CN106103623A - Polarizer adhesive composition, bonding sheet and the polarizer with adhesive phase - Google Patents
Polarizer adhesive composition, bonding sheet and the polarizer with adhesive phase Download PDFInfo
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- CN106103623A CN106103623A CN201580013854.6A CN201580013854A CN106103623A CN 106103623 A CN106103623 A CN 106103623A CN 201580013854 A CN201580013854 A CN 201580013854A CN 106103623 A CN106103623 A CN 106103623A
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- polarizer
- methyl
- adhesive composition
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- adhesive phase
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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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(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
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
-
- 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
- G02F1/133528—Polarisers
-
- 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
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Nonlinear Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
The present invention provides a kind of warpage (bending) that can suppress liquid crystal cell and can form the polarizer adhesive composition of adhesive phase of excellent in te pins of durability.Polarizer adhesive composition is characterised by, 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, (B1) isocyanate compound and (B2) metallo-chelate by the monomer component copolymerization of (methyl) alkyl acrylate that the carbon number comprising alkyl is 4~18 and carboxyl group-containing monomer containing (A).
Description
Technical field
The present invention relates to polarizer adhesive composition.
Background technology
Liquid crystal cell has liquid crystal layer by the structure clamped by 2 pieces of substrates (such as glass plate), and polarizer is via adhesive
Layer adheres to the surface of described substrate.Polarizer lacks dimensionally stable due to easy thermal contraction under hot and humid thermal environment
Property, warpage can occur at liquid crystal cell.In recent years, as the slimming of liquid crystal cell (for example constitutes the substrate of liquid crystal cell
Slimming) and the slimming of polarizer, the warpage of the liquid crystal cell under hot and humid thermal environment becomes all the more problem.Liquid crystal
The reason that structure cell warpage can enumerate such as adhesive phase cannot catch up with the thermal contraction (change in size) of polarizer, adhesive phase should
It is low that power alleviates characteristic.
In addition, under hot and humid thermal environment, the interface being susceptible to polarizer with substrate produces bubble or bonding
The unfavorable conditions such as oxidant layer fracture, polarizer stripping.So, it is desirable to polarizer adhesive has high-durability.
The generally means of suppression liquid crystal cell warpage can enumerate the highly-flexible using the change in size coping with polarizer
The method of property adhesive phase.But, the cohesiveness of this adhesive phase is not enough, can produce durability and deteriorate and processability deterioration
Etc. problem.
For example, patent document 1 with the stress relief characteristic caused by the change in size of durability or optics (glass
Warpage), releasable be problem, disclose containing specific (methyl) acrylic polymer and isocyanates crosslinking agent
Pressure sensitive adhesive composition for optical members, pressure sensitive adhesive, patent document 2, discloses as problem with heavy industry fissility (リ ワ Network) or durability
Adhesive composition containing specific copolymer, metal-chelating species curing agent and isocyanates curing agent.
Prior art literature
Patent document
Patent document 1: Japanese Patent Laid-Open 2006-219526 publication
Patent document 2: Japanese Patent Laid-Open 2009-132752 publication
Content of the invention
The technical problem to be solved
The problem of the present invention is to provide a kind of warpage (bending) that can suppress liquid crystal cell and can form durability
The polarizer adhesive composition of excellent adhesive phase, the polarizer use with the adhesive phase being formed by described composition
Bonding sheet and the polarizer with adhesive phase with described adhesive phase.
Solve the technical scheme that technical problem is used
The present inventor conducts in-depth research for solving above-mentioned technical problem.It is found that using the degree of branching specific
In the range of (methyl) acrylic copolymer and by isocyanate compound and metallo-chelate the field being used as crosslinking agent
Under conjunction, the warpage (bending) of liquid crystal cell can be suppressed, and the adhesive phase of excellent in te pins of durability can be formed.Above-mentioned patent literary composition
Offer not mentioned any content with regard to this degree of branching in 1 and 2.That is, the inventors discovered that, by use, there is following specific structure
The polarizer adhesive composition becoming can solve the problem that above-mentioned technical problem, thus completes invention.
For example, following [1]~[9] of the present invention.
[1] a kind of polarizer adhesive composition, it is characterised in that containing (A) is 4~18 by the carbon number comprising alkyl
(methyl) alkyl acrylate and the monomer component copolymerization of carboxyl group-containing monomer obtain and utilize gel permeation chromatography/multi-angle
(methyl) acrylic copolymer below 0.55 for the degree of branching that laser light scattering detector (GPC-MALS) measures and (B1)
Isocyanate compound and (B2) metallo-chelate.
[2] the polarizer adhesive composition described in above-mentioned [1], wherein, described (methyl) acrylic copolymer
(A) it is the copolymer being obtained in the presence of peroxide type polymerization initiator by described copolymerization.
[3] above-mentioned [1] or [2] described in polarizer adhesive composition, wherein, described (methyl) acrylic compounds is common
The weight average molecular weight (Mw) that polymers (A) utilizes gel permeation chromatography (GPC method) to measure is 200,000~1,500,000.
[4] the polarizer adhesive composition described in any one of above-mentioned [1]~[3], wherein, described (methyl) third
The degree of branching that olefin(e) acid analog copolymer (A) utilizes GPC-MALS to measure is 0.10~0.54.
[5] the polarizer adhesive composition described in any one of above-mentioned [1]~[4], wherein, described (methyl) third
Olefin(e) acid analog copolymer (A) be also with carboxyl group-containing monomer beyond the copolymer that obtains of the monomer copolymerization of polar functionalities.
[6] the polarizer adhesive composition described in any one of above-mentioned [1]~[5], wherein, containing of peroxide
Amount relative to (methyl) acrylic copolymers (A) of 100 mass parts below 0.1 mass parts.
[7] the polarizer adhesive composition described in any one of above-mentioned [1]~[6], wherein, by described polarizer
Gel fraction with the adhesive of adhesive composition formation is 20~70 mass %.
[8] a kind of polarizer bonding sheet, it is characterised in that have by described in any one of above-mentioned [1]~[7] is inclined
The adhesive phase that the piece adhesive composition that shakes is formed.
[9] a kind of polarizer with adhesive phase, it is characterised in that there is polarizer and at described polarizer at least
The adhesive phase being formed with adhesive composition by the polarizer described in any one of above-mentioned [1]~[7] on the face of one side.
The effect of invention
Utilize the present invention, it is possible to provide a kind of warpage (bending) that can suppress liquid crystal cell and excellent in te pins of durability can be formed
Adhesive phase polarizer adhesive composition, have the adhesive phase being formed by above-mentioned composition polarizer bonding
Piece and the polarizer with adhesive phase with above-mentioned adhesive phase.
Detailed description of the invention
Below, to the polarizer adhesive composition of the present invention, polarizer bonding sheet and inclined with adhesive phase
The piece that shakes illustrates.Hereinafter, the polarizer adhesive composition of the present invention is also referred to as " adhesive composition ", this
Bright polarizer bonding sheet is also referred to as " bonding sheet ".
[polarizer adhesive composition]
The polarizer adhesive composition of the present invention contains (methyl) acrylic copolymer (A), isocyanates chemical combination
Thing (B1) and metallo-chelate (B2).Above-mentioned adhesive composition as required also can be containing selected from silane coupler (C), anti-quiet
At least one in electricity agent (D) and organic solvent (E).
Hereinafter also isocyanate compound (B1) and metallo-chelate (B2) are referred to as " crosslinking agent (B) ".This
In bright, by by (methyl) acrylic copolymer (A) and these crosslinking agents and with and crosslinking forms adhesive phase.
[(methyl) acrylic copolymer (A)]
(methyl) acrylic copolymer (A) is by (methyl) alkyl acrylate that the carbon number comprising alkyl is 4~18
The copolymer that monomer component copolymerization with carboxyl group-containing monomer obtains.As the monomer component of copolymer (A), other also can enumerate and contain
The monomer of the polar functionalities beyond carboxylic monomer, other monomers in addition.
Acrylic acid and methacrylic acid are referred to as and are denoted as " (methyl) acrylic acid " by this specification.In addition, by polymer
Included in the construction unit coming from certain monomer a be denoted as " monomer a unit.”
(methyl) acrylic copolymer (A) utilizes gel permeation chromatography/multi-angle laser light scattering detector (GPC-
MALS) degree of branching measuring 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.In addition, in branched shaped polymer, be polymerized under the little occasion of degree of branching numerical value
The branch of thing molecule is many, is shown as having high side chain, and under the big occasion of degree of branching numerical value, the branch of polymer molecule is few, is shown as
There is low side chain.
The degree of branching (methyl) acrylic copolymer (A) within the above range has characteristics that (1) at room temperature
Because of a large amount of generation that interweave produced by the mutual side chain of polymer molecule, even if its result is polymer molecular weight and adhesive phase
Gel fraction is designed to low, and the coherency of polymer is also able to maintain that, obtains adhesion characteristic, processes adhesive phase punching press etc.
