CN104379694B - Polarization plates adhesive composite, with the polarization plates of bonding agent and display device - Google Patents

Polarization plates adhesive composite, with the polarization plates of bonding agent and display device Download PDF

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CN104379694B
CN104379694B CN201380029297.8A CN201380029297A CN104379694B CN 104379694 B CN104379694 B CN 104379694B CN 201380029297 A CN201380029297 A CN 201380029297A CN 104379694 B CN104379694 B CN 104379694B
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acrylic acid
acid series
methyl
series copolymer
polarization plates
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CN104379694A (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
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polarising Elements (AREA)
  • Adhesive Tapes (AREA)

Abstract

The present invention provides a kind of polarization plates adhesive composite, said composition contains: comprise from the construction unit of (methyl) alkyl acrylate with from having the construction unit of monomer of carboxyl and acrylic acid series copolymer A that weight average molecular weight is 300,000～700,000, comprise the construction unit from (methyl) alkyl acrylate, construction unit from the monomer with carboxyl, and from having the construction unit of monomer of hydroxyl and acrylic acid series copolymer B that weight average molecular weight is 1,000,000～2,000,000, and the isocyanate-based cross-linking agent that content is below 20 mass parts of total amount 100 mass parts relative to acrylic acid series copolymer A and acrylic acid series copolymer B, and constituted with glass transition temperature be more than or equal to acrylic acid series copolymer B of the glass transition temperature of acrylic acid series copolymer A.

Description

Polarization plates adhesive composite, with the polarization plates of bonding agent and display device
Technical field
The present invention relates to polarization plates adhesive composite, with the polarization plates of bonding agent and display device.
Background technology
In recent years, as the display device 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 liquid crystal composition being oriented in prescribed direction and is held on the structure of the blooming such as the liquid crystal cells between 2 support substrates such as glass and polarization plates, phase retardation film, brightness enhancement film laminating.Blooming lamination each other, blooming use bonding agent when being attached at liquid crystal cells.
Liquid crystal indicator is widely used as display devices such as PC, TV, automobile navigation instruments, for instance, the many harsh environment condition of hot and humid water quantities, low humidity the various environmental conditions such as dry environment condition under use.Therefore, even if require possess life-time service, with the sticking part (that is, the interface between bond layer and liquid crystal cells or polarizing coating) of bonding agent laminating without peeling off stripping or not producing fracture at bond layer and be difficult to produce such high-durability energy such as bubble at bond layer.
Additionally, polarization plates has the polarizing coating (polaroid) using PVA etc..When stretched film is used for this polarizing coating, if be exposed to such as hot and humid under in this harsh environment, then easily produce along with the change in size shunk, expand, polarization plates produce stress.When relaxing not over the bonding agent that is configured between polarization plates and liquid crystal cells along with the stress of change in size, polarization plates produces residual stress unevenly.Its result, at surface and the back side of display floater, the position of 2 polarization plates configured in the way of the tensile axis of polarizing coating crosses one another produces deviation mutually.Therefore, bleach from the 4 of the display part of liquid crystal indicator periphery light leaks, produce to be referred to as the inequality of so-called " white macula (white け) ".
The occurrence frequency of above-mentioned white macula, emergence pattern are different according to the size of display floater.From this viewpoint, general small-sized display panel uses softer soft bonding agent, and larger display panels uses harder rigid bonding agent.If being intended to this rigid bonding agent is applied to small-sized display panel, then easily concentrate on limit end along with the stress of contraction etc., there is panel periphery and the trend of above-mentioned white macula occurs significantly.On the other hand, when manufacturing large-sized bonding agent for larger display panels purposes, owing to cannot effectively utilize the end of whole bonding agent (former anti-), become one of reason of yield rate step-down.Additionally, soft bonding agent is due to softness, there is also the trend being easily attached to processing blades and punch press process difference.
