mentioned glass plate of above-mentioned test film and the fitting part of polaroid M) as creep value.
[mensuration of bonding force]
By the polaroid of band adhesive phase that obtained by embodiment comparative example (by PET film/adhesive phase/polaroid structure The duplexer become) 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/polaroid 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 Polaroid end is pullled by degree, measures bonding force (peel strength).
[bending (warpage)]
By the polaroid of band adhesive phase that obtained by embodiment comparative example (by PET film/adhesive phase/polaroid structure The duplexer become) cut into the size in 35mm × 400mm (tensile axis direction), prepare test film.PET film is shelled from test film From, with laminating roll, the duplexer being made up of adhesive phase/polaroid is bonded in the way of making adhesive phase connect with glass plate 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.Unilateral end is fixed on metope perpendicular to the ground, uses 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 polaroid of band adhesive phase that obtained by embodiment comparative example (by PET film/adhesive phase/polaroid structure The duplexer become) 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/polaroid 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 bread boards.It is 60 by above-mentioned bread board (thermostability) or temperature under conditions of temperature is 80 DEG C DEG C/humidity is that (humidity resistance) is placed 500 hours, according to following benchmark to foaming in adhesive phase and breaking under conditions of 90%RH Split and carry out observing and evaluating.Foam and occur under condensing hypodynamic occasion, break at stress and alleviate not enough occasion Lower generation.
(foaming)
AA: have no foaming completely.
BB: foaming area is less than overall 5%.
CC: foaming area is overall more than 5%.
(fracture)
AA: have no fracture completely.
BB: area of fracture is less than overall 5%.
CC: area of fracture is overall more than 5%.
[table 2]
In the compositions of comparative example 2, owing to employing (methyl) acrylic copolymer and gel that the degree of branching is 0.59 It is the highest that mark is designed to 57 mass %, and the therefore bending evaluation poor (more than 5.0mm) after 24 hours, although it addition, durable Foaming is not observed in property evaluation, but there occurs to rupture in many places.
In the compositions of comparative example 3, owing to employing (methyl) acrylic copolymer and gel that the degree of branching is 0.59 Mark is designed as 0 mass %, therefore there occurs a large amount of foaming in durability evaluation.
In the compositions of comparative example 1, although employing (methyl) acrylic copolymer that the degree of branching is 0.54, but due to It is the highest that gel fraction is designed to 65 mass %, and unsatisfactory (more than 5.0mm) is evaluated in the bending after 24 hours, it addition, Although not observing foaming in durability evaluation, but there occurs to rupture in many places.
And in the compositions of embodiment, owing to employing the structure having from (methyl) acrylic compounds macromonomer (methyl) acrylic copolymer below 0.55 of unit and the degree of branching and gel fraction design below 30 mass %, Therefore high (below 3.5mm) is evaluated in bending after 24 hours, it addition, foam in durability evaluation and the generation ruptured is also can In the range of permission.

Claims (10)

1. a polaroid adhesive composition, this polaroid adhesive composition contains (A) by the carbon number comprising alkyl It it is (methyl) alkyl acrylate of 4～the 18 and copolymer composition copolymerization of polymerism macromonomer obtains and utilizes gel to ooze The degree of branching that chromatography/multi-angle laser light scattering detector (GPC-MALS) measures thoroughly (methyl) acrylic acid below 0.55 Analog copolymer,
The gel fraction of the binding agent formed by described compositions is below 30 mass %.
2. polaroid adhesive composition as claimed in claim 1, it is characterised in that described (methyl) acrylic copolymer Thing (A) be by described (methyl) alkyl acrylate and polymerism macromonomer, the most also with the monomer of polar functionalities Copolymerization and the copolymer that obtains.
3. adhesive composition as claimed in claim 1 or 2, it is characterised in that the list of the polar functionalities in described copolymerization The consumption of body in the copolymer composition of 100 mass % below 10 mass %.
4. the polaroid adhesive composition as according to any one of claims 1 to 3, 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.
5. the polaroid adhesive composition as according to any one of Claims 1 to 4, it is characterised in that hand over possibly together with (B) Connection agent.
6. polaroid adhesive composition as claimed in claim 5, it is characterised in that described cross-linking agent (B) is selected from different At least one in cyanate esters (B1), metallo-chelate (B2) and epoxide (B3).
7. the polaroid adhesive composition as described in claim 5 or 6, it is characterised in that the content of described cross-linking agent (B) Relative to (methyl) acrylic copolymer (A) described in 100 mass parts below 5 mass parts.
8. a polaroid adhesive phase, it is characterised in that by the polaroid according to any one of claim 1～7 with viscous Mixture composite is formed, and gel fraction is below 30 mass %.
9. a polaroid bonding sheet, it is characterised in that there is the adhesive phase described in claim 8.
10. the polaroid of a band adhesive phase, it is characterised in that have at least one party's of polaroid and described polaroid Adhesive phase described in claim 8 on face.
CN201580014225.5A 2014-03-18 2015-02-20 Polaroid adhesive composition, adhesive phase, bonding sheet and the polaroid of band adhesive phase Pending CN106164718A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101120070A (en) * 2005-02-16 2008-02-06 日本合成化学工业株式会社 Resin composition, adhesive for optical member, and method for producing adhesive for optical member
CN102119349A (en) * 2008-08-11 2011-07-06 住友化学株式会社 Optical film with adhesive and optical laminate using same
TW201132722A (en) * 2010-01-26 2011-10-01 Nitto Denko Corp Adhesive optical film and image display device
CN102618183A (en) * 2011-01-25 2012-08-01 住友化学株式会社 Adhesive sheet and optical film and optical laminating body having the adhesive sheet
JP2013082772A (en) * 2011-10-06 2013-05-09 Nitto Denko Corp Optical adhesive, adhesive layer, optical film, and image display device
CN103261350A (en) * 2010-12-13 2013-08-21 日东电工株式会社 Adhesive composition for optical films, adhesive layer for optical films, adhesive optical film and image display device