Property, the deformation of adhesive phase and the excellent adhesive phase of keeping property such as extrusion is few;(2) polymer under high temperature (for example: 60 DEG C)
The mutual above-mentioned interlaced sections of molecule relaxes, and therefore adhesive phase presents excellent flexibility (curved in the warpage of polarizer
Bent) suppression aspect is excellent, simultaneously because the above-mentioned intertexture of part residual and present excellent durability.
With regard to above-mentioned (1) and (2), in the present invention, a part for crosslinking agent uses metallo-chelate (B2), utilizes
Coordinate bond between (methyl) acrylic copolymer (A)/metallo-chelate (B2) forms crosslinking (quasi-crosslink (Japanese: doubtful
Frame)).Therefore, when above-mentioned room temperature, described crosslinking is maintained, and polymer plays coherency, and described in when above-mentioned high temperature
Crosslinked part releasing, adhesive phase presents more excellent flexibility.
Warpage with regard to polarizer is suppressed this point, thus it is speculated that caused by being due to the fact that.With at such as polarizer/viscous
The such structure of mixture layer/clung body use glass plate illustrate as a example by the occasion of clung body.Polarizer and glass
The respective percent thermal shrinkage of plate is different, and the percent thermal shrinkage (change in size) of polarizer 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 polarizer, it is impossible to alleviates
Stress at adhesive phase, stress concentrates on glass plate, and therefore warpage occurs on a glass.And use the adhesive of the present invention
The adhesive phase that composition is formed contains high branched-chain polymer and uses metallo-chelate in a part for crosslinking agent, because of
The part releasing of the lax and above-mentioned crosslinking of a part for this above-mentioned intertexture under hot and humid thermal environment, so adhesive
Layer can catch up with the change in size of polarizer, so stress will not be produced, stress is not centered on glass plate.In addition, polarizer is also
Shrink without anisotropically uniform heat, the birefringence of polarizer will not be induced.As described above, in the present invention, adhesive
Layer can absorb alleviation stress with the change in size of polarizer, (negative thus without applying excessive stress to glass plate
Lotus), 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 piece.Even if particularly the thickness at the glass plate of the liquid crystal cell constituting slimming is little to about 0.1~1.0mm
Occasion under, be also applied for the laminating purposes of this substrate and polarizer.
" (methyl) alkyl acrylate "
As (methyl) alkyl acrylate, (methyl) alkyl acrylate that the carbon number of alkyl can be used to be 4~18
(CH2=CR1-COOR2;R1For hydrogen atom or methyl, R2Alkyl for carbon number is 4~18), wherein, the carbon number of abovementioned alkyl enters one
Step is preferably 4~12.
As (methyl) alkyl acrylate that the carbon number of alkyl is 4~18, the such as positive fourth of (methyl) acrylic acid can be enumerated
Ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate,
(methyl) heptylacrylate, (methyl) 2-EHA, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer,
(methyl) acrylic acid nonyl ester, (methyl) decyl acrylate, (methyl) acrylic acid undecyl ester, (methyl) lauryl base
Ester, (methyl) octadecyl acrylate, (methyl) acrylic acid isooctadecane base ester.These materials can be used alone a kind, it is possible to
Use two or more.
In 100 mass % of the monomer component forming (methyl) acrylic copolymer (A), the carbon number of alkyl is 4~18
The total amount of (methyl) alkyl acrylate from the viewpoint of presenting good bonding force and durability, preferably 99.8~
20 mass %, more preferably 99.5~30 mass %, be still more preferably 99~50 mass %.
As the monomer component of (methyl) acrylic copolymer (A), (methyl) that the carbon number of alkyl can be used to be 1~3
Alkyl acrylate (CH2=CR3-COOR4;R3For hydrogen atom or methyl, R4Alkyl for carbon number is 1~3).
As (methyl) alkyl acrylate that the carbon number of alkyl is 1~3, can enumerate such as (methyl) methyl acrylate,
(methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate.These materials can be used alone a kind,
It is used as two or more.
The carbon number of alkyl be the consumption of (methyl) alkyl acrylate of 1~3 from the viewpoint of stress relief characteristic,
In the monomer component of 100 mass % preferably below 60 mass %, further preferably below 50 mass %, still more preferably
Below 40 mass %.
" carboxyl group-containing monomer "
As carboxyl group-containing monomer, can enumerate for example (methyl) β-acryloxypropionic acid, (methyl) acrylic acid 5-carboxylic pentyl ester,
(methyl) third containing carboxyl such as succinic acid list (methyl) acryloyl-oxy ethyl ester, single (methyl) acrylic acid ω-carboxyl pla-pcl
Olefin(e) acid ester;Acrylic acid, methacrylic acid, itaconic acid, butenoic acid, fumaric acid, maleic acid.
Carboxyl group-containing monomer in this specification also includes the monomer of the anhydride group being condensed containing 2 carboxyl dehydration,
The such as carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride can be enumerated.
Carboxyl group-containing monomer can be used alone a kind, it is possible to use two or more.
This carboxyl contained in carboxyl group-containing monomer is handed over as with isocyanate compound (B1) or metallo-chelate (B2)
The cross-linking functional group of connection plays a role.The consumption of carboxyl group-containing monomer in the monomer component of 100 mass % be preferably 0.01~
15 mass %, more preferably 0.05~10 mass %, be still more preferably 0.1~5 mass %.For example, (methyl) third
The acid number of olefin(e) acid analog copolymer (A) is preferably 0.1~117mgKOH/g, more preferably 0.4~78mmKOH/g.
If the consumption of carboxyl group-containing monomer is below above-mentioned higher limit, then by (methyl) acrylic copolymer (A) and friendship
The crosslink density that connection agent (B) is formed will not become too high, can obtain the adhesive phase of stress relief excellent.If containing carboxylic
The consumption of base monomer more than above-mentioned lower limit, then can be effectively formed cross-linked structure, is had suitably strong at normal temperatures
The adhesive phase of degree.
" monomer of polar functionalities "
As the monomer of polar functionalities, can enumerate beyond such as hydroxyl monomer, carboxyl group-containing monomer containing acid-based monomers,
Emulsion stability, amide-containing monomer, the monomer of nitrogenous system heterocycle, cyano-containing monomer.As the monomer of polar functionalities, preferably
Use has the list of the polar group (cross-linking functional group) that the cross-linking functional group can being had reacts with crosslinking agent (B)
Body.
(methyl) acrylic copolymer (A) preferably by with carboxyl group-containing monomer, simultaneously also with this monomer beyond contain
The copolymer that the monomer copolymerization of polar group obtains.Wherein, from the viewpoint improving the base material adaptation with blooming such as polarizer
Consider, preferably while using carboxyl group-containing monomer, also use 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.
This hydroxyl contained in hydroxyl monomer is as the isocyanates contained with isocyanate compound (B1)
Base crosslinked cross-linking functional group play a role.The consumption of hydroxyl monomer in the monomer component of 100 mass % be preferably 0~
15 mass %, more preferably 0.05~10 mass %, be still more preferably 0.1~7 mass %.If hydroxyl monomer
Consumption below above-mentioned higher limit, then formed by (methyl) acrylic copolymer (A) and isocyanate compound (B1)
Crosslink density will not become too high, can obtain the adhesive phase of stress relief excellent.If the consumption of hydroxyl monomer
More than above-mentioned lower limit, then can be effectively formed cross-linked structure, be there is the adhesive phase of suitable intensity at normal temperatures.
As the acidic group in this specification, such as phosphate, sulfate can be enumerated.As phosphorous acid-based monomers, can enumerate
Side chain has (methyl) acrylic monomer of phosphate, as sulfur-bearing acid-based monomers, can enumerate and there is on side chain sulphur
(methyl) acrylic monomer of acidic group.
As emulsion stability, such as (methyl) acrylate, (methyl) acrylic acid diethyl can be enumerated
(methyl) acrylate containing amino such as base amino ethyl ester.As amide-containing monomer, can enumerate such as (methyl) acrylamide,
N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-propyl group (methyl) acrylamide, N-hexyl (methyl) third
Acrylamide.As the monomer of nitrogenous system heterocycle, such as pyrrolidones, acryloyl morpholine, caprolactam can be enumerated.As
Cyano-containing monomer, can enumerate such as cyano group (methyl) acrylate, (methyl) acrylonitrile.
The monomer of polar functionalities can be used alone a kind, it is possible to use two or more.
" other monomers "
The monomer component forming (methyl) acrylic copolymer (A) is not damaging (methyl) acrylic copolymer (A)
Physical property in the range of can be containing such as (methyl) alkyl acrylate epoxide alkyl ester, single many alkylene glycols of (methyl) alkyl acrylate epoxide
Ester (ア Le U キ シ Port リ ア Le キ レ Application グ リ U Le モ ノ (メ タ) ア Network リ レ ト), contain ester ring type group or aromatic ring
Other (methyl) acrylate such as (methyl) acrylate.