In order to improve above-mentioned white macula, it is proposed that add low-molecular weight polymer in adhesive composite to relax the bonding agent of stress.Such as, the polarization plates adhesive composite being made up of the low molecular weight propylene acid based copolymer that high-molecular-weight propylene acid based copolymer, weight average molecular weight are less than 30,000 and multi-functional compounds is disclosed.By having the characteristic following change in size produced by polarization plates so that the irregular colour of periphery and central part is 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 acid series copolymer (A) and (methyl) acrylic acid series copolymer (B) that weight average molecular weight is 105～1,350,000 together contain with isocyanate compound with the ratio of regulation, make, under hot and humid, there is durability, and white macula is suppressed (for example, referring to patent documentation 2).
Prior art literature
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 conventional technology, disclose in order to prevent with white macula be representative the generation of irregular colour and use the technology of (methyl) acrylic acid series copolymer varied in size of weight average molecular weight, but simply mixing uses the multiple copolymer that only molecular weight is different, it is difficult to maintain well the durability of foaming or stripping, fracture etc., is also difficult to prevent the generation of white macula simultaneously.
Bonding agent is from the adjustment just carrying out the composition of bonding agent according to purposes, size in the past.On the other hand, for can be applicable to larger display panels purposes and small-sized display panel purposes, and the generation of white macula and the bonding agent of durability, excellent in workability independently can be prevented not yet to be suggested with size be truth.
The present invention is based on foregoing and completes.Under above-mentioned condition, it is necessary to there is the high-durability being not likely to produce foaming or stripping etc., and independently suppress the polarization plates adhesive composite of the generation of irregular colour (especially white macula) with size and with the polarization plates of bonding agent.Furthermore, it is necessary to demonstrate the display device of the few image of irregular colour.
The present invention is based on following opinion and reaches.That is,
Think when mixing uses two or more resin varied in size of weight average molecular weight, in two or more resin, the resin that molecular weight is little does not have hydroxyl isopolarity group, with the molecular weight resin-phase ratio more than this resin with polar group, it is shown through reducing molecular weight and durability downward trend with the reactivity hour of cross-linking agent, but it is conceived to the glass transition temperature of resin, the reactivity with isocyanate-based cross-linking agent is regulated, it is possible to reach the durability of bonding agent and prevent the generation of irregular colour by copolymer composition.
Concrete method for reaching above-mentioned problem is as follows.
1st present invention is a kind of polarization plates adhesive composite, it contains: acrylic acid series copolymer A, it comprises the construction unit from (methyl) alkyl acrylate and the construction unit from the monomer with carboxyl, and weight average molecular weight is 300000～700000；Acrylic acid series copolymer B, its comprise the construction unit from (methyl) alkyl acrylate, from have carboxyl monomer construction unit and from the construction unit of the monomer with hydroxyl, and weight average molecular weight is 1000000～2000000；And isocyanate-based cross-linking agent, its scope that content is below 20 mass parts relative to aforesaid propylene acid based copolymer A and total amount 100 mass parts of aforesaid propylene acid based copolymer B, the glass transition temperature (TgA) of the aforesaid propylene acid based copolymer A glass transition temperature (TgB) be more than or equal to aforesaid propylene acid based copolymer B.
2nd present invention is a kind of polarization plates with bonding agent, wherein, has polaroid and is formed at the bond layer on above-mentioned polaroid by giving the polarization plates adhesive composite of the above-mentioned invention of the 1st.
According to the present invention, it is provided that a kind of have a high-durability being not likely to produce foaming or stripping etc., and independently suppress the polarization plates adhesive composite of the generation of irregular colour (especially white macula) with size and with the polarization plates of bonding agent.Additionally,
According to the present invention, it is provided that a kind of display device demonstrating the few image of irregular colour.
Detailed description of the invention
Hereinafter, to the polarization plates adhesive composite of the present invention and use its polarization plates with bonding agent and display device to be described in detail.
< polarization plates adhesive composite >
The polarization plates of present invention adhesive composite uses acrylic acid series copolymer A, acrylic acid series copolymer B and isocyanate-based cross-linking agent to constitute, described acrylic acid series copolymer A comprises the construction unit from (methyl) alkyl acrylate and the construction unit from the monomer with carboxyl, and weight average molecular weight is 300000～700000；Described acrylic acid series copolymer B comprise the construction unit from (methyl) alkyl acrylate, from have carboxyl monomer construction unit and from the construction unit of the monomer with hydroxyl, and weight average molecular weight is 1000000～2000000.And then, in the polarization plates adhesive composite of the present invention, the content of the isocyanate-based cross-linking agent scope that total amount 100 mass parts is below 20 mass parts relative to aforesaid propylene acid based copolymer A and aforesaid propylene acid based copolymer B, and the glass transition temperature (TgB) of the glass transition temperature (TgA) of aforesaid propylene acid based copolymer A and aforesaid propylene acid based copolymer B meets the relation of TgA >=TgB.