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2603494B2 (en) * 1988-01-29 1997-04-23 日東電工株式会社 Acrylic pressure-sensitive adhesive
JPH0782542A (en) * 1993-09-09 1995-03-28 Sekisui Chem Co Ltd Pressure-sensitive adhesive for polarizing plate or phase plate
JP3557429B2 (en) * 1995-02-06 2004-08-25 綜研化学株式会社 Pressure sensitive adhesive for liquid crystal element and liquid crystal element
JPH1046124A (en) * 1996-08-01 1998-02-17 Nippon Synthetic Chem Ind Co Ltd:The Self-adhesive composition
JPH10183085A (en) * 1996-10-22 1998-07-07 Sekisui Chem Co Ltd Self-adhesive composition and self-adhesive article
JPH10140122A (en) * 1996-11-14 1998-05-26 Nippon Synthetic Chem Ind Co Ltd:The Self-adhesive composition
JP4521522B2 (en) * 2004-11-08 2010-08-11 綜研化学株式会社 Optical member and manufacturing method thereof
JP3916638B2 (en) 2004-12-02 2007-05-16 日東電工株式会社 Adhesive optical film and image display device
KR100932888B1 (en) * 2006-07-21 2009-12-21 주식회사 엘지화학 Optically compensated acrylic pressure sensitive adhesive composition, polarizing plate and liquid crystal display device comprising the same
JP5770413B2 (en) 2008-12-25 2015-08-26 チェイル インダストリーズ インコーポレイテッド Adhesive composition and optical member using the same
JP2010185016A (en) * 2009-02-12 2010-08-26 Nippon Shokubai Co Ltd Solvent type repeelable adhesive composition and repeelable adhesive product
JP5679641B2 (en) * 2009-06-26 2015-03-04 日東電工株式会社 Adhesive tape
JP5496583B2 (en) * 2009-09-02 2014-05-21 株式会社日本触媒 Solvent-type re-peeling pressure-sensitive adhesive composition and re-peeling pressure-sensitive adhesive product
JP2014145054A (en) * 2013-01-30 2014-08-14 Sekisui Chem Co Ltd Adhesive sheet for optical use and optical laminate

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101120070A (en) * 2005-02-16 2008-02-06 日本合成化学工业株式会社 Resin composition, adhesive for optical member, and method for producing adhesive for optical member
CN102119349A (en) * 2008-08-11 2011-07-06 住友化学株式会社 Optical film with adhesive and optical laminate using same
TW201132722A (en) * 2010-01-26 2011-10-01 Nitto Denko Corp Adhesive optical film and image display device
CN103261350A (en) * 2010-12-13 2013-08-21 日东电工株式会社 Adhesive composition for optical films, adhesive layer for optical films, adhesive optical film and image display device
CN102618183A (en) * 2011-01-25 2012-08-01 住友化学株式会社 Adhesive sheet and optical film and optical laminating body having the adhesive sheet
JP2013082772A (en) * 2011-10-06 2013-05-09 Nitto Denko Corp Optical adhesive, adhesive layer, optical film, and image display device

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110997320A (en) * 2017-08-10 2020-04-10 综研化学株式会社 Laminate and touch panel
CN111742023A (en) * 2018-03-27 2020-10-02 综研化学株式会社 Adhesive tape
CN111045128A (en) * 2018-10-11 2020-04-21 住友化学株式会社 Optical laminate and display device
CN111196910A (en) * 2018-11-16 2020-05-26 东洋油墨Sc控股株式会社 Adhesive sheet, laminate, and display
CN114621710A (en) * 2020-12-10 2022-06-14 安佐化学有限公司 Adhesive for invisible car cover and preparation method and application thereof
CN115109524A (en) * 2021-03-18 2022-09-27 安佐化学有限公司 Photocuring adhesive for invisible car cover and preparation method and application thereof

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