As (methyl) alkyl acrylate epoxide alkyl ester, such as (methyl) methoxyethyl methyl esters, (methyl) third can be enumerated
Olefin(e) acid 2-methoxy acrylate, (methyl) acrylic acid 2-ethoxy ethyl ester, (methyl) acrylic acid 3-methoxyl group propyl ester, (methyl) propylene
Acid 3-ethyoxyl propyl ester, (methyl) acrylic acid 4-methoxybutyl, (methyl) acrylic acid 4-Ethoxybutyl.
As list (methyl) alkyl acrylate epoxide many alkylene glycols ester, for example single (methyl) methoxyethyl two can be enumerated
Glycol ester, list (methyl) methoxyethyl DPG ester, single (methyl) ethioxy triglycol ester, single (first
Base) ethioxy binaryglycol ester, singly (methyl) methoxyethyl triglycol ester.
As (methyl) acrylate containing ester ring type group or aromatic ring, such as (methyl) acrylate can be enumerated
Ester, (methyl) benzyl acrylate, (methyl) phenyl acrylate.
In above-mentioned copolymerization, total consumption of other (methyl) acrylate above-mentioned preferably exists in the monomer component of 100 mass %
Below 60 mass %, further preferably below 40 mass %.
In addition, in the range of not damaging the physical property of (methyl) acrylic copolymer (A), it is possible to use such as benzene second
Alkene, methyl styrene, dimethyl styrene, trimethyl styrene, propylstyrene, butylstyrene, hexyl benzene ethene, heptyl
The ring-alkylated styrenes such as styrene and octyl styrene, fluorobenzene ethene, chlorostyrene, bromstyrol, Dowspray 9, iodobenzene second
The styrene monomers such as alkene, nitrostyrolene, acetylbenzene ethene and methoxy styrene;The copolymerizable lists such as vinyl acetate
Body.
In above-mentioned copolymerization, total consumption of above-mentioned co-polymerized monomer in the monomer component of 100 mass % preferably in 40 matter
Amount below %, further preferably below 20 mass %.
Other monomers can be used alone a kind, it is possible to use two or more.
" manufacturing condition of (methyl) acrylic copolymer (A) "
(methyl) acrylic copolymer (A) preferably passes through above-mentioned common in the presence of peroxide type polymerization initiator
Copolymer obtained by poly-.That is, by using peroxide type polymerization initiator as polymerization initiator, have and obtain the degree of branching
The tendency of copolymer within the above range.
(methyl) acrylic copolymer (A) may utilize such as solution polymerization process, mass polymerization, emulsion polymerization, hangs
The known so far polymerizations such as floating polymerization manufacture, wherein preferred solution polymerization process.Specifically, it is by polymer solvent and list
Body becomes to be distributed in reaction vessel, adds polymerization initiator under the inert gas atmospheres such as nitrogen, and reaction starts temperature and is set as
Usual 40~100 DEG C, preferably 50~80 DEG C, make reaction system maintain at a temperature of usual 50~90 DEG C, preferably 70~90 DEG C
React 4~20 hours.
As peroxide type polymerization initiator, can enumerate for example:
Two (peroxidating 2-ter /-butylisopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-two (peroxidating uncle
Butyl) the dialkyl group peroxidating such as hexane, tert-butyl cumyl peroxide, two tertiary hexyl peroxide, di-tert-butyl peroxide
(for example: the compound representing with R-O-O-R, the R in formula is separately the substituted alkyl of alkyl or aryl to species;With R-
The compound that O-O-A-O-O-R represents, the R in formula is separately the substituted alkyl of alkyl or aryl, and A is the hydrocarbon of divalent
Base);
Diisobutyl peroxide, two (3,5,5-trimethyl acetyl base) peroxide, dilauroyl peroxide, peroxidating
Dibenzoyl, benzoyl (3-methyl benzoyl) peroxide, two (3-methyl benzoyl) peroxide, two (4-first
Base benzoyl) diacyl peroxide class (for example: the compound representing with R-COO-OCO-R, the R in formula such as peroxide
It is separately alkyl or aryl);
Peroxy dicarbonate di-n-propyl ester, di-isopropyl peroxydicarbonate, peroxy dicarbonate two (4-t-butylcyclohexyl
Base) ester, peroxy dicarbonate two (2-ethylhexyl) peroxy dicarbonate such as ester, peroxide-butyl carbonate (for example:
The compound representing with R-OCO-O-O-COO-R, the R in formula is separately alkyl or cycloalkyl);
The withered ester of peroxidating neodecanoic acid, peroxidating neodecanoic acid 1,1,3,3-tetramethyl butyl ester, the tertiary own ester of peroxidating neodecanoic acid, mistake
The oxidation neodecanoic acid tert-butyl ester, the new heptanoic acid tert-butyl ester of peroxidating, the tertiary own ester of peroxidating neopentanoic acid, tert-Butyl peroxypivalate, mistake
Oxidation-2 ethyl hexanoic acid 1,1,3,3-tetramethyl butyl ester, 2,5-dimethyl-2,5-two (peroxidating 2-ethyl hexyl acyl group) hexane,
The tertiary own ester of peroxidating 2 ethyl hexanoic acid, the peroxidating 2 ethyl hexanoic acid tert-butyl ester, the peroxidating 3,5,5 Trimethylhexanoic acid tert-butyl ester, mistake
The oxidation laurate tert-butyl ester, the tertiary own ester of perbenzoic acid, 2,5-dimethyl-2,5-two (benzoyl peroxide base) hexane, mistake
The peroxyesters such as the acetic oxide tert-butyl ester, peroxidating 3-methylbenzoate, peroxidized t-butyl perbenzoate (for example:
With R1-O-O-CO-R2The compound representing, the R in formula1For the substituted alkyl of alkyl or aryl, R2For alkyl, aryl or aryl
Substituted alkyl;The compound representing with R-CO-O-O-A-O-O-CO-R, the R in formula is separately alkyl or aryl, A
Alkyl for divalent);
The tertiary own ester of isopropyl peroxide list carbonic acid, isopropyl peroxide list t-butyl carbonate, peroxidating-2-ethylhexyl list
(for example: the compound representing with R-O-O-COO-R, the R in formula is separately for the peroxidating monocarbonate classes such as t-butyl carbonate
For alkyl).
In peroxide type polymerization initiator, owing to (methyl) acrylic copolymer of high side chain can be obtained, thus
Preferably peroxyesters, the peroxide type polymerization initiator further preferably representing with following formula (1).
[formula 1]
In formula (1), RA~RFIt is separately hydrogen atom, alkyl or aryl, owing to the copolymerization of high side chain can be obtained
Thing, thus alkyl, phenyl that preferred carbon number is 1~10, further preferred carbon number is the alkyl of 1~8, still more preferably carbon number
Being the alkyl of 1~4, particularly preferred carbon number is the alkyl of 1~2.
With in the peroxide type polymerization initiator that formula (1) represents, preferably tert-Butyl peroxypivalate, peroxidating new penta
The tertiary own ester of acid, new peroxide tert-butyl caprate, the new heptanoic acid tert-butyl ester of peroxidating, peroxide-2-ethyl hexanoic acid tert-butyl, peroxidating
The withered ester of neodecanoic acid, owing to can obtain the copolymer of high side chain, thus particularly preferred tert-Butyl peroxypivalate, peroxidating are new
The tertiary own ester of valeric acid, new peroxide tert-butyl caprate, the new heptanoic acid tert-butyl ester of peroxidating, peroxide-2-ethyl hexanoic acid tert-butyl.
Peroxide type polymerization initiator can be used alone a kind, it is possible to use two or more.In addition, be also not limited in polymerization
In repeatedly add peroxide type polymerization initiator.
As polymerization initiator, as long as the degree of branching is within the above range, peroxide type initiators can also used
Use azo-initiator simultaneously.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-dimethyl-penten
Nitrile), 2,2 '-azo two (2-methylbutyronitrile), 1,1 '-azo two (hexamethylene-1-nitrile), 2-(carbamoyl azo) isobutyronitrile,
2-phenylazo-4-methoxyl group-2,4-methyl pentane nitrile, two acidified 2,2 '-azos two (2-amidine propane), 2,2 '-azo
Two (N, N '-dimethyleneisobutylamidine), 2,2 '-azo two [2-methyl-N-(2-ethoxy)-propionamide], 2,2 '-azo two
(isobutyramide) dihydrate, 4,4 '-azo two (4-cyanopentanoic acid), 2,2 '-azo two (2-cyano group propyl alcohol), dimethyl-2,
The azo-compounds such as 2 '-azo two (2 Methylpropionic acid ester), 2,2 '-azo two [2-methyl-N-(2-ethoxy) propionamide].This
A little polymerization initiators can be used alone a kind, it is possible to use two or more.
