CN104379694A - Adhesive composition for polarizing plates, polarizing plate with adhesive, and display device - Google Patents

Adhesive composition for polarizing plates, polarizing plate with adhesive, and display device Download PDF

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Publication number
CN104379694A
CN104379694A CN201380029297.8A CN201380029297A CN104379694A CN 104379694 A CN104379694 A CN 104379694A CN 201380029297 A CN201380029297 A CN 201380029297A CN 104379694 A CN104379694 A CN 104379694A
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acrylic copolymer
methyl
polarization plates
structural unit
monomer
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CN104379694B (en
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川口太郎
中野宏人
安田直人
西田雅树
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TOKYO
Nippon Carbide Industries Co Inc
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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
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/066—Copolymers with monomers not covered by C08L33/06 containing -OH groups
    • 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
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • 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
    • G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals

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

Abstract

The present invention provides an adhesive composition for polarizing plates, which contains: an acrylic copolymer (A) that has a weight average molecular weight of from 300,000 to 700,000 (inclusive) and contains a constituent unit derived from an alkyl (meth)acrylate and a constituent unit derived from a monomer having a carboxy group; an acrylic copolymer (B) that has a weight average molecular weight of from 1,000,000 to 2,000,000 (inclusive) and contains a constituent unit derived from an alkyl (meth)acrylate, a constituent unit derived from a monomer having a carboxy group and a constituent unit derived from a monomer having a hydroxyl group; and 20 parts by mass or less of an isocyanate-based crosslinking agent relative to 100 parts by mass of the total amount of the acrylic copolymer (A) and the acrylic copolymer (B). This adhesive composition for polarizing plates is configured such that the glass transition temperature of the acrylic copolymer (A) is not less than the glass transition temperature of the acrylic copolymer (B).

Description

Polarization plates adhesive composite, with the polarization plates of caking agent and display unit
Technical field
The present invention relates to polarization plates adhesive composite, with the polarization plates of caking agent and display unit.
Background technology
In recent years, as the display unit of display image, the device of various display mode such as liquid crystal indicator, organic electroluminescent is popularized widely.Wherein, liquid crystal indicator generally has the structure that the liquid crystal composition being oriented in prescribed direction is held on liquid crystal cells between 2 supporting substrates such as glass, fits with the blooming such as polarization plates, phase retardation film, brightness enhancement film.Blooming lamination each other, blooming use caking agent when being attached at liquid crystal cells.
Liquid crystal indicator is widely used as display unit such as PC, TV, automobile navigation instruments, such as, uses under the various envrionment conditions such as the envrionment conditions of harshness, the dry environment condition of low humidity that hot and humid amount of moisture is many.Therefore, even if when requiring to possess life-time service, also can not peel off with the sticking part of caking agent laminating (that is, the interface between bond layer and liquid crystal cells or polarizing coating) or not produce at bond layer and rupture and be difficult to produce such high-durability energy such as bubble at bond layer.
In addition, polarization plates has the polarizing coating (polaroid) using PVA etc.When stretched film being used for this polarizing coating, if be exposed in the environment of such as hot and humid lower this harshness, then easily produce along with the dimensional change of shrinking, expand, in polarization plates, produce stress.When stress along with dimensional change is not relaxed by the caking agent be configured between polarization plates and liquid crystal cells, in polarization plates, produce residual stress unevenly.Its result, at surface and the back side of display panel, the position of 2 polarization plates that the mode crossed one another with the tensile axis of polarizing coating configures produces mutually departs from.Therefore, bleach from 4 periphery light leaks of the display part of liquid crystal indicator, produce the inequality being called as so-called " hickie (Bai order け) ".
Occurrence frequency, the emergence pattern of above-mentioned hickie are different according to the size of display panel.From this viewpoint, general small-sized display panel uses softer soft caking agent, and larger display panels uses harder rigid caking agent.If wish is by this rigid adhesive application in small-sized display panel, then the stress along with contraction etc. easily concentrates on limit end, there is the trend that above-mentioned hickie appears in panel periphery significantly.On the other hand, in order to larger display panels purposes manufacture large-sized caking agent time, due to the end of whole caking agent (former anti-) effectively cannot be utilized, become one of reason of yield rate step-down.In addition, due to softness, also there is the trend being easily attached to processing blades and punch press process difference in soft caking agent.
In order to improve above-mentioned hickie, proposing and adding low-molecular weight polymer to relax the caking agent of stress in adhesive composite.Such as, disclose by high-molecular-weight propylene acid based copolymer, weight-average molecular weight be less than 30,000 low molecular weight propylene acid based copolymer and the polarization plates adhesive composite that forms of multi-functional compounds.By having the characteristic of following the dimensional change that polarization plates produces, make the irregular colour of periphery and central part few (for example, referring to patent documentation 1).
In addition, disclose a kind of polarization plates adhesive composite, wherein, weight-average molecular weight be 65 ~ 950,000 (methyl) acrylic copolymer (A) and weight-average molecular weight be 105 ~ 1,350,000 (methyl) acrylic copolymer (B) together contain with the ratio specified and isocyanate compound, make, under hot and humid, there is weather resistance, and hickie suppressed (for example, referring to patent documentation 2).
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 10-279907 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2011-231189 publication
Summary of the invention
But, as above-mentioned technology in the past, disclose the technology in order to prevent the generation of the irregular colour taking hickie as representative from using (methyl) acrylic copolymer varied in size of weight-average molecular weight, but the multiple multipolymer that just only molecular weight used in combination is different, be difficult to the weather resistance maintaining foaming or stripping, fracture etc. well, be also difficult to the generation preventing hickie simultaneously.
Caking agent is from the past just according to purposes, size and carry out the adjustment of the composition of caking agent.On the other hand, for can be applicable to larger display panels purposes and small-sized display panel purposes, and independently can prevent the generation of hickie with size and the caking agent of weather resistance, excellent in workability to be not yet suggested be truth.
The present invention completes based on foregoing.Under above-mentioned condition, need that there is the high-durability not easily producing foaming or stripping etc., and independently suppress the polarization plates adhesive composite of the generation of irregular colour (especially hickie) and the polarization plates with caking agent with size.In addition, the display unit demonstrating the few image of irregular colour is needed.
The present invention reaches based on following opinion.That is,
Think two or more resin varied in size of weight-average molecular weight used in combination time, in two or more resin, the resin that molecular weight is little does not have hydroxyl isopolarity group, the resin-phase ratio of this resin is greater than with the molecular weight with polar group, illustrate by reducing molecular weight and weather resistance downward trend with the reactivity hour of linking agent, but be conceived to the second-order transition temperature of resin, regulate the reactivity with isocyanate-based linking agent by copolymer composition, the weather resistance of caking agent can be reached and prevent the generation of irregular colour.
Concrete method for reaching above-mentioned problem is as follows.