Additionally, the polarization plates of the present invention with adhesive composite except acrylic acid series copolymer A and acrylic acid series copolymer B, it is possible to comprise other compositions such as cross-linking agent, silane coupler, other additive as required further.
The technology of the multiple copolymer composition bonding agent that conventional known use molecular weight is different.But, only reduce the molecular weight of a part of copolymer, although can expect that stress relaxes effect produced by the irregular colours such as white macula, but durability is remarkably decreased, it is impossible to suppress the generation of foaming or stripping etc..Therefore, in the present invention,
Use the high isocyanate-based cross-linking agent of Polarity comparision as while cross-linking agent using the ratio of regulation, at least make the acrylic acid series copolymer B of high molecular side has hydroxyl as polar group, and the glass transition temperature (TgB) that the glass transition temperature (TgA) of the acrylic acid series copolymer A of low-molecular-weight side is be more than or equal to acrylic acid series copolymer B.Thus, the reaction of the isocyanate-based cross-linking agent of the acrylic acid series copolymer A of promotion and low-molecular-weight side.To Surge chamber retentivity, and the embrittlement quantified along with low molecule is prevented, the generation reaching the irregular colour (especially white macula) preventing bonding agent independently from the size with size and the raising of durability by making acrylic acid series copolymer low molecule quantify.
The polarization plates adhesive composite of the present invention is due to excellent in preventing durability and irregular colour (especially white macula), while the larger display panels (i.e. large-scale display device) of more than 19 inches can be performed well in, it also is able to perform well in the small-sized display panel (i.e. compact display apparatus) less than 19 inches (and then, less than 10 inches).In other words, the polarization plates adhesive composite of the present invention is while manufacturing the bonding agent of larger display panels purposes, it is possible to manufacture the bonding agent of small-sized display panel purposes from the end of whole bonding agent (former anti-), therefore yield rate improves.Therefore, it is possible to measure according to demand and manufacture the bonding agent of size, also there is the advantage without stock, keeping.
Should illustrating, in this specification, (methyl) acrylic acid refers to acrylic or methacrylic acid, and (methyl) acrylate refers to acrylate or methacrylate.
Hereinafter each composition is described in detail.
-acrylic acid series copolymer A-
The polarization plates adhesive composite of the present invention contains at least one of acrylic acid series copolymer A, aforesaid propylene acid based copolymer A comprises the construction unit from (methyl) alkyl acrylate and the construction unit from the monomer with carboxyl, and weight average molecular weight is 300000～700000.This acrylic acid series copolymer A at least makes (methyl) alkyl acrylate and the copolymer having the monomer copolymerization of carboxyl and obtaining, it is also possible to is other monomer of further copolymerization and has the copolymer of the construction unit from this monomer further.
As (methyl) alkyl acrylate constituting acrylic acid series copolymer A, such as, (methyl) acrylic acid methyl ester. can be enumerated, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) acrylic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, (methyl) acrylic acid ester in the positive last of the ten Heavenly stems, positive ten diester of (methyl) acrylic acid and (methyl) octadecyl acrylate etc..Wherein, from the viewpoint of being easily adjusted the cohesiveness of bonding agent and engaging force, it is preferred to the Arrcostab of (methyl) acrylic acid carbon number 1～4, it is preferred to the Arrcostab of acrylic acid carbon number 1～4, it is particularly preferred to for n-butyl acrylate.
It is preferably 65.0～99.5 mass %, more preferably 65.0～94.5 mass %, it is particularly preferred to be 75.0～90.0 mass % from the ratio in the acrylic acid series copolymer A of the construction unit of (methyl) alkyl acrylate.(methyl) alkyl acrylate is contained as constituting the main constituent of copolymer, if it contains ratio in above-mentioned scope, then can be adjusted to best elastic modelling quantity, guaranteeing durability, adhesive in be advantageous for.