Relative to the monomer component of formation (methyl) acrylic copolymer (A) of 100 mass parts, with usual 0.001~5
Mass parts, the amount of preferably 0.005~3 mass parts use peroxide type polymerization initiator.In addition, azo-initiator is preferably not
Use, its consumption relative to the peroxide type polymerization initiator of 100 mass parts preferably below 0.5 mass parts, excellent further
It is selected in below 0.2 mass parts, be still more preferably 0 mass parts.But, for the purpose of reducing the monomer reacting later half middle remaining
It is then used for not limiting.In addition, in above-mentioned polymerisation, it is also possible to suitably add and add polymerization initiator, chain tra nsfer
Agent, monomer component, polymer solvent.
As for the polymer solvent in polymerisation in solution, such as benzene,toluene,xylene etc. can be enumerated aromatic hydrocarbon;Just
The aliphatic hydrocarbons such as pentane, n-hexane, normal heptane, normal octane;The ester ring type hydrocarbon such as pentamethylene, hexamethylene, cycloheptane, cyclooctane
Class;Diethyl ether, diisopropyl ether, 1,2-dimethoxy-ethane, butyl oxide, oxolane, dioxane (dioxane), methyl phenyl ethers anisole, benzene
The ethers such as ether, diphenyl ether;The halogenated hydrocarbons such as chloroform, carbon tetrachloride, 1,2-dichloroethanes, chlorobenzene;Ethyl acetate, acetic acid third
The esters such as ester, butyl acetate, methyl propionate;The ketones such as acetone, MEK, diethyl ketone, methylisobutylketone, cyclohexanone;N, N-bis-
The amide-types such as NMF, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE;The nitrile such as acetonitrile, benzonitrile;Diformazan is sub-
The sulfoxide type such as sulfone, sulfolane.These polymer solvents can be used alone a kind, it is possible to use two or more.
In the adhesive composition of the present invention, cause as polymerization when manufacturing (methyl) acrylic copolymer (A)
The available following formula of the reacted survival rate (%) of the peroxide type polymerization initiator elapsed time t that agent is preferably used is tried to achieve.
Survival rate (%)=exp (-kdT) × 100 (%)
In formula, kdFor thermal decomposition rate constant, with Arrhenius formula kd=A × exp (-Δ E/RT) represents, wherein A
For frequency factor, Δ E is the activation energy of polymerization initiator in pyrolysis, and R is gas constant (8.314J/ mole of K), T
For absolute temperature (K);T is the reaction time.
Can use in such as Japan Oil Co (Japan Oil Co) organic peroxide catalogue (the 10th edition) described
Numerical value obtain frequency factor (A) and the activation energy (Δ E) of above-mentioned peroxide type polymerization initiator.For example, peroxidating new penta
The Δ of tert-butyl acrylate E=119.1kJ/ mole, A=6.93 × 1017Hour-1, the Δ E=of the tertiary own ester of peroxidating neopentanoic acid
118.5kJ/ mole, A=6.45 × 1017Hour-1, Δ E=105.3kJ/ mole of the withered ester of peroxidating neodecanoic acid, A=3.94 ×
1016Hour-1。
So, owing to the k at given temperature can be calculatedd, it is thus possible to calculate at given temperature through out-of-date according to above formula
Between the survival rate (%) of reacted peroxide type polymerization initiator of t.Therefore, it is possible to used in by above-mentioned copolymerization
Amount × the survival rate (%) of peroxide type polymerization initiator calculates peroxide type polymerization contained in adhesive composition
The remaining quantity of initiator.
" physical property of (methyl) acrylic copolymer (A) and content "
(methyl) acrylic copolymer (A) utilizes the weight average molecular weight (Mw) that GPC method measures with polystyrene conversion value
Meter is 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.
Make Mw also have high side chain within the above range, thus can moderately be interweaved between copolymer (A) chain, adhesive phase
Durability or processability will not deteriorate.Particularly when Mw is more than 400,000, then can obtain the high adhesive phase of coherency.
(methyl) acrylic copolymer (A) utilizes the molecular weight distribution (Mw/Mn) that GPC method measures generally below 50,
Preferably below 30, further preferably below 20.
The glass transition temperature (Tg) of (methyl) acrylic copolymer (A) can be by the monomer for example constituting this polymer
Unit and content ratio thereof utilize Fox formula to calculate.For example, it is possible to according to the glass transition temperature tried to achieve by Fox formula
(Tg) condition reaching usually-70~0 DEG C, preferably-60~-30 DEG C synthesizes (methyl) acrylic copolymer (A).Logical
Cross use and there is (methyl) acrylic copolymer (A) of such glass transition temperature (Tg), can obtain under normal temperature viscous
The excellent adhesive composition of conjunction property.
Fox formula: 1/Tg=(W1/Tg1)+(W2/Tg2)+…+(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 homopolymers that each monomer is constituted, W1、W2、……、WmFor deriving from construction unit above-mentioned of each monomer
Weight fraction in copolymer (A).
The glass transition temperature of the homopolymers being made up of each monomer in above-mentioned Fox formula can use such as " polymer hand
Volume " numerical value described in (Polymer Handbook) fourth edition (Wiley-Interscience 1999).
The content of (methyl) acrylic copolymer (A) in the adhesive composition of the present invention being somebody's turn to do in 100 mass %
Composition is usually in the solid constituent in addition to organic solvent (E) 50~99.99 mass %, more preferably 60~
99.95 mass %, particularly preferably 80~99.90 mass %.If the content of (methyl) acrylic copolymer (A) is above-mentioned
In the range of, then can obtain the balance of the performance as adhesive, and adhesion characteristic is excellent.
[isocyanate compound (B1)]
As isocyanate compound (B1), generally use isocyanation esterification more than 2 for the isocyanates radix in 1 molecule
Compound.Make (methyl) acrylic copolymer (A) crosslinked by utilizing isocyanate compound (B1), crosslinked can be formed
(network polymers).
The isocyanates radix of isocyanate compound (B1) generally more than 2, preferably 2~8, more preferably 3
~6.If isocyanates radix is within the above range, then at (methyl) acrylic copolymer (A) and isocyanate compound
(B1) on this aspect of cross-linking reaction efficiency and keep adhesive this aspect of flexibility on be preferred.
As the diisocyanate cpd that isocyanates radix in 1 molecule is 2, for example aliphatic two isocyanic acids can be enumerated
Ester, alicyclic diisocyanate, aromatic diisocyanates.As aliphatic vulcabond, can enumerate ethylidene diisocyanate,
Tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl isophthalic acid, 5-pentane two is different
Cyanate, 3-methyl isophthalic acid, the carbon number such as 5-pentane diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate is 4
The aliphatic vulcabond of~30.As alicyclic diisocyanate, IPDI, cyclopenta two can be enumerated different
Cyanate, cyclohexyl diisocyanate, the sub-XDI of hydrogenation, HTDI, hydrogenation hexichol first
The carbon numbers such as alkane diisocyanate, the hydrogenation sub-XDI of tetramethyl are the alicyclic diisocyanate of 7~30.As
Aromatic diisocyanates, can enumerate for example phenylene vulcabond, toluene di-isocyanate(TDI), sub-XDI,
The carbon numbers such as naphthalene diisocyanate, diphenyl ether diisocyanate, '-diphenylmethane diisocyanate, diphenylpropane diisocyanate are 8
The aromatic diisocyanates of~30
As isocyanate compound more than 3 for the isocyanates radix in 1 molecule, such as aromatics polyisocyanate can be enumerated
Ester, aliphatic polymeric isocyanate, alicyclic polymeric isocyanate.Specifically, can enumerate 2,4,6-triisocyanate toluene, 1,3,5-
Triisocyanate benzene, 4,4', 4 "-triphenylmethane triisocyanates.
In addition, as isocyanate compound (B1), can enumerate such as isocyanates radix 2 or more than 3 above-mentioned different
The polymer (such as dimer or tripolymer, biuret body, isocyanuric acid ester body) of cyanate esters, derivative are (for example many
The addition reaction product of diisocyanate cpd more than unit's alcohol and 2 molecules), polymer.As many in said derivative
Unit's alcohol, low molecular weight polyols can enumerate the alcohol of more than the such as ternarys such as trimethylolpropane, glycerine, pentaerythrite;High score
Sub-weight polyalcohol can enumerate such as PPG, PEPA, acrylic polyol, polybutadiene polyol, poly-isoamyl
Diene polyol.
Such isocyanate compound can enumerate the tripolymer of such as '-diphenylmethane diisocyanate, polymethylene polyphenyl
The biuret body of base PIC, hexamethylene diisocyanate or toluene di-isocyanate(TDI) or isocyanuric acid ester body, three hydroxyls
Methylpropane and product (the such as toluene di-isocyanate(TDI) or Asia of toluene di-isocyanate(TDI) or sub-XDI
Three molecule addition products of XDI), the product (example of trimethylolpropane and hexamethylene diisocyanate
The three molecule addition products such as hexamethylene diisocyanate), polyethers PIC, polyester PIC.