1st the present invention is a kind of polarization plates adhesive composite, it contains: acrylic copolymer A, it comprises from the structural unit of (methyl) alkyl acrylate with from the structural unit of monomer with carboxyl, and weight-average molecular weight is 300000 ~ 700000; Acrylic copolymer B, its comprise from (methyl) alkyl acrylate structural unit, from have carboxyl monomer structural unit and from the structural unit of monomer with hydroxyl, and weight-average molecular weight is 1000000 ~ 2000000; And isocyanate-based linking agent, it is the scope of below 20 mass parts relative to the content of total amount 100 mass parts of the sour based copolymer A of aforesaid propylene and aforesaid propylene acid based copolymer B, and the second-order transition temperature (TgA) of aforesaid propylene acid based copolymer A is more than or equal to the second-order transition temperature (TgB) of aforesaid propylene acid based copolymer B.
2nd the present invention is a kind of polarization plates with caking agent, wherein, and the bond layer that there is polaroid and be formed on above-mentioned polaroid by the polarization plates adhesive composite giving the above-mentioned invention of the 1st.
According to the present invention, provide a kind of and there is the high-durability not easily producing foaming or stripping etc., and independently suppress the polarization plates adhesive composite of the generation of irregular colour (especially hickie) and the polarization plates with caking agent with size.In addition,
According to the present invention, provide a kind of display unit demonstrating the few image of irregular colour.
Embodiment
Below, to polarization plates adhesive composite of the present invention and use its polarization plates with caking agent and display unit to be described in detail.
< polarization plates adhesive composite >
Polarization plates adhesive composite of the present invention uses acrylic copolymer A, acrylic copolymer B and isocyanate-based linking agent to form, described acrylic copolymer A comprises from the structural unit of (methyl) alkyl acrylate with from the structural unit of monomer with carboxyl, and weight-average molecular weight is 300000 ~ 700000; Described acrylic copolymer B comprise from (methyl) alkyl acrylate structural unit, from have carboxyl monomer structural unit and from the structural unit of monomer with hydroxyl, and weight-average molecular weight is 1000000 ~ 2000000.And then, in polarization plates adhesive composite of the present invention, the content of isocyanate-based linking agent is the scope of below 20 mass parts relative to total amount 100 mass parts of the sour based copolymer A of aforesaid propylene and aforesaid propylene acid based copolymer B, and the second-order transition temperature (TgA) of aforesaid propylene acid based copolymer A meets the relation of TgA >=TgB with the second-order transition temperature (TgB) of aforesaid propylene acid based copolymer B.
In addition, polarization plates adhesive composite of the present invention, except acrylic copolymer A and acrylic copolymer B, can comprise other compositions such as linking agent, silane coupling agent, other additive as required further.
The multiple multipolymer that known use molecular weight was different in the past forms the technology of caking agent.But only reduce the molecular weight of a part of multipolymer, although can expect that stress relaxes the effect produced irregular colours such as hickies, weather resistance significantly declines, the generation of foaming or stripping etc. cannot be suppressed.Therefore, in the present invention,
Use the high isocyanate-based linking agent of Polarity comparision as while linking agent using the ratio of regulation, at least make to there is hydroxyl as polar group in the acrylic copolymer B of high molecular side, and the second-order transition temperature (TgA) of the acrylic copolymer A of lower molecular weight side is more than or equal to the second-order transition temperature (TgB) of acrylic copolymer B.Thus, the reaction with the isocyanate-based linking agent of the acrylic copolymer A of lower molecular weight side is promoted.Surge chamber retentivity is given by making acrylic copolymer low molecule quantize, and prevent from, along with the embrittlement of low molecule quantification, independently reaching with the size of size the generation of irregular colour (especially hickie) and the raising of weather resistance that prevent caking agent.
Polarization plates adhesive composite of the present invention is owing to preventing excellence in weather resistance and irregular colour (especially hickie), while the larger display panels (i.e. large-scale display device) of more than 19 inches can be performed well in, also can perform well in being less than the small-sized display panel (i.e. compact display apparatus) of 19 inches (and then, be less than 10 inches).In other words, polarization plates adhesive composite of the present invention is while the caking agent manufacturing larger display panels purposes, and can manufacture the caking agent of small-sized display panel purposes from the end of whole caking agent (former anti-), therefore yield rate improves.Therefore, it is possible to measure according to demand and manufacture the caking agent of size, also there is the advantage without the need to stock, keeping.
Should illustrate, in this specification sheets, (methyl) vinylformic acid refers to acrylic or methacrylic acid, and (methyl) acrylate refers to acrylate or methacrylic ester.
Below each composition is described in detail.
-acrylic copolymer A-
Polarization plates adhesive composite of the present invention contains at least one of acrylic copolymer A, aforesaid propylene acid based copolymer A comprises from the structural unit of (methyl) alkyl acrylate with from the structural unit of monomer with carboxyl, and weight-average molecular weight is 300000 ~ 700000.This acrylic copolymer A at least makes (methyl) alkyl acrylate and has the monomer copolymerization of carboxyl and the multipolymer that obtains, also can be other monomer of further copolymerization and have the multipolymer of the structural unit from this monomer further.
As (methyl) alkyl acrylate forming acrylic copolymer A, such as, (methyl) methyl acrylate can be enumerated, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, positive ten diester of (methyl) vinylformic acid and (methyl) octadecyl acrylate etc.Wherein, from the viewpoint of the cohesive force of easy adjustment caking agent and engaging force, be preferably the alkyl ester of (methyl) vinylformic acid carbonatoms 1 ~ 4, preferably the alkyl ester of vinylformic acid carbonatoms 1 ~ 4, is particularly preferably n-butyl acrylate.
Be preferably 65.0 ~ 99.5 quality % from the ratio in the acrylic copolymer A of the structural unit of (methyl) alkyl acrylate, be more preferably 65.0 ~ 94.5 quality %, be particularly preferably 75.0 ~ 90.0 quality %.(methyl) alkyl acrylate is contained as the principal constituent forming multipolymer, if it contains ratio in above-mentioned scope, then can be adjusted to best Young's modulus, guaranteeing weather resistance, adhesive in be favourable.
The optimal way of the acrylic copolymer A in the present invention is: except containing (methyl) alkyl acrylate as except principal constituent, the monomer that further copolymerization is different from above-mentioned (methyl) alkyl acrylate, this monomer can form homopolymer, and the second-order transition temperature that this homopolymer has is 30 DEG C ~ 90 DEG C with the absolute value of the difference of the second-order transition temperature of the polymkeric substance making above-mentioned (methyl) alkyl acrylate (carbonatoms of preferred alkyl is 1 ~ 4) homopolymerization obtain.This mode can improve second-order transition temperature, namely improves the polarity of resin and improves the reactivity with isocyanate-based linking agent, improving weather resistance further.
Wherein, as the monomer of homopolymer that can form the second-order transition temperature of absolute value in above-mentioned scope with above-mentioned difference, be preferably methyl acrylate, tert-butyl acrylate, acrylate, n-BMA.As particularly preferred acrylic copolymer A, it is the pattern of n-butyl acrylate and methyl acrylate and/or tert-butyl acrylate copolymerization.
Except containing (methyl) alkyl acrylate as except principal constituent, during containing above-mentioned monomer (being preferably methyl acrylate, tert-butyl acrylate) different from it, the ratio of structural unit in acrylic copolymer A from this monomer is preferably 5 ~ 30 quality %, is more preferably 5 ~ 20 quality %.If should containing ratio be in above-mentioned scope, then improve with isocyanate-based linking agent reactive in be favourable.