Acrylic acid series copolymer in the present invention A's it is preferable that: except contain (methyl) alkyl acrylate as main constituent except, the monomer that further copolymerization is different from above-mentioned (methyl) alkyl acrylate, this monomer can form homopolymer, and the absolute value of the glass transition temperature that this homopolymer has and the difference of the glass transition temperature of the polymer making above-mentioned (methyl) alkyl acrylate (carbon number of preferred alkyl is 1～4) homopolymerization obtain is 30 DEG C～90 DEG C.This mode can improve glass transition temperature, namely improves the polarity of resin and improves and the reactivity of isocyanate-based cross-linking agent, improves durability further.
Wherein, as the monomer of the homopolymer that can form the glass transition temperature in above-mentioned scope of the absolute value with above-mentioned difference, it is preferred to acrylic acid methyl ester., tert-butyl acrylate, acrylate, n-BMA.As particularly preferred acrylic acid series copolymer A, it it is the pattern of n-butyl acrylate and acrylic acid methyl ester. and/or tert-butyl acrylate copolymerization.
Except containing (methyl) alkyl acrylate as main constituent, when containing above-mentioned monomer (be preferably acrylic acid methyl ester., tert-butyl acrylate) different from it, it is preferably 5～30 mass %, more preferably 5～20 mass % from ratio in acrylic acid series copolymer A of the construction unit of this monomer.If should containing ratio be in above-mentioned scope, then improve with isocyanate-based cross-linking agent reactive in be advantageous for.
As the monomer with carboxyl constituting acrylic acid series copolymer A, it is however preferred to have (methyl) acrylic monomer of carboxyl.Example as the monomer with carboxyl, it is possible to enumerate acrylic acid, methacrylic acid, ω-carboxyl-polycaprolactone list (methyl) acrylate etc..Wherein, when copolyreaction with the reactive high of other monomer and can reduce unreacted monomer in consider, it is preferred to acrylic acid.
It is preferably 0.5～5 mass %, more preferably 0.5～3 mass % from having the construction unit of monomer of the carboxyl ratio in acrylic acid series copolymer A.If the monomer with carboxyl is in above-mentioned scope containing ratio, then consider to be advantageous in the viewpoint guaranteeing property working life and can moderately adjust resin's crosslinkage.
The weight average molecular weight of acrylic acid series copolymer A is 300000～700000.Weight average molecular weight is represent in above-mentioned scope that in the multiple resins contained in polarization plates adhesive composite, acrylic acid series copolymer A is the resin of low-molecular-weight side.If additionally, the weight average molecular weight of acrylic acid series copolymer A becomes too small less than 300000, then easily it is peeling and durability (being particularly applied to durability during large scale (such as more than 19 inches) purposes) declines.In turn, if the weight average molecular weight of acrylic acid series copolymer A becomes excessive more than 700000, then molecular dimension is close to acrylic acid series copolymer B, by with acrylic acid series copolymer A and with and the stress that produces relaxes and diminishes, it is impossible to suppress the generation of irregular colour (especially white macula).This situation occurs when being particularly applied to large scale (such as more than 19 inches) purposes significantly.
Glass transition temperature (TgA) as acrylic acid series copolymer A, it is preferred to the scope of-50 DEG C～-30 DEG C, more preferably the scope of-48 DEG C～-40 DEG C.If TgA is more than-50 DEG C, then can being adjusted on elastic modelling quantity, durability, white macula are excellent.If additionally, TgA is less than-30 DEG C, then will not damage viscosity terrifically and excellent in cohesiveness, suitable laminating.
As the content in the polarization plates adhesive composite of acrylic acid series copolymer A, suitably can select meeting in the aftermentioned scope containing ratio A/B, all solids composition relative to polarization plates adhesive composite, it is preferably the scope of 50 mass %～74 mass %, more preferably the scope of 54 mass %～69 mass %.If the content of acrylic acid series copolymer A is in above-mentioned scope, then give flexibility to bonding agent, relaxed the generation suppressing irregular colour (especially white macula) by stress.