In isocyanate compound (B1), can carry on good curing performance and this aspect of light leak performance, preferably trihydroxy methyl third
(chemical society (is ground) by Soken Chemical & Engineering Co., Ltd. for alkane and the product of toluene di-isocyanate(TDI) or sub-XDI
The L-45 manufacturing, the TD-75 etc. that Soken Chemical & Engineering Co., Ltd. manufactures), hexamethylene diisocyanate or toluene di-isocyanate(TDI)
Isocyanuric acid ester body (TSE-100 that Asahi Chemical Industry Co., Ltd (Asahi Chemical Industry Gong She) manufactures, Japanese polyurethane strain formula meeting
Society (Japan Port リ ウ レ タ Application society) manufacture 2050 etc.).
Isocyanate compound (B1) can be used alone a kind, it is possible to use two or more.
[metallo-chelate (B2)]
In the present invention, a part of crosslinking agent (B) uses metallo-chelate (B2).Metallo-chelate (B2) is by joining
Position key makes (methyl) acrylic copolymer (A) crosslinked.Therefore, during high temperature above-mentioned crosslinking a part releasing, adhesive phase in
Reveal more excellent flexibility.
As metallo-chelate (B2), can enumerate such as alkoxide, acetylacetone,2,4-pentanedione, ethyl acetoacetate etc. to aluminium, iron, copper,
The compound of the polyvalent metal coordination such as zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium.Wherein, particularly preferred aluminium chelate compound (is combined
Grind the M-12AT etc. that KCC manufactures).Specifically, aluminium isopropoxide, secondary butyric acid aluminium, acetoacetate aluminium ethide can be enumerated
Diisopropyl ester, tri ethylacetoacetate aluminium, praseodynium aluminium.
Metallo-chelate (B2) can be used alone a kind, it is possible to use two or more.
In the adhesive composition of the present invention, the total content phase of isocyanate compound (B1) and metallo-chelate (B2)
0.01~5 mass parts is usually for (methyl) acrylic copolymers (A) of 100 mass parts, more preferably 0.05~
2.5 mass parts, are still more preferably 0.1~1 mass parts.If this content is within the above range, then durable in easy acquirement
It is preferred on property and this aspect of the balance of stress relief characteristic.
In the adhesive composition of the present invention, the content of metallo-chelate (B2) is relative to the isocyanates of 100 mass parts
Compound (B1) is usually 10~1000 mass parts, more preferably 50~600 mass parts, be still more preferably 100~
400 mass parts.If this content is within the above range, then in amount of bow suppression and improve the base material with blooming such as polarizer
It is preferred on this aspect of adaptation.
[silane coupler (C)]
Preferably the polarizer adhesive composition of the present invention is possibly together with silane coupler (C).Silane coupler (C) makes to glue
The clung body strong bond such as mixture layer and glass plate, contribute to preventing the stripping under high humid and warm environment.
As silane coupler (C), such as vinyltrimethoxy silane, VTES, first can be enumerated
The silane coupler containing polymerism unsaturated group such as base acryloxypropyl trimethoxy silane;3-glycidoxy third
Base trimethoxy silane, 3-glycidoxypropyl group triethoxysilane, 3-glycidoxypropyl dimethoxysilane,
3-glycidoxypropyl diethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane etc. contain epoxy
The silane coupler of base;3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330,
The silane coupler containing amino such as N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane;3-chloro propyl group three
The silane coupler containing halogen such as methoxy silane.
The content of the silane coupler (C) in the polarizer adhesive composition of the present invention is relative to 100 mass parts
(methyl) acrylic copolymer (A) generally below 1 mass parts, preferably 0.01~1 mass parts, more preferably 0.05
~0.5 mass parts.If content is within the above range, then has and prevent polarizer under high humid and warm environment from peeling off or hot environment
The tendency that lower silane coupler (C) is oozed out.
[antistatic agent (D)]
Antistatic agent can be used to for example reduce the sheet resistance value of polarizer adhesive composition of the present invention
(D).Antistatic agent (D) can enumerate such as surfactant, ionic compound, electric conductive polymer.
As surfactant, can enumerate such as quaternary ammonium salt, amidoquat salt, pyridine salt, have primary amino radical~
The cationic surface active agent of the cationic groups such as tertiary amino;There are sulphonate-base, sulfuric ester alkali, phosphate alkali etc.
The anionic surfactant of anionic group;Alkyl betaines bases, alkyl imidazole betaines, alkyl amine
Amphoteric surfactant, fatty acid glycerine esters, sorbitan fatty acid ester class, the polyoxy second such as class, amino acid sulfuric acid ester
Allylic alkylation amine, polyoxyethylene alkyl amine fatty acid ester, N-ethoxy-N-2-hydroxyalkyl amine, alkyl diethanolamide class
Deng nonionic surface active agent.
In addition, surfactant also can enumerate the reactive emulsifier with polymerizable group, it be also possible to use and make containing upper
State the polymer types of surfactants obtained by the monomer component molecular weight of surfactant or reactive emulsifier.
Ionic compound is made up of cationic moiety and anionicsite, and at room temperature (23 DEG C/50%RH) are in solid-state
Or any one in liquid.
The cationic moiety constituting ionic compound both can be appointing in mineral-type cation or organic cation
One, it is also possible to be both.Mineral-type cation preferred as alkali ion and alkaline-earth metal ion, further preferred antistatic
The excellent Li of property+、Na+And K+.As organic cation, such as pyridylium, piperidines cation, pyrrolidones can be enumerated
Cationoid, pyrrolin cation, pyrroles's cation, glyoxaline cation, tetrahydropyrimidine cation, dihydro-pyrimidin cation, pyrrole
Azoles cation, pyrazine cation (ピ ラ ゾ リ ニ ウ system カ チ オ Application), tetraalkylammonium cation, trialkylsulfonium cation, four alkane
Base phosphine cation and their derivative.
As long as constitute ionic compound anionicsite can with cationic moiety ionic bonding and form ion
The material of type compound is then not specially limited.Specifically, F can be enumerated-、Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、
PF6 -、SCN-、ClO4 -、NO3 -、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO2)2N-、(F2SO2)2N-、(CF3SO2)3C-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、F(HF)n -、(CN)2N-、C4F9SO3 -、(C2F5SO2)2N-、C3F7COO-(CF3SO2)
(CF3CO)N-.Wherein, the anion containing fluorine atom is preferred because providing the ionic compound of low melting point, particularly preferably
(F2SO2)2N-(CF3SO2)2N-。
Ionic compound preferred bis-trifluoromethylsulfoandimide lithium, double difluoro sulfimide lithium, three (trifyls)
Methane lithium, bis-trifluoromethylsulfoandimide potassium, double difluoro sulfimide potassium, hexafluorophosphoric acid 1-ethylpyridine, hexafluorophosphoric acid 1-butyl
Pyridine, hexafluorophosphoric acid 1-hexyl-4-picoline, hexafluorophosphoric acid 1-octyl group-4-picoline, 1-octyl group-4-picoline two
Fluorine sulfimide, 1-octyl group-4-picoline bis-trifluoromethylsulfoandimide, tetrafluoro boric acid (N, N-diethyl-N-methyl-N-(2-
Methoxy ethyl) ammonium, N, N-diethyl-N-methyl-N-(2-methoxy ethyl) ammonium bis-trifluoromethylsulfoandimide, 1-octylpyridinium
Fluorine thionyl imide (1-オ Network チ Le ピ リ ジ ニ ウ system Off Le オ ロ ス ホ ニ ウ system イ ミ De), 1-octyl group-3-picoline, three
Fluorine thionyl imide (ト リ Off Le オ ロ ス Le ホ ニ ウ system イ ミ De).
As electric conductive polymer, such as polythiophene, polyaniline, polypyrrole and their derivative can be enumerated.
The content of the antistatic agent (D) in the polarizer adhesive composition of the present invention is relative to (the first of 100 mass parts
Base) acrylic copolymer (A) generally below 3 mass parts, preferably 0.01~3 mass parts, more preferably 0.05~
2.5 mass parts.
[organic solvent (E)]
The adhesive composition of the present invention preferably comprises organic solvent (E) to regulate its coating.Organic solvent can
Enumerate the polymer solvent of explanation in (methyl) acrylic copolymer (A) hurdle.For example, can be by containing of obtaining in above-mentioned copolymerization
Have polymer solution and isocyanate compound (B1) and the metal-chelating of (methyl) acrylic copolymer (A) and polymer solvent
Thing (B2) mixing carrys out modulating adhesive composition.In the adhesive composition of the present invention, the content of organic solvent is usually 50~
90 mass %, preferably 60~85 mass %.