As the monomer with carboxyl forming acrylic copolymer A, preferably there is (methyl) acrylic monomer of carboxyl.As the example of monomer with carboxyl, vinylformic acid, methacrylic acid, ω-carboxyl-polycaprolactone list (methyl) acrylate etc. can be enumerated.Wherein, when copolyreaction and the reactivity of other monomer high and can reduce unreacted monomer in consider, be preferably vinylformic acid.
The ratio of structural unit in acrylic copolymer A from the monomer with carboxyl is preferably 0.5 ~ 5 quality %, is more preferably 0.5 ~ 3 quality %.If have the monomer of carboxyl containing ratio be in above-mentioned scope, then guaranteeing property working life and can moderately adjust resin's crosslinkage viewpoint consider be favourable.
The weight-average molecular weight of acrylic copolymer A is 300000 ~ 700000.Weight-average molecular weight is that in multiple resins that in above-mentioned scope, expression contains in polarization plates adhesive composite, acrylic copolymer A is the resin of lower molecular weight side.In addition, if the weight-average molecular weight of acrylic copolymer A is less than 300000 and become too small, to be then easily peeling and weather resistance (being especially applied to weather resistance during large size (such as more than 19 inches) purposes) declines.Conversely, if the weight-average molecular weight of acrylic copolymer A is greater than 700000 and becomes excessive, then molecular dimension is close to acrylic copolymer B, and the stress produced by also using with acrylic copolymer A relaxes and diminishes, and cannot suppress the generation of irregular colour (especially hickie).This situation occurs when being especially applied to large size (such as more than 19 inches) purposes significantly.
As the second-order transition temperature (TgA) of acrylic copolymer A, be preferably the scope of-50 DEG C ~-30 DEG C, be more preferably the scope of-48 DEG C ~-40 DEG C.If TgA is more than-50 DEG C, then can at the enterprising Row sum-equal matrix of Young's modulus, weather resistance, hickie are excellent.In addition, if TgA is less than-30 DEG C, then viscosity and excellent in tackiness, suitably laminating can not be damaged terrifically.
As the content in the polarization plates adhesive composite of acrylic copolymer A, suitably can select in the scope meeting the aftermentioned ratio A/B of containing, relative to all solids composition of polarization plates adhesive composite, be preferably the scope of 50 quality % ~ 74 quality %, be more preferably the scope of 54 quality % ~ 69 quality %.If the content of acrylic copolymer A is in above-mentioned scope, then give flexibility to caking agent, relaxed the generation suppressing irregular colour (especially hickie) by stress.
-acrylic copolymer B-
Polarization plates adhesive composite of the present invention contains at least one of acrylic copolymer B, aforesaid propylene acid based copolymer B comprise from (methyl) alkyl acrylate structural unit, from have carboxyl monomer structural unit and from the structural unit of monomer with hydroxyl, and weight-average molecular weight is 1000000 ~ 2000000.This acrylic copolymer B at least makes (methyl) alkyl acrylate, has the monomer of carboxyl and has the monomer copolymerization of hydroxyl and the multipolymer obtained, and also can be other monomer of further copolymerization and have the multipolymer of the structural unit from this monomer further.
As (methyl) alkyl acrylate forming acrylic copolymer B, such as, (methyl) methyl acrylate can be enumerated, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, positive ten diester of (methyl) vinylformic acid and (methyl) octadecyl acrylate etc.Wherein, from the viewpoint of the cohesive force of easy adjustment caking agent and engaging force, be preferably the alkyl ester of (methyl) vinylformic acid carbonatoms 1 ~ 8, be preferably the alkyl ester of vinylformic acid carbonatoms 1 ~ 8, be particularly preferably n-butyl acrylate, tert-butyl acrylate, methyl acrylate, 2-EHA.
The ratio of structural unit in acrylic copolymer B from (methyl) alkyl acrylate is preferably 93 ~ 99.4 quality %, is more preferably 96 ~ 99.4 quality %.(methyl) alkyl acrylate is contained as the principal constituent forming multipolymer, if it contains ratio is in above-mentioned scope, then can be adjusted to best Young's modulus and weather resistance, adhesion properties in favourable.
As the monomer with carboxyl forming acrylic copolymer B, preferably there is (methyl) acrylic monomer of carboxyl.As the example of monomer with carboxyl, vinylformic acid, methacrylic acid, ω-carboxyl-polycaprolactone list (methyl) acrylate etc. can be enumerated.Wherein, when copolyreaction and the reactivity of other monomer high and can reduce unreacted monomer in consider, be preferably vinylformic acid.
The ratio of structural unit in acrylic copolymer B from the monomer with carboxyl is preferably 0.5 ~ 5 quality %, is more preferably 0.5 ~ 3 quality %.If have the monomer of carboxyl containing ratio be in above-mentioned scope, then guaranteeing property working life and can moderately adjust resin's crosslinkage viewpoint consider be favourable.
As the monomer with hydroxyl forming acrylic copolymer B, preferably there is (methyl) acrylic monomer of hydroxyl, be more preferably (methyl) CALCIUM ACRYLATE with hydroxyl.As the example of monomer with hydroxyl, (methyl) vinylformic acid 2-hydroxy methacrylate can be enumerated, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid 3-methyl-3-hydroxybutyl, (methyl) vinylformic acid 1, 3-dimethyl-3-hydroxybutyl, (methyl) vinylformic acid 2, 2, 4-trimethylammonium-3-hydroxyl pentyl ester, the own ester of (methyl) vinylformic acid 2-ethyl-3-hydroxyl, polypropylene glycol list (methyl) acrylate, polyethyleneglycol (methyl) acrylate and poly-(ethylene glycol and 1,2-propylene glycol) single (methyl) acrylate etc.
Wherein, consider in and crosslinking reaction excellence when being set to the composition of the multipolymer comprising gained high at polymerisation reactivity, be preferably (methyl) hydroxyalkyl acrylates, more preferably (methyl) vinylformic acid carbonatoms of alkyl portion is the hydroxyalkyl acrylate of 1 ~ 4, more preferably vinylformic acid 2-hydroxy methacrylate, vinylformic acid 2-hydroxy propyl ester, vinylformic acid 4-hydroxybutyl.
The ratio of structural unit in acrylic copolymer B from the monomer with hydroxyl is preferably 0.1 ~ 2.0 quality %, is more preferably 0.1 ~ 1.0 quality %.If what have the monomer of hydroxyl is in above-mentioned scope containing ratio, then can guarantee the reactivity with isocyanate-based linking agent, to maintaining well, weather resistance is favourable.
The weight-average molecular weight of acrylic copolymer B is 1000000 ~ 2000000.Weight-average molecular weight is that in multiple resins that in above-mentioned scope, expression contains in polarization plates adhesive composite, acrylic copolymer B is the resin of high molecular side.In addition, if the weight-average molecular weight of acrylic copolymer B is less than 1000000 and diminish, be then easily peeling, and weather resistance (being especially applied to weather resistance during large size (such as more than 19 inches) purposes) declines.If the weight-average molecular weight of acrylic copolymer B is greater than 2000000 and become excessive, then and decline by the stress alleviation effects caused by acrylic copolymer A.Therefore, become and be difficult to follow contraction, in caking agent, easily produce fracture or peel off, weather resistance is deteriorated, and cannot suppress the generation of the irregular colour (especially hickie) when being especially applied to small size (such as 10 are less than inch) purposes simultaneously.