-acrylic acid series copolymer B-
The polarization plates adhesive composite of the present invention contains at least one of acrylic acid series copolymer B, aforesaid propylene acid based copolymer B comprise the construction unit from (methyl) alkyl acrylate, from have carboxyl monomer construction unit and from the construction unit of the monomer with hydroxyl, and weight average molecular weight is 1000000～2000000.This acrylic acid series copolymer B is at least make (methyl) alkyl acrylate, have the monomer of carboxyl and have the monomer copolymerization of hydroxyl and the copolymer that obtains, it is also possible to is other monomer of further copolymerization and has the copolymer of the construction unit from this monomer further.
As (methyl) alkyl acrylate constituting acrylic acid series copolymer B, such as, (methyl) acrylic acid methyl ester. can be enumerated, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) acrylic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, (methyl) acrylic acid ester in the positive last of the ten Heavenly stems, positive ten diester of (methyl) acrylic acid and (methyl) octadecyl acrylate etc..Wherein, from the viewpoint of being easily adjusted the cohesiveness of bonding agent and engaging force, it is preferably the Arrcostab of (methyl) acrylic acid carbon number 1～8, it is preferably the Arrcostab of acrylic acid carbon number 1～8, it is particularly preferred to for n-butyl acrylate, tert-butyl acrylate, acrylic acid methyl ester., 2-EHA.
It is preferably 93～99.4 mass %, more preferably 96～99.4 mass % from ratio in acrylic acid series copolymer B of the construction unit of (methyl) alkyl acrylate.(methyl) alkyl acrylate is contained as constituting the main constituent of copolymer, if it contains ratio is in above-mentioned scope, then can be adjusted to best elastic modelling quantity and durability, adhesion properties in favourable.
As the monomer with carboxyl constituting acrylic acid series copolymer B, it is however preferred to have (methyl) acrylic monomer of carboxyl.Example as the monomer with carboxyl, it is possible to enumerate acrylic acid, methacrylic acid, ω-carboxyl-polycaprolactone list (methyl) acrylate etc..Wherein, when copolyreaction with the reactive high of other monomer and can reduce unreacted monomer in consider, it is preferred to acrylic acid.
It is preferably 0.5～5 mass %, more preferably 0.5～3 mass % from having the construction unit of monomer of the carboxyl ratio in acrylic acid series copolymer B.If the monomer with carboxyl is in above-mentioned scope containing ratio, then consider to be advantageous in the viewpoint guaranteeing property working life and can moderately adjust resin's crosslinkage.
As the monomer with hydroxyl constituting acrylic acid series copolymer B, it is however preferred to have (methyl) acrylic monomer of hydroxyl, more preferably there is (methyl) acrylate of hydroxyl.Example as the monomer with hydroxyl, (methyl) acrylic acid 2-hydroxy methacrylate can be enumerated, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxybutyl, (methyl) acrylic acid 3-methyl-3-hydroxybutyl, (methyl) acrylic acid 1, 3-dimethyl-3-hydroxybutyl, (methyl) acrylic acid 2, 2, 4-trimethyl-3-hydroxyl pentyl ester, (methyl) acrylic acid 2-ethyl own ester of-3-hydroxyl, polypropylene glycol list (methyl) acrylate, polyethyleneglycol (methyl) acrylate and poly-(ethylene glycol and 1,2-propylene glycol) single (methyl) acrylate etc..
Wherein, the cross-linking reaction during composition of and the copolymer that be set to comprise gained high at polymerisation reactivity excellent in consider, it is preferably (methyl) hydroxyalkyl acrylates, more preferably (methyl) acrylic acid carbon number of alkyl portion is the hydroxyalkyl acrylate of 1～4, more preferably acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxy propyl ester, acrylic acid 4-hydroxybutyl.
It is preferably 0.1～2.0 mass %, more preferably 0.1～1.0 mass % from having the construction unit of monomer of the hydroxyl ratio in acrylic acid series copolymer B.If the monomer with hydroxyl is in above-mentioned scope containing ratio, then may insure that and the reactivity of isocyanate-based cross-linking agent, favourable to maintaining durability well.