In addition, " solid constituent " in this specification refers to have except above-mentioned in composition contained in adhesive composition
Whole compositions beyond machine solvent (E), " solid component concentration " refers to the adhesive relative to 100 mass % for the above-mentioned solid constituent
The ratio of composition.
[peroxide]
(peroxide is crosslinked preferably not to blend the peroxide as crosslinking agent in the adhesive composition of the present invention
Agent).The content of peroxide includes that the peroxide type polymerization being used during the synthesis of (methyl) acrylic copolymer (A) draws
Send out including the remaining quantity of agent, relative to (methyl) acrylic copolymers (A) of 100 mass parts preferably below 0.1 mass parts,
Further preferably below 0.05 mass parts, still more preferably below 0.01 mass parts.By using isocyanates chemical combination
Thing (B1) and metallo-chelate (B2) do not use peroxide crosslinking agent as crosslinking agent, can suppress because of the peroxide of residual
Compound and the deterioration of adhesive phase that causes.
[additive]
The adhesive composition of the present invention is in addition to mentioned component, in the range of not damaging effect of the present invention, also may be used
Containing beyond antioxidant, light stabilizer, preventing metal corrosion agent, tackifier, plasticizer, crosslinking accelerator, above-mentioned (A)
One kind or two or more in (methyl) acrylic polymer and heavy industry remover (Japanese: リ ワ Network).
[modulation of polarizer adhesive composition]
The polarizer adhesive composition of the present invention can be by utilizing known so far method to (methyl) acrylic compounds
Copolymer (A) and isocyanate compound (B1) and metallo-chelate (B2) and other compositions using as desired are carried out
Mixing is modulated.Can enumerate for example obtained containing this polymer when synthesis (methyl) acrylic copolymer (A)
In polymer solution blend isocyanate compound (B1) with metallo-chelate (B2) and use as desired other become
Point.
The gel fraction of the adhesive being formed by the adhesive composition of the present invention is preferably 20~70 mass %, further
It is preferably 24~60 mass %, be still more preferably 30~55 mass %.Above-mentioned gel fraction is for example to remember according to embodiment
The condition carrying is measured the numerical value obtaining to the adhesive being used.
[adhesive phase]
The adhesive phase of the present invention can be obtained by for example carrying out the cross-linking reaction in above-mentioned adhesive composition, specifically
It is can be by making (methyl) acrylic polymer (A) crosslinking with isocyanate compound (B1) and metallo-chelate (B2)
Arrive.
The formation condition of adhesive phase is for example as described below.It is coated on the adhesive composition of the present invention on supporting mass,
Temperature is different because of solvent species, but generally 50~150 DEG C, preferably carry out at 60~100 DEG C usually 1~10 minute,
The drying of preferably 2~7 minutes, to remove solvent, forms film.The thickness of dry coating is usually 5~75 μm, and preferably 10
~50 μm.
Adhesive phase is preferably formed under the following conditions.It is coated on the adhesive composition of the present invention on supporting mass,
After pasting cover layer on the film that formed under these conditions, usual 5~60 DEG C, preferably 15~40 DEG C and usual 30~
Maintenance usual more than 3 days, preferably 7~10 days in the environment of 70%RH, preferably 40~70%RH.If in curing as described above
Under the conditions of carry out crosslinking, then can be efficiently formed crosslinked (network polymers).
As the coating process of adhesive composition, known method can be used, for example, pass through spin-coating method, cutter coating, roller
Coating, stick coating method, scraper coating, die coating method, gravure coating method etc. form the coating drying means of specific thickness.
As supporting mass and cover layer, the such as polyester films such as polyethylene terephthalate (PET) can be enumerated;Poly-second
The plastic foil of the polyolefin films etc. such as alkene, polypropylene, vinyl-vinyl acetate copolymer.
The adhesive phase being formed by the adhesive composition of the present invention is from suppression polarizer distortion, cohesiveness, bonding force, again
From the viewpoint of fissility, gel fraction is preferably 20~70 mass %, more preferably 24~60 mass %, further
It is preferably 30~55 mass %.Owing to (methyl) acrylic copolymer (A) is even if gel fraction also has within the above range
High side chain, thus can moderately be interweaved between the side chain of copolymer (A), durability or the processability of adhesive phase will not
Deteriorate.Particularly when gel fraction is more than 30 mass %, then can obtain the high adhesive phase of coherency.If gel divides
Number exceeds above-mentioned scope, then adhesive phase cannot fully absorb and alleviate by the change in size of polarizer under hot and humid thermal environment
Caused stress.
[polarizer bonding sheet]
The polarizer bonding sheet of the present invention has the adhesive phase being formed by above-mentioned polarizer adhesive composition.Make
For bonding sheet, can enumerate and for example only there is the double-sided adhesive sheet of above-mentioned adhesive phase, there is base material and be formed on base material two sides
Above-mentioned adhesive phase double-sided adhesive sheet, there is base material and the one side of the above-mentioned adhesive phase being formed on the face of base material one side
Bonding sheet and these bonding sheets are pasted with the cover layer through lift-off processing with base material on the face not contacted of adhesive phase
Bonding sheet.
As base material and cover layer, the such as polyester films such as polyethylene terephthalate (PET) can be enumerated;Polyethylene,
The plastic foil of the polyolefin film such as polypropylene, vinyl-vinyl acetate copolymer etc..
The formation condition of the adhesive phase condition described with [adhesive phase] hurdle is identical.
The thickness of adhesive phase is usually 5~75 μm from the viewpoint of maintaining bond properties, preferably 10~50 μm.Base
The thickness of material and cover layer is not particularly limited, but usually 10~125 μm, preferably 25~75 μm.
[with the polarizer of adhesive phase]
The polarizer with adhesive phase of the present invention is characterized by polarizer and at above-mentioned polarizer at least
The adhesive phase being formed by polarizer adhesive composition of the present invention on the face of side.In addition, in this specification, " polarizer "
Use with the implication comprising " polarizing coating ".
Polarizer can use known so far polarizing coating.Can enumerate and for example have by making to be made up of polyvinyl alcohol resin
Film in multilayer containing stretched film and the diaphragm being configured in above-mentioned stretched film obtained from stretching after polarized component
Film.As polyvinyl alcohol resin, such as polyvinyl alcohol, polyvinyl formal, Pioloform, polyvinyl acetal, ethene second can be enumerated
Vinyl acetate copolymer saponified.Polarized component can enumerate such as iodine or dichroic dye.As diaphragm, can enumerate for example
The cellulose membranes such as tri acetyl cellulose, polycarbonate membrane, poly (ether sulfone) film.
The thickness of polarizer is usually 30~250 μm, preferably 50~200 μm.
The method forming adhesive phase on polarizer surface is not particularly limited, and can enumerate use direct stick coating method etc. partially
Shaking makes its method being dried, is had the polarizer bonding sheet of the present invention after being coated with above-mentioned adhesive composition on piece surface
Adhesive phase be transferred to polarizer surface after make its method curing.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 polarizer is usually 5~75 μm in terms of dry film thickness, preferably 10~50 μ
m.As long as in addition, on the face of the adhesive phase at least one party that is formed at polarizer, adhesive phase can be enumerated and is only formed at partially
The shake form on piece one side, adhesive phase is formed at the form on polarizer two sides.
Furthermore it is also possible to be laminated such as protective layer, antiglare layer, phase separation layer, angle of visibility on above-mentioned polarizer to improve layer
Etc. the layer with other functions.
By the polarizer with adhesive phase of the present invention obtaining in the manner described above is arranged on the base of liquid crystal cell
Plate manufactures liquid crystal cell on surface.Here liquid crystal cell has liquid crystal layer by the construction clamped by 2 pieces of substrates.
The substrate with liquid crystal cell can enumerate such as glass plate.The thickness of substrate is usually 0.1~1mm, is preferably
0.15~0.8mm.Especially in the present invention, sticking up of polarizer and substrate can be suppressed by using above-mentioned adhesive composition
Bent.Therefore, though above-mentioned adhesive composition under the little occasion of substrate thickness (for example: below 0.8mm, preferably 0.15~
0.7mm), it is also possible to be suitably used for the laminating of polarizer and substrate.
Embodiment
Carry out more specific description to the present invention below based on embodiment, but the present invention is not limited to these embodiments.With
In the record of lower embodiment etc., if no special instructions, " part " expression " mass parts ".
[GPC and GPC-MALS]
Gel permeation chromatography (GPC method) is used to utilize gel permeation chromatography/multi-angle laser light according to following condition
Weight average molecular weight (Mw) and number-average molecular weight (Mn) to (methyl) acrylic copolymer for the scatter detector (GPC-MALS) is entered
Row measures, and obtains the degree of branching according to following condition.