As the second-order transition temperature (TgB) of acrylic copolymer B, be preferably the scope of-50 DEG C ~-40 DEG C, be more preferably the scope of-50 DEG C ~-45 DEG C.If TgB is more than-50 DEG C, then can at the enterprising Row sum-equal matrix of Young's modulus, weather resistance, hickie are excellent.In addition, if TgB is less than-40 DEG C, then viscosity and excellent in tackiness, suitably laminating can not be damaged terrifically.
As the content in the polarization plates adhesive composite of acrylic copolymer B, suitably can select in the scope meeting the aftermentioned ratio A/B of containing, relative to all solids composition of polarization plates adhesive composite, be preferably the scope of 17 ~ 37 quality %, be more preferably the scope of 21 ~ 32 quality %.If the content of acrylic copolymer B is in above-mentioned scope, then can keep the ratio of the high molecular weight components in caking agent, weather resistance improves.
In acrylic copolymer A in the present invention and acrylic copolymer B, (methyl) alkyl acrylate forming respective multipolymer, the monomer with carboxyl can be mutually different in acrylic copolymer A and acrylic copolymer B, also can be identical.
In the present invention, the second-order transition temperature (TgA of aforesaid propylene acid based copolymer A; DEG C) with the second-order transition temperature (TgB of aforesaid propylene acid based copolymer B; DEG C) meet the relation of TgA >=TgB.If TgA is less than TgB, then except molecular weight is smaller, due to not enough with the reactivity of isocyanate-based linking agent, easily produce the faults such as foaming or stripping, poor durability.Wherein, from the view point of preventing effectiveness and the further raising weather resistance of irregular colour (especially hickie), as the difference (TgA-TgB of TgA and TgB; DEG C), be preferably the scope of 1 ~ 5 DEG C, be more preferably the scope of 1 ~ 3 DEG C.
In this specification sheets, the second-order transition temperature (Tg) of acrylic copolymer is mole average glass transition temperature obtained by following calculating.Tg in following formula 1, Tg 2, and Tg nbe the second-order transition temperature of composition 1, composition 2 and ingredient n homopolymer separately, be converted into absolute temperature (゜ K) and calculate.M 1, m 2, and m nit is the molar fraction of respective composition.
[calculating formula of second-order transition temperature (Tg)]
[several 1]
1 Tg = m 1 Tg 1 + m 2 Tg 2 + . . . . . . . + m n Tg n
Should illustrate, " second-order transition temperature (Tg) of homopolymer " mentioned here is applied to L.E.Nielsen (L.E. ニ ー Le セ Application) work, and little wild wood a surname controls the second-order transition temperature translating the monomer recorded in " character (high-molecular mechanical Quality) of high molecular mechanics " 11st ~ 35 pages.
In addition, the weight-average molecular weight (MwA) of aforesaid propylene acid based copolymer A is preferably less than 0.5 relative to the ratio (MwA/MwB) of the weight-average molecular weight (MwB) of the sour based copolymer B of aforesaid propylene.MwA/MwB is less than 0.5 preventing effectiveness that can improve irregular colour (especially hickie) further.Wherein, MwA/MwB, due to reason similar to the above, is more preferably less than 0.35.
As the aforesaid propylene acid based copolymer A relative to aforesaid propylene acid based copolymer B containing ratio (A/B), be preferably the scope of 60/40 ~ 80/20 in quality criteria.If containing ratio A/B be more than the ratio of lower limit, then the ratio of the acrylic copolymer A of molecular weight is more, the improvement effect of the irregular colour (especially hickie) therefore caused by counter stress mitigation is high, and the second-order transition temperature of acrylic copolymer A and B meets the relation of TgA >=TgB, thus the worry that the many caused weather resistance of the ratio of acrylic copolymer A decline is also few.In addition, be below the ratio of the upper limit by making containing ratio A/B, can keep low molecule quantize caused by stress alleviation effects and the balance of maintenance of the weather resistance caused by relative quantity of acrylic copolymer B maintaining high molecular side.
Wherein, as containing ratio A/B, due to above-mentioned same reason, the scope of 65/35 ~ 75/25 is more preferably.
In above-mentioned, as the array mode of the acrylic copolymer A in the present invention and acrylic copolymer B, preferably following (1) the 1st mode ~ (3) the 3rd mode.That is,
(1) the 1st mode:
Acrylic copolymer A comprise the alkyl ester from (methyl) vinylformic acid carbonatoms 1 ~ 4 structural unit, from (methyl) acrylic acid structural unit and the structural unit from " can be formed and have and make the alkyl ester homopolymerization of above-mentioned (methyl) vinylformic acid carbonatoms 1 ~ 4 and the absolute value of the difference of the second-order transition temperature of the polymkeric substance obtained is the monomer of the homopolymer of the second-order transition temperature of 30 ~ 90 DEG C "
Acrylic copolymer B comprise the alkyl ester from (methyl) vinylformic acid carbonatoms 1 ~ 8 structural unit, from (methyl) acrylic acid structural unit and the structural unit from (methyl) hydroxyalkyl acrylates.
(2) the 2nd modes:
Acrylic copolymer A comprises from the structural unit of n-butyl acrylate, from the structural unit of (methyl) acrylic monomer and the structural unit from methyl acrylate and/or tert-butyl acrylate with carboxyl,
Acrylic copolymer B comprises from the structural unit of n-butyl acrylate, from the structural unit of (methyl) acrylic monomer and the structural unit from (methyl) hydroxyalkyl acrylates with carboxyl.
(3) the 3rd modes:
Acrylic copolymer A comprises from the structural unit of n-butyl acrylate, from (methyl) acrylic acid structural unit and methyl acrylate and/or tert-butyl acrylate,
Acrylic copolymer B comprises from the structural unit of n-butyl acrylate, from (methyl) acrylic acid structural unit and the structural unit from (methyl) hydroxyalkyl acrylates.
The polymerization process of the acrylic copolymer in the present invention has no particular limits, can the method such as applying soln polymerization, letex polymerization, suspension polymerization.Fairly simple and can to carry out at short notice from the viewpoint for the treatment of process, be preferably solution polymerization.
Solution polymerization is generally the chain-transfer agent loading the organic solvent of regulation, monomer, polymerization starter and use as required in polymerization tank, in nitrogen gas stream or under the backflow of organic solvent, stirs reacting by heating a few hours.As above-mentioned polymerization starter, have no particular limits, such as, can use Azo.
The weight-average molecular weight (Mw) of acrylic copolymer can be adjusted to required molecular weight by the kind of adjustment temperature of reaction, time, quantity of solvent, catalyzer or amount.
In this specification sheets, the weight-average molecular weight (Mw) of acrylic copolymer is the value measured by following method.That is, measured by following (1) ~ (3).