Determinator: HLC-8320GPC (TOSOH Co., Ltd's (ソ (strain)) production)
The composition of GPC post: following 4 pedestals (all being produced by TOSOH Co., Ltd)
(1) TSKgel HxL-H (guard column)
(2)TSKgel GMHxL
(3)TSKgel GMHxL
(4)TSKgel G2500HxL
Flow velocity: 1.0mL/ minute
Column temperature: 40 DEG C
Sample solution concentration: 1.5% (w/v) (diluting with oxolane)
Mobile phase solvent: oxolane
Detector: DAWN HELEOS (MALS detector)+Optilab rEX (RI detector)
Polystyrene standard conversion (measures the occasion of Mw and Mn)
[synthesis example 1]
98.8 parts of propylene are added in the reaction unit possessing mixer, reflux cooler, thermometer and nitrogen ingress pipe
Acid N-butyl, 1 part of acrylic acid 4-hydroxy butyl ester, 0.2 part of acrylic acid and 100 parts of ethyl acetate solvents, import nitrogen and rise
Temperature is to 80 DEG C.Then, add the tert-Butyl peroxypivalate of 0.1 part, carry out the polymerization of 6 hours in a nitrogen atmosphere in 80 DEG C
Reaction.After reaction terminates, being diluted with ethyl acetate, prepared solid component concentration is the polymer solution of 30 mass %.Institute
The weight average molecular weight (Mw) of (methyl) the acrylic copolymer A obtaining is 700,000, and molecular weight distribution (Mw/Mn) is 7.1, branched
Degree is 0.51, and acid number is 1.6mgKOH/g.
[synthesis example 2~12]
Except the monomer component used in polymerisation and polymerization initiator are changed to content described in table 1 with
Outward, synthesizing according to the mode identical with synthesis example 1, prepared solid component concentration is the polymer solution of 30 mass %.Knot
Fruit is shown in table 1.
[table 1]
[embodiment 1]
(1) modulation of adhesive composition
By (methyl) acrylic polymer solution (solid component concentration is 30 mass %) being obtained by synthesis example 1 and
(methyl) acrylic polymer contained relative in this solution of 100 parts (solid constituent amounts) is 0.05 part, and (solid becomes
Component) as isocyanate compound Soken Chemical & Engineering Co., Ltd. manufacture " TD-75 " (solid constituent is 75 mass %,
Ethyl acetate solution), 0.14 part (solid constituent amount) as metallo-chelate Soken Chemical & Engineering Co., Ltd. manufacture " M-
12AT " (solid constituent is 10 mass %, toluene, acetylacetone,2,4-pentanedione solution), the SHIN-ETSU HANTOTAI's chemistry work as silane coupler of 0.2 part
" KBM-403 " (solid constituent is 100%) and the conduct of 1 part that industry Co., Ltd. (SHIN-ETSU HANTOTAI's chemistry work (strain)) manufactures are prevented
" AS-804 " (solid constituent is 100%) that Di-ichi Kogyo Seiyaku Co., Ltd.'s (the first work (strain)) of electrostatic agent manufactures
Mix, obtain adhesive composition.
(2) making of bonding sheet
After froth breaking, with scraper in the upper coating of polyethylene terephthalate film (PET film) through lift-off processing by upper
State the adhesive composition that (1) obtains, be dried 3 minutes at 90 DEG C, form the film that desciccator diaphragm thickness is 20 μm.At film
Fit through the PET film of lift-off processing on the reverse side of the sticking veneer of above-mentioned PET film further, quiet under 23 DEG C/50%RH environment
Put 7 days after curing, obtain having by the bonding sheet of the adhesive phase that the thickness clamped by 2 pieces of PET film is 20 μm.
(3) making of the polarizer with adhesive phase
After froth breaking, with scraper in the upper coating of polyethylene terephthalate film (PET film) through lift-off processing by upper
State the adhesive composition that (1) obtains, be dried 3 minutes at 90 DEG C, form the piece with the film that desciccator diaphragm thickness is 20 μm.
Make sheet above and polarizer (thickness: 110 μm, Rotating fields: tri acetyl cellulose film/polyvinyl alcohol film/tri acetyl cellulose
Film) fit in the way of making above-mentioned film connect with polarizer, stand after within 7 days, curing under conditions of 23 DEG C/50%RH,
Obtain having the polarizer with adhesive phase of PET film and adhesive phase that thickness is 20 μm and polarizer.
[embodiment 2~11, comparative example 1~2]
Except (methyl) acrylic polymer solution in embodiment 1 being changed to by gathering that synthesis example 2~12 obtains
Polymer solution and by blend composition be changed to content described in table 2 beyond, obtain according to the same manner as in Example 1
The polarizer of adhesive composition, bonding sheet and band adhesive phase.
[evaluation]
[gel fraction]
The adhesive gathering about 0.1g from the bonding sheet being obtained by embodiment comparative example is placed in sample bottle, adds
The ethyl acetate of 30mL after shaking 4 hours, was carried out by the content to this sample bottle for the 200 stainless steel wire nettings of purpose
Filter, measures dry weight carry out the drying of 2 hours to the residue on wire netting after at 100 DEG C.Following formula is utilized to obtain bonding
The gel fraction of agent.
Gel fraction (%)=(dry weight/adhesive gathers weight) × 100 (%)
[creep value]
By the polarizer with adhesive phase that obtained by embodiment comparative example (by PET film/adhesive phase/polarizer
The duplexer constituting) cut into the size of wide 10mm × long 100mm, peel off the above-mentioned PET film through lift-off processing, through alkali
So that above-mentioned adhesive phase connects with above-mentioned glass plate and fitting area reaches the mode of 10mm × 10mm on the glass plate processing
Fit, obtain evaluation bonding processing polarizer test film.
To evaluation bonding processing polarizer test film carry out autoclave process (50 DEG C, 5 atmospheric pressure), 23 DEG C/
24 hours are stood under 50%RH atmosphere.Then above-mentioned test film is set to fixing card in the chamber BOX of micro-creep analyzer
The a length of 15mm of disc portion.With tensile load, the stretching time of 1000 seconds of 800g, along be parallel to this polarizer with above-mentioned
Above-mentioned evaluation in above-mentioned test film is bonded by the composition surface between glass and the direction for the length direction of above-mentioned polarizer
Processing polarizer is pullled, and measures the deviation distance (μm) of the above-mentioned glass plate of above-mentioned test film and the fitting part of polarizer
As creep value.
[mensuration of bonding force]
By the polarizer with adhesive phase that obtained by embodiment comparative example (by PET film/adhesive phase/polarizer structure
The duplexer becoming) cut into the size of 70mm × 25mm, prepare test film.PET film is peeled off from test film, will with laminating roll
The duplexer being made up of adhesive phase/polarizer is bonded to the glass plate of 2mm with glass plate in the way of making adhesive phase connect
One side on.Obtained duplexer is being adjusted to the autoclave of 50 DEG C/5 atmospheric pressure holding 20 minutes.Then, 23
DEG C/50%RH environment under place after 1 hour, along relative to the direction that glass pane surface is 90 DEG C with the speed of 300mm/ minute
Polarizer end is pullled by degree, measures bonding force (peel strength).
[bending (warpage)]
By the polarizer with adhesive phase that obtained by embodiment comparative example (by PET film/adhesive phase/polarizer structure
The duplexer becoming) cut into the size in 35mm × 400mm (tensile axis direction), prepare test film.PET film is shelled from test film
From the duplexer being made up of adhesive phase/polarizer being bonded in the way of making adhesive phase connect with glass plate with laminating roll
To the one side of the glass plate of 0.7mm, 40mm × 410mm.Obtained duplexer is being placed under 23 DEG C/50%RH environment
After 24 hours, keep 72 hours in the stove of 60 DEG C.It is fixed on unilateral end on metope perpendicular to the ground, use ruler
The amount tilting opposite side extremities is measured.Implement to measure after just taking out from stove and after 24 hours.
[endurancing]
By the polarizer with adhesive phase that obtained by embodiment comparative example (by PET film/adhesive phase/polarizer structure
The duplexer becoming) cut into the size of 150mm × 250mm, prepare test film.PET film is peeled off from test film, uses laminating roll
The duplexer being made up of adhesive phase/polarizer is bonded in the way of making adhesive phase connect with glass plate the glass of 2mm
On the one side of plate.Obtained duplexer is adjusted to the autoclave of 50 DEG C/5 atmospheric pressure holding 20 minutes, prepares examination
Test plate.Make 2 pieces of identical breadboards.By above-mentioned breadboard, under conditions of temperature is 80 DEG C, (heat resistance) or temperature are 60
DEG C/humidity under conditions of be 90%RH (humidity resistance) place 500 hours, according to following benchmark, foaming and fracture are entered
Row is observed and evaluates.Foaming occurs under the hypodynamic occasion of cohesion, breaks at and occurs under the not enough occasion of stress relief.
(foaming)
AA: have no foaming completely.
BB: foaming area is less than overall 1%.
CC: foaming area overall more than 1% less than 5%.
DD: foaming area is overall more than 5%.
(fracture)
AA: have no fracture completely.