(1) by acrylic copolymer solution coat on releasing sheet (releasing sheet), make its dry 2 minutes at 100 DEG C, obtain membranaceous acrylic copolymer.
(2) with tetrahydrofuran (THF), the membranaceous acrylic copolymer obtained in above-mentioned (1) is dissolved as solids component 0.2 quality %.
(3) gel permeation chromatography (GPC) is used to measure the weight-average molecular weight (Mw) of (methyl) acrylic copolymer by following condition.
< condition >
GPC:HLC-8220GPC (TOSOH Co., Ltd. system)
Chromatographic column: TSK-GEL GMHXL (using 4)
Mobile phase solvent: tetrahydrofuran (THF)
Standard test specimen: polystyrene standard
Flow velocity: 0.6ml/min
Column temperature: 40 DEG C
-isocyanate-based linking agent-
Polarization plates adhesive composite of the present invention contains at least one in isocyanate-based linking agent.This linking agent is the compound with polarity, when comprising the composition of this linking agent, obtains effect of the present invention (prevent irregular colour (especially hickie) and improve weather resistance) further.
As isocyanate-based linking agent, first phenylene diisocyanate based compound preferably can be enumerated.As first phenylene diisocyanate based compound, dipolymer or the trimer of isocyanic ester can be used, or the various toluene from isocyanic ester such as the adducts of isocyanic ester and TriMethylolPropane(TMP) polyvalent alcohol supports diisocyanate cpd.
First phenylene diisocyanate based compound can use the commercially available product of listing, as the example of commercially available product, can use " CORONATE L " (trade(brand)name) of Nippon Polyurethane Industry Co., Ltd. etc. well.
Content in the polarization plates adhesive composite of isocyanate-based linking agent is set to the scope of below 20 mass parts relative to total amount 100 mass parts of acrylic copolymer.If the content of isocyanate-based linking agent is greater than 20 mass parts; then cohesive force becomes too much; be exposed to hot and humid under time and polarization plates (especially as the cellulose triacetate (TAC) of its protection sheet material) between connectivity easily decline, cannot suppress peel off generation.As the content of isocyanate-based linking agent, be preferably the scope of 8 ~ 20 mass parts, be more preferably the scope of 10 ~ 15 mass parts.When the content of isocyanate-based linking agent is more than 8 mass parts, good cohesive force is shown to the string stress of the polarization plates after suppression laminating bond layer, more effectively suppresses the generation of hickie.
-epoxy linking agent-
Polarization plates adhesive composite of the present invention comprises epoxy linking agent while preferably comprising above-mentioned isocyanate-based linking agent.When polarization plates adhesive composite comprises epoxy linking agent, easily adjust cohesive force, though be exposed to hot and humid under also can suppress abnormal appearance.
As the example of epoxy linking agent, two (N, the N-glycidyl aminomethyl) hexanaphthene of 1,3-, N, N, N can be enumerated ', N '-four glycidyl group m-xylene diamine etc.
In addition, epoxy linking agent can use the commercially available product of listing, as the example of commercially available product, can use " TETRAD-X " of Mitsubishi Gas Chemical Co., Ltd well, " TETRAD-C " (trade(brand)name) etc.
As the content in the polarization plates adhesive composite of epoxy linking agent, relative to the total amount of acrylic copolymer A and acrylic copolymer B, be preferably the scope of 0.001 ~ 0.1 quality %.If the content of epoxy linking agent is in above-mentioned scope, then can adjust the cohesive force of bond layer, can suppress the stripping in weather resistance (humidity resistance) generation in consider be favourable.
-silane coupling agent-
Polarization plates adhesive composite of the present invention preferably comprises silane coupling agent.When polarization plates adhesive composite comprises silane coupling agent, the display unit (such as liquid crystal indicator) being provided with polarization plates, even if under being exposed to hot and humid environment, is not easily peeled off between bond layer and polarization plates or liquid crystal cells.Polarization plates adhesive composite of the present invention is thought of as preferably to the aspect of the good engaging force of level and smooth glass display.
As silane coupling agent, such as, the silane compound containing polymerizability unsaturated group such as vinyltrimethoxy silane, vinyltriethoxysilane and 3-methacryloxypropyl trimethoxy silane can be enumerated; 3-mercaptopropyi Trimethoxy silane, 3-Mercaptopropyltriethoxysilane and 3-mercaptopropyi dimethoxymethylsilane etc. are containing the silane based compound of sulfydryl; And 3-glycidoxypropyltrime,hoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane etc. have the silane compound of epoxy construction; 3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane and N-(2-aminoethyl)-3-aminopropyltriethoxy dimethoxysilane etc. are containing amino silane compound; And three-(3-trimethoxy-silylpropyl) isocyanuric acid esters etc.They can be used alone one, also can combinationally use two or more.
Silane coupling agent can use the commercially available product of listing, as the example of commercially available product, can use " KBM-403 " (trade(brand)name) etc. of Shin-Etsu Chemial Co., Ltd well.
As the content in the polarization plates adhesive composite of silane coupling agent, relative to total amount 100 mass parts of acrylic copolymer A and acrylic copolymer B, be preferably the scope of 0.01 ~ 2.0 quality %.If the content of silane coupling agent is in above-mentioned scope, then can improve the connectivity of bond layer further.
Polarization plates adhesive composite of the present invention, can suitable various additive or the solvent etc. such as combined with ultraviolet radiation absorption agent further except mentioned component.
< is with the polarization plates > of caking agent
Polarization plates with caking agent of the present invention at least arranges polaroid and forms by giving already described polarization plates adhesive composite of the present invention and the bond layer that is formed on polaroid.
As polaroid, generally use such as polyvinyl alcohol (PVA) film etc.Polaroid such as can as remain between the protection sheet materials such as cellulose triacetate (TAC) such as with the polarization plates that 3-tier architecture (such as TAC/ polaroid/TAC) is formed.
By at least one side already described polarization plates adhesive composite of the present invention being imparted to the polarization plates of the 3-tier architecture of such as TAC/ polaroid/TAC, above bond layer is set, thus makes the polarization plates with caking agent.In this case, also composition can be imparted in polarization plates, but when being preferably imparted to use on strippable protection sheet material (releasing sheet).The imparting of polarization plates adhesive composite can be carried out well by employing the coating process such as pickling process, coating method, ink jet method of the polarization plates adhesive composite of liquid.Wherein, coating method is preferably.
Specifically; polarization plates adhesive composite of the present invention is coated on protection sheet material (releasing sheet); make it dry; after protection sheet material forms bond layer; this bond layer to be transferred in polarization plates and to carry out slaking, thus making the polarization plates with caking agent.
The adhesive composite be imparted on protection sheet material (releasing sheet) preferably uses hot air dryer etc. to carry out drying in 70 ~ 120 DEG C of dryings condition of about 1 ~ 3 minute.
And then, from the view point of the contact surface protected bonded object, preferably the protection sheet material (releasing sheet) for the protection of exposed surface is snugly set in the exposed surface being arranged at the adhesive linkage in polarization plates.As this protection sheet material, in order to the stripping between adhesive linkage easily can be carried out, preferably use the synthetic resin sheet materials such as the polyester having implemented demoulding process with releasing agents such as fluorine resin, paraffin, organosilicons.When being attached at the sheet glass etc. of display panel, protection sheet material is peeled off, make the surface of the layer of adhesive material exposed be sealed at glass substrate etc.
In addition, the surface-protective sheet on this surface of protection can be set further on the surface (exposed surface) of side of the bond layer not arranging polarization plates.Surface-protective sheet preferably uses bond processing to the protective membrane etc. of the one side of PET film.
As the thickness of bond layer, have no particular limits, with dried thickness gauge, be preferably 1 ~ 100 μm, be more preferably 5 ~ 50 μm, more preferably 15 ~ 30 μm.
Polarization plates with caking agent of the present invention is that more than 19 inches wide (260mm × 415mm) also can apply in the size of the liquid crystal cells of lamination.If the size of liquid crystal cells is more than 19 inches wide (260mm × 415mm), then the heat of polarization plates, humidity the expansion caused by impact, shrink and become large.Therefore, in the past with caking agent polarization plates be exposed to hot and humid under time stress suppress insufficient, therefore, when the light source igniting of large-scale display device (such as liquid crystal indicator) etc., the generation of " hickie " produced at frame (ベ セ Le) periphery cannot be suppressed.On the other hand, polarization plates with caking agent of the present invention becomes the formation making the kind of the resin design of multipolymer and linking agent suitable with amount, even if be therefore exposed to hot and humid under also fully suppress stress, also the liquid crystal cells of the size of more than 19 inches wide (260mm × 415mm) is suitable for, in addition, even if be applied to the compact display apparatus (liquid crystal indicator) being less than 19 inches (and then, be less than 10 inches) also can suppress hickie generation by the stress retentivity of appropriateness.
< display unit >
Display unit of the present invention arranges the display panel showing image and at least the already described of the present invention of one side being arranged at display panel is formed with the polarization plates of caking agent.
As display panel, the display panels, organic EL display panel etc. that are sealed with liquid crystalline cpd can be enumerated.
As the example of display unit of the present invention, the liquid crystal indicator possessing following structure can be enumerated: the two sides polarization plates with caking agent of the present invention being configured at display panels with bond layer in the mode that each face contacts with the surface (surface of such as glass substrate) of display panels, via bond layer, polarization plates is engaged in the structure (structure of polarization plates/layer of adhesive material/display panels/layer of adhesive material/polarization plates) on the two sides of display panels.
Below, polarization plates adhesive composite of the present invention is shown, with the polarization plates of caking agent and display unit and their optimal way.
< 1 > polarization plates adhesive composite, wherein, containing acrylic copolymer A, acrylic copolymer B and isocyanate-based linking agent, aforesaid propylene acid based copolymer A comprises from the structural unit of (methyl) alkyl acrylate with from the structural unit of monomer with carboxyl, and weight-average molecular weight is 300000 ~ 700000; Aforesaid propylene acid based copolymer B comprise from (methyl) alkyl acrylate structural unit, from have carboxyl monomer structural unit and from the structural unit of monomer with hydroxyl, and weight-average molecular weight is 1000000 ~ 2000000; Above-mentioned isocyanate-based linking agent is the scope of below 20 mass parts relative to the content of total amount 100 mass parts of the sour based copolymer A of aforesaid propylene and aforesaid propylene acid based copolymer B, and the second-order transition temperature (TgA) of aforesaid propylene acid based copolymer A is more than or equal to the second-order transition temperature (TgB) of aforesaid propylene acid based copolymer B.
The polarization plates adhesive composite of < 2 > as described in above-mentioned < 1 >, wherein, the second-order transition temperature (TgB) of aforesaid propylene acid based copolymer B is-50 DEG C ~-40 DEG C.
The polarization plates adhesive composite of < 3 > as described in above-mentioned < 1 > or above-mentioned < 2 >, wherein, the weight-average molecular weight (MwA) of aforesaid propylene acid based copolymer A is less than 0.5 relative to the ratio (MwA/MwB) of the weight-average molecular weight (MwB) of the sour based copolymer B of aforesaid propylene.
The polarization plates adhesive composite of < 4 > according to any one of above-mentioned < 1 > ~ above-mentioned < 3 >, wherein, aforesaid propylene acid based copolymer A counts 60/40 ~ 80/20 relative to the ratio (A/B) that contains of the sour based copolymer B of aforesaid propylene with quality criteria.
The polarization plates adhesive composite of < 5 > according to any one of above-mentioned < 1 > ~ above-mentioned < 4 >, wherein, aforesaid propylene acid based copolymer A comprises the structural unit of the alkyl ester from (methyl) vinylformic acid carbonatoms 1 ~ 4, from (methyl) acrylic acid structural unit, and from forming the structural unit of monomer of homopolymer, the second-order transition temperature that this homopolymer has with make the alkyl ester homopolymerization of above-mentioned (methyl) vinylformic acid carbonatoms 1 ~ 4 and the absolute value of the difference of the second-order transition temperature of polymkeric substance that obtains is 30 DEG C ~ 90 DEG C,
Aforesaid propylene acid based copolymer B comprise the alkyl ester from (methyl) vinylformic acid carbonatoms 1 ~ 8 structural unit, from (methyl) acrylic acid structural unit and the structural unit from (methyl) hydroxyalkyl acrylates.
< 6 > polarization plates with caking agent, wherein, the bond layer that there is polaroid and be formed on above-mentioned polaroid by the polarization plates adhesive composite given according to any one of above-mentioned < 1 > ~ above-mentioned < 5 >.
< 7 > display unit, wherein, the polarization plates with caking agent described in above-mentioned < 6 > of the display panel possessing display image and at least one side being configured at display panel.
Embodiment
Below, specifically describe the present invention further by embodiment, but the present invention only otherwise surmounting its purport is then not limited to following examples.Should illustrate, unless otherwise specified then " part " is quality criteria.
(Production Example A1)
In the reactor possessing thermometer, stirrer, nitrogen ingress pipe and reflux cooling pipe, add two methyl pentane nitrile (ABVN) 0.1 mass parts of n-butyl acrylate (BA) 79.0 mass parts, methyl acrylate (MA) 20.0 mass parts, vinylformic acid (AA) 1.0 mass parts, ethyl acetate (EAc) 110 mass parts and azo and after mixing, carry out nitrogen displacement in reactor.Thereafter, the mixture in reactor is warming up to 65 DEG C by the mixture stirring gained, keeps 8 hours and carries out polyreaction.After polyreaction terminates, be adjusted to solids component 37.0 quality % with diluted ethyl acetate reaction mixture.So, the solution (acrylic copolymer A) of BA/MA/AA copolymer A 1 is obtained.
For the BA/MA/AA copolymer A 1 of gained, carry out the mensuration of weight-average molecular weight (Mw) and the calculating of second-order transition temperature (Tg) by method shown below.Result is shown in following table 1.
Weight-average molecular weight is measured for chromatographic column with TSK-GELGMHXL (the styrenic weighting agent of TOSOH) by gel permeation chromatography (GPC) according to already described method, carries out polystyrene conversion and obtain.
Tg is mole average glass transition temperature using the calculating formula of already described second-order transition temperature (Tg) and calculate.