BB: area of fracture is less than overall 1%.
CC: area of fracture overall more than 1% less than 5%.
DD: area of fracture is overall more than 5%.
[table 2]
In table 2, the amount of peroxide type polymerization initiator calculates by the following method.By above-mentioned survival rate formula: exp (-
kdT) × 100 (%) calculate, for example in embodiment 1, and kd=A × exp (-Δ E/RT), A=6.93 × 1017Hour-1, Δ E=
119.1kJ/ mole, R=8.314J/ mole of K, T=353K, reaction time t=6 hour, used in above-mentioned copolymerization
The amount × survival rate (%) of peroxide type polymerization initiator calculate 5 × 10-3Mass parts.
Comparative example 1 and 2 employs (methyl) acrylic copolymer that the degree of branching is 0.59.Therefore, at gel fraction
In high system (comparative example 1), bending evaluation difference (more than 5.0mm) after 24 hours, although in addition, in durability evaluation not
Observe foaming, but there occurs to rupture in many places.And in the low system (comparative example 2) of gel fraction, there occurs a large amount of foaming.
Owing to the copolymer in comparative example 1 is linear polymer, presenting of cohesiveness only relies upon crosslinking agent and copolymerization
The bonding of Wu Zhong functional group.Therefore, gel fraction must be set to height to maintain cohesiveness.But, gel fraction is high
When, due to stress relief characteristic step-down in the system of comparative example 1, therefore observe the deterioration of bending and durability (resistance to fracture).
And in an embodiment, owing to employing the degree of branching (methyl) acrylic copolymer below 0.55, and by different
Cyanate esters and metallo-chelate are simultaneously used as crosslinking agent, and the therefore bending after 24 hours is evaluated high (below 3.0mm), resistance to
In long property evaluation, the generation of foaming and fracture is also within the scope of can allow for.
Produce a large amount of side chain by making polymer, increase being bonded between crosslinking agent and functional group in copolymer, utilize and prop up
Change part there occurs intertexture, even if therefore also presenting cohesiveness under low gel fraction.Accordingly, because it is slow to interweave under high temperature
Solve, thus bendability is good and also shows the tendency that durability improves.
Claims (9)
1. a polarizer adhesive composition, it is characterised in that contain:
(A) the monomer component copolymerization by (methyl) alkyl acrylate that the carbon number comprising alkyl is 4~18 and carboxyl group-containing monomer
Obtain and utilize the degree of branching that gel permeation chromatography/multi-angle laser light scattering detector (GPC-MALS) measures 0.55
(methyl) acrylic copolymer below,
(B1) isocyanate compound and
(B2) metallo-chelate.
2. polarizer adhesive composition as claimed in claim 1, it is characterised in that described (methyl) acrylic copolymer
Thing (A) is the copolymer being obtained by described copolymerization in the presence of peroxide type polymerization initiator.
3. polarizer adhesive composition as claimed in claim 1 or 2, it is characterised in that described (methyl) acrylic compounds
The weight average molecular weight (Mw) that copolymer (A) utilizes gel permeation chromatography (GPC method) to measure is 200,000~1,500,000.
4. the polarizer adhesive composition as according to any one of claims 1 to 3, it is characterised in that described (methyl)
The degree of branching that acrylic copolymer (A) utilizes GPC-MALS to measure is 0.10~0.54.
5. the polarizer adhesive composition as according to any one of Claims 1 to 4, it is characterised in that described (methyl)
Acrylic copolymer (A) be also with carboxyl group-containing monomer beyond the copolymer that obtains of the monomer copolymerization of polar functionalities.
6. the polarizer adhesive composition as according to any one of Claims 1 to 5, it is characterised in that peroxide
Content relative to (methyl) acrylic copolymers (A) of 100 mass parts below 0.1 mass parts.
7. the polarizer adhesive composition as according to any one of claim 1~6, it is characterised in that by described polarization
The gel fraction of the adhesive that piece adhesive composition is formed is 20~70 mass %.
8. a polarizer bonding sheet, it is characterised in that have and used by the polarizer according to any one of claim 1~7
The adhesive phase that adhesive composition is formed.
9. the polarizer with adhesive phase, it is characterised in that there is polarizer and at least one party at described polarizer
The adhesive phase being formed by the adhesive composition of the polarizer according to any one of claim 1~7 on face.
Applications Claiming Priority (3)
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JP2014-055116 | 2014-03-18 | ||
JP2014055116 | 2014-03-18 | ||
PCT/JP2015/054775 WO2015141380A1 (en) | 2014-03-18 | 2015-02-20 | Adhesive composition for polarizing plate, adhesive sheet and polarizing plate with adhesive layer |
Publications (1)
Publication Number | Publication Date |
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CN106103623A true CN106103623A (en) | 2016-11-09 |
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CN201580013854.6A Pending CN106103623A (en) | 2014-03-18 | 2015-02-20 | Polarizer adhesive composition, bonding sheet and the polarizer with adhesive phase |
Country Status (4)
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JP (1) | JP6530376B2 (en) |
KR (1) | KR20160134679A (en) |
CN (1) | CN106103623A (en) |
WO (1) | WO2015141380A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108165189A (en) * | 2016-12-07 | 2018-06-15 | 琳得科株式会社 | Adherence composition, battery adhesive sheet and lithium ion battery |
CN110662813A (en) * | 2017-07-25 | 2020-01-07 | 大塚化学株式会社 | Adhesive composition and adhesive film |
CN115287022A (en) * | 2022-08-24 | 2022-11-04 | 苏州赛伍应用技术股份有限公司 | Environment-friendly high-solid low-viscosity adhesive as well as preparation method and application thereof |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6880647B2 (en) * | 2016-10-20 | 2021-06-02 | 東洋インキScホールディングス株式会社 | Acrylic resin composition, acrylic film, decorative film and decorative molded body |
JP6879414B1 (en) | 2020-06-30 | 2021-06-02 | 東洋インキScホールディングス株式会社 | Adhesives and adhesive sheets |
WO2022064796A1 (en) * | 2020-09-25 | 2022-03-31 | 綜研化学株式会社 | Adhesive layer-equipped irregularly shaped polarizing plate |
KR102612236B1 (en) * | 2020-12-11 | 2023-12-08 | 삼성에스디아이 주식회사 | Adhesive composition for polarizing plate, polarizing plate comprising the same and optical display apparatus comprising the same |
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JP2006077139A (en) * | 2004-09-10 | 2006-03-23 | Toyo Ink Mfg Co Ltd | Removable pressure sensitive adhesive and removable pressure sensitive adhesive sheet |
JP4883749B2 (en) | 2005-02-08 | 2012-02-22 | 日東電工株式会社 | Optical member pressure-sensitive adhesive composition, optical member pressure-sensitive adhesive layer and production method thereof, optical member with pressure-sensitive adhesive, and image display device |
WO2007029298A1 (en) * | 2005-09-02 | 2007-03-15 | Toyo Ink Mfg. Co., Ltd. | Pressure-sensitive adhesive agent and method for production thereof, and pressure-sensitive adhesive sheet |
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JP5554735B2 (en) * | 2010-08-24 | 2014-07-23 | 綜研化学株式会社 | Adhesive for polarizing plate and polarizing plate with adhesive using the same |
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2015
- 2015-02-20 JP JP2016508612A patent/JP6530376B2/en active Active
- 2015-02-20 KR KR1020167025364A patent/KR20160134679A/en unknown
- 2015-02-20 WO PCT/JP2015/054775 patent/WO2015141380A1/en active Application Filing
- 2015-02-20 CN CN201580013854.6A patent/CN106103623A/en active Pending
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108165189A (en) * | 2016-12-07 | 2018-06-15 | 琳得科株式会社 | Adherence composition, battery adhesive sheet and lithium ion battery |
CN108165189B (en) * | 2016-12-07 | 2021-11-09 | 琳得科株式会社 | Adhesive composition, adhesive sheet for battery, and lithium ion battery |
CN110662813A (en) * | 2017-07-25 | 2020-01-07 | 大塚化学株式会社 | Adhesive composition and adhesive film |
CN110662813B (en) * | 2017-07-25 | 2021-09-07 | 大塚化学株式会社 | Adhesive composition and adhesive film |
CN115287022A (en) * | 2022-08-24 | 2022-11-04 | 苏州赛伍应用技术股份有限公司 | Environment-friendly high-solid low-viscosity adhesive as well as preparation method and application thereof |
CN115287022B (en) * | 2022-08-24 | 2023-12-15 | 苏州赛伍应用技术股份有限公司 | Environment-friendly high-solid low-adhesive and preparation method and application thereof |
Also Published As
Publication number | Publication date |
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WO2015141380A1 (en) | 2015-09-24 |
JP6530376B2 (en) | 2019-06-12 |
JPWO2015141380A1 (en) | 2017-04-06 |
KR20160134679A (en) | 2016-11-23 |
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