(Production Example A2 ~ A11)
The ratio being used for the n-butyl acrylate (BA) of the synthesis of BA/MA/AA copolymer A 1, methyl acrylate (MA) and vinylformic acid (AA) in Production Example A1 is changed to as described in Table 1, simultaneously by adjustment quantity of solvent or catalytic amount, be as described in Table 1 by molecular-weight adjusting, in addition, the solution (acrylic copolymer A) of BA/MA/AA copolymer A 2 ~ A11 is obtained in the same manner as Production Example A1.
In addition, for each multipolymer, the mensuration of Mw and the calculating of Tg is carried out in the same manner as the copolymer A 1 of Production Example A1.Result is shown in following table 1.
(Production Example A12 ~ A14)
By in Production Example A1 for the synthesis of n-butyl acrylate (BA), methyl acrylate (MA) and vinylformic acid (AA) change to the formation monomer shown in following table 2 and synthesize, obtained the solution (acrylic copolymer A) of copolymer A 12 ~ A11 by the method same with Production Example A1.
In addition, for each multipolymer, the mensuration of Mw and the calculating of Tg is carried out in the same manner as the copolymer A 1 of Production Example A1.Result is shown in following table 2.
(Production Example B1)
In the reactor possessing thermometer, stirrer, nitrogen ingress pipe and reflux cooling pipe, add two methyl pentane nitrile (ABVN) 0.03 mass parts of n-butyl acrylate (BA) 89.0 mass parts, methyl acrylate (MA) 9.5 mass parts, vinylformic acid (AA) 1.0 mass parts, vinylformic acid 2-hydroxy methacrylate (2HEA) 0.5 mass parts, ethyl acetate (EAc) 90 mass parts and azo and after mixing, carry out nitrogen displacement in reactor.Thereafter, the mixture in reactor is warming up to 65 DEG C by the mixture stirring gained, keeps 8 hours and carries out polyreaction.After polyreaction terminates, be adjusted to solids component 17.0 quality % with diluted ethyl acetate reaction mixture.So, the solution (acrylic copolymer B) of BA/MA/AA/2HEA multipolymer B1 is obtained.
In addition, for multipolymer B1, the mensuration of Mw and the calculating of Tg is carried out in the same manner as the copolymer A 1 of Production Example A1.Result is shown in following table 1.
(Production Example B2 ~ B5, B7 ~ B9)
The ratio being used for the n-butyl acrylate (BA) of the synthesis of BA/MA/AA/2HEA multipolymer B1, methyl acrylate (MA), vinylformic acid (AA) and vinylformic acid 2-hydroxy methacrylate (2HEA) in Production Example B1 is changed to as described in Table 1, simultaneously by adjustment quantity of solvent or catalytic amount, be as described in Table 1 by molecular-weight adjusting, in addition, the solution (acrylic copolymer B) of BA/MA/AA/2HEA multipolymer B2 ~ B5, B7 ~ B9 is obtained in the same manner as Production Example B1.
In addition, for each multipolymer, the mensuration of Mw and the calculating of Tg is carried out in the same manner as the multipolymer B1 of Production Example B1.Result is shown in following table 1.
(Production Example B6)
The ratio being used for the n-butyl acrylate (BA) of the synthesis of BA/MA/AA/2HEA multipolymer B1, vinylformic acid (AA) and vinylformic acid 2-hydroxy methacrylate (2HEA) in Production Example B1 is changed to as described in Table 1, and methyl acrylate (MA) 9.5 parts is replaced with 2-EHA (2EHA) 15 parts, simultaneously by adjustment quantity of solvent or catalytic amount, be as described in Table 1 by molecular-weight adjusting, in addition, the solution (acrylic copolymer B) of BA/2EHA/AA/2HEA multipolymer B6 is obtained in the same manner as Production Example B1.
In addition, for each multipolymer, the mensuration of Mw and the calculating of Tg is carried out in the same manner as the multipolymer B1 of Production Example B1.Result is shown in following table 1.
(Production Example B10 ~ B13)
By in Production Example B1 for the synthesis of n-butyl acrylate (BA), methyl acrylate (MA), vinylformic acid (AA) and vinylformic acid 2-hydroxy methacrylate (2HEA) change to the formation monomer shown in following table 2 and synthesize, obtained the solution (acrylic copolymer B) of multipolymer B10 ~ B13 by the method same with Production Example B1.
In addition, for each multipolymer, the mensuration of Mw and the calculating of Tg is carried out in the same manner as the multipolymer B1 of Production Example B1.Result is shown in following table 2.
(embodiment 1)
-preparation of adhesive composite-
Using the solution (solids component of BA/MA/AA multipolymer: 70.0 mass parts) of the BA/MA/AA multipolymer obtained in the above-mentioned Production Example A1 of acrylic copolymer A of 189.2 mass parts, the solution as the BA/MA/AA/2HEA multipolymer B1 obtained in the above-mentioned Production Example B1 of acrylic copolymer B (solids component of BA/MA/AA/2HEA multipolymer: 30.0 mass parts) of 176.5 mass parts, CORONATEL as isocyanate compound (the isocyanic ester based compound of Japanese polyurethane industrial of 20 mass parts, effective constituent: 15 mass parts), TETRAD-X as the epoxy compounds (epoxy compounds of gas chemical company of Mitsubishi of 0.02 mass parts, effective constituent: 0.02 mass parts), and 0.1 KBM-403 (silane coupling agent of chemical industrial company of SHIN-ETSU HANTOTAI as silane compound (SC agent) of mass parts, effective constituent: 0.1 mass parts) be uniformly mixed fully and obtain adhesive composite.
Now, the weight-average molecular weight (MwA) of BA/MA/AA copolymer A 1 (acrylic copolymer A) is 0.33 with the molecular weight ratio (MwA/MwB) of the weight-average molecular weight (MwB) of BA/MA/AA/2HEA multipolymer (acrylic copolymer B), for Tg, acrylic copolymer A is higher than acrylic copolymer B.
-making of optical film sample-
By adhesive composite with dried glue spread for 25g/cm 2mode coat the releasing agent treated side having carried out surface-treated stripping film with silicon-type releasing agent.Then, use hot air circulation type drying machine to make its dry 90 seconds at 100 DEG C, stripping film forms bond layer.Next, cellulose triacetate (TAC) rete (is pressed on the polarisation basilar membrane based on the two sides of the polaroid of polyvinyl alcohol (PVA) film with the laminar structure of TAC film/PVA film/TAC film by polarisation basilar membrane; About 190 μm) the back side overlappingly with the surface of above-mentioned bond layer to fit, the pressing by pressurization niproll.After pressing, 23 DEG C, slaking 10 days under the envrionment conditions of 65%RH, make there is the laminar structure of stripping film/bond layer/polarisation basilar membrane polarizing coating as optical film sample.
-evaluate-
Use the polarizing coating of above-mentioned making, carry out following evaluation.Evaluation result is shown in following table 1.
(1) tackiness
By the method being benchmark with JIS Z 0237, measure the value (angle=30 ° of tilted plate) of tilting Rolling Ball Tack, evaluated according to following metewand by the ball quantity stopped.
< metewand >
A: ball quantity is more than 7.
B: ball quantity is 5 ~ 6.
C: ball quantity is 3 ~ 4.
D: ball quantity is less than 3.
(2) weather resistance
(2-1) 4.3 inches (dry (Dry), wet (Wet))
The test film (4.3 inches) of 54mm × 96mm (long limit) that the polarizing coating made in above-mentioned " making of optical film sample " cuts in the mode that is 45 ° relative to the long limit of absorption axes by preparation, peels off stripping film from this test film.Closely sealed by the one side of the surface of layer of adhesive material of will expose due to stripping and the non-alkali glass plate (#1737, CORNING Inc.) of 0.7mm, test film is overlapped on sheet glass, uses laminating machine to carry out attaching and making layered product.Then, to this layered product implement autoclave process (50 DEG C, 5kg/cm 2, 20 minutes), 23 DEG C, place 24 hours under the condition of 65%RH.Thereafter, under dry (Dry) environment (80 DEG C, 0%RH) of high temperature low humidity conditions and wet (WET) environment (60 DEG C, 90%RH) of hot and humid condition, 500 hours are placed respectively.After storage period, by the state of visual observation foaming, stripping, evaluate according to following metewand.
< metewand >
A: do not observe foaming completely, peel off.
B: almost do not observe foaming, peel off.
C: observe some foaming, stripping.
D: observe obvious foaming, stripping.
(2-2) 19 inches (dry (Dry), wet (Wet))
Except the dimension modifying of the test film obtained by cutting polarizing coating in above-mentioned " (2-1) 4.3 inches (dry (Dry); wet (Wet)) " is beyond 240mm × 427mm (19 inches), by evaluating with " (2) weather resistance (4.3 inches: dry (Dry), wet (Wet)) " same method.
(3) irregular colour
(3-1) hickie phenomenon (4.3 inches)
Prepare 2 cut into above-mentioned " (2-1) 4.3 inches (dry (Dry); wet (Wet)) " in be of a size of the test film of the polarizing coating of same size, non-alkali glass plate (the #1737 of 0.7mm is attached in the mutually perpendicular mode of polarizing axis, CORNING Inc.) two sides, make test sample.Then, to this test sample implement autoclave process (50 DEG C, 5kg/m 2, 20 minutes), 23 DEG C, place 24 hours under the condition of 50%RH.Thereafter, place 500 hours under dry environment (70 DEG C, 0%RH).After placement, 23 DEG C, be placed in respectively on the backlight of liquid-crystal display, with the state of visual observation hickie under the condition of 50%RH.
< metewand >
A: do not observe hickie completely.
B: almost do not observe hickie.
C: observe some hickies.
D: observe a lot of hickie.
(3-2) hickie phenomenon (7 inches)
Except the dimension modifying of the test film obtained by cutting polarizing coating in above-mentioned " (3-1) hickie phenomenon (4.3 inches) " is except 88mm × 156mm (7.0 inches), evaluate with the method same with " (3-1) hickie phenomenon (4.3 inches) ".
(3-3) hickie phenomenon (19 inches)
Except the dimension modifying of the test film obtained by cutting polarizing coating in above-mentioned " (3-1) hickie phenomenon (4.3 inches) " is except 240mm × 427mm (19 inches), evaluate with the method same with " (3-1) hickie phenomenon (4.3 inches) ".
(embodiment 2 ~ 21, comparative example 1 ~ 6)
Except by the monomer of acrylic copolymer in embodiment 1 composition or physical property (Tg, Mw), weight-average molecular weight, the changing to except as Suo Shi following table 1 ~ table 2 containing ratio, cross-linked dosage of acrylic copolymer A, B, prepare adhesive composite similarly to Example 1, make polarizing coating, evaluate simultaneously.
[table 1]
[table 2]
As the above Table 1 to Table 2, in embodiment, have nothing to do with DRY environment and wet (WET) environment, the generation of foaming or peeling off can be suppressed, good weather resistance can be obtained.In addition, have nothing to do with the size of size, effectively can suppress the generation of hickie.In addition, being involved in of the bubble easily do not produced when fitting, shows good tackiness.
Full content disclosed in Japanese publication 2012-128291 is incorporated by reference into the present specification.
With by referring to introduce each document, patent application and technological standard be concrete and separately by the situation equal extent ground recorded, the whole documents recorded, patent application and technological standard are incorporated by reference into the present specification in this specification sheets.

Claims (7)

1. a polarization plates adhesive composite, wherein, contains:
Acrylic copolymer A, it comprises from the structural unit of (methyl) alkyl acrylate with from the structural unit of monomer with carboxyl, and weight-average molecular weight is 300000 ~ 700000;
Acrylic copolymer B, its comprise from (methyl) alkyl acrylate structural unit, from have carboxyl monomer structural unit and from the structural unit of monomer with hydroxyl, and weight-average molecular weight is 1000000 ~ 2000000; And
Isocyanate-based linking agent, it is the scope of below 20 mass parts relative to the content of total amount 100 mass parts of described acrylic copolymer A and described acrylic copolymer B,
The glass transition temperature Tg A of described acrylic copolymer A is more than or equal to the glass transition temperature Tg B of described acrylic copolymer B.
2. polarization plates adhesive composite as claimed in claim 1, wherein, the glass transition temperature Tg B of described acrylic copolymer B is-50 DEG C ~-40 DEG C.
3. polarization plates adhesive composite as claimed in claim 1 or 2, wherein, the weight-average molecular weight MwA of described acrylic copolymer A is less than 0.5 relative to the ratio MwA/MwB of the weight-average molecular weight MwB of described acrylic copolymer B.
4. the polarization plates adhesive composite according to any one of claims 1 to 3, wherein, described acrylic copolymer A counts 60/40 ~ 80/20 relative to the ratio A/B that contains of described acrylic copolymer B with quality criteria.
5. the polarization plates adhesive composite according to any one of Claims 1 to 4, wherein,
Described acrylic copolymer A comprise the alkyl ester from (methyl) vinylformic acid carbonatoms 1 ~ 4 structural unit, from (methyl) acrylic acid structural unit and from the structural unit of monomer that can form homopolymer, the second-order transition temperature that this homopolymer has with make the alkyl ester of described (methyl) vinylformic acid carbonatoms 1 ~ 4 carry out homopolymerization and the absolute value of the difference of the second-order transition temperature of polymkeric substance that obtains is 30 DEG C ~ 90 DEG C
Described acrylic copolymer B comprise the alkyl ester from (methyl) vinylformic acid carbonatoms 1 ~ 8 structural unit, from (methyl) acrylic acid structural unit and the structural unit from (methyl) hydroxyalkyl acrylates.
6. the bond layer that with a polarization plates for caking agent, wherein, there is polaroid and require the polarization plates adhesive composite according to any one of 1 ~ 5 by entitle and be formed on described polaroid.
7. a display unit, wherein, possesses the polarization plates with caking agent according to claim 6 of the display panel demonstrating image and at least one side being configured at display panel.
CN201380029297.8A 2012-06-05 2013-05-31 Polarization plates adhesive composite, with the polarization plates of bonding agent and display device Active CN104379694B (en)

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TW201406895A (en) 2014-02-16

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