The weight average molecular weight of acrylic acid series copolymer B is 1000000～2000000.Weight average molecular weight is represent in above-mentioned scope that in the multiple resins contained in polarization plates adhesive composite, acrylic acid series copolymer B is the resin of high molecular side.If additionally, the weight average molecular weight of acrylic acid series copolymer B diminishes less than 1000000, being then easily peeling, and durability (being particularly applied to durability during large scale (such as more than 19 inches) purposes) declines.If the weight average molecular weight of acrylic acid series copolymer B becomes excessive more than 2000000, then and by the stress alleviation effects caused by acrylic acid series copolymer A decline.Therefore, become to be difficult to follow contraction, easily producing fracture in bonding agent or peel off, durability is deteriorated, the generation of the irregular colour (especially white macula) when simultaneously cannot suppress to be particularly applied to small size (such as 10 less than inch) purposes.
Glass transition temperature (TgB) as acrylic acid series copolymer B, it is preferred to the scope of-50 DEG C～-40 DEG C, more preferably the scope of-50 DEG C～-45 DEG C.If TgB is more than-50 DEG C, then can being adjusted on elastic modelling quantity, durability, white macula are excellent.If additionally, TgB is less than-40 DEG C, then will not damage viscosity terrifically and excellent in cohesiveness, suitable laminating.
As the content in the polarization plates adhesive composite of acrylic acid series copolymer B, suitably can select meeting in the aftermentioned scope containing ratio A/B, all solids composition relative to polarization plates adhesive composite, it is preferably the scope of 17～37 mass %, more preferably the scope of 21～32 mass %.If the content of acrylic acid series copolymer B is in above-mentioned scope, then can keeping the ratio of high molecular weight components in bonding agent, durability improves.
In acrylic acid series copolymer A in the present invention and acrylic acid series copolymer B, (methyl) alkyl acrylate constituting respective copolymer, the monomer with carboxyl can be mutually different in acrylic acid series copolymer A and acrylic acid series copolymer B, it is also possible to identical.
In the present invention, the glass transition temperature (TgA of aforesaid propylene acid based copolymer A；DEG C) with the glass 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 the reactive deficiency with isocyanate-based cross-linking agent, it is easy to produce the faults such as foaming or stripping, poor durability.Wherein, from the view point of the preventing effectiveness of irregular colour (especially white macula) and further raising durability, as the difference (TgA-TgB of TgA and TgB；DEG C), it is preferred to the scope of 1～5 DEG C, more preferably the scope of 1～3 DEG C.
In this specification, the glass transition temperature (Tg) of acrylic acid series copolymer is by mole average glass transition temperature obtained calculated below.Tg in following formula1、Tg2, and TgnIt is the glass transition temperature of composition 1, composition 2 and the respective homopolymer of ingredient n, is converted into absolute temperature (K) and calculates.m1、m2, and mnIt it is the molar fraction of respective composition.
[calculating formula of glass transition temperature (Tg)]
[several 1]
1 Tg = m 1 Tg 1 + m 2 Tg 2 + . . . . . . . + m n Tg n
Should illustrate, " glass transition temperature (Tg) of homopolymer " mentioned here is applied to L.E.Nielsen (L.E. ニ Le セ Application) work, and little wild wood a surname controls the glass transition temperature translating the monomer recorded in " character (property of high-molecular mechanical) of high molecular mechanics " the 11st～35 page.
Additionally, the ratio (MwA/MwB) of the weight average molecular weight (MwB) that the weight average molecular weight (MwA) of aforesaid propylene acid based copolymer A is relative to aforesaid propylene acid based copolymer B is preferably less than 0.5.MwA/MwB is less than 0.5 preventing effectiveness that can improve irregular colour (especially white macula) further.Wherein, MwA/MwB is due to reason similar to the above, 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 more than the ratio that ratio A/B is lower limit, then the ratio of the acrylic acid series copolymer A of molecular weight is more, therefore counter stress relaxes the improvement effect height of caused irregular colour (especially white macula), and the glass transition temperature of acrylic acid series copolymer A and B meets the relation of TgA >=TgB, thus the worry that the many caused durability of the ratio of acrylic acid series copolymer A decline is also few.Additionally, by making containing below the ratio that ratio A/B is the upper limit, it is possible to keep low molecule to quantify the balance of caused stress alleviation effects and the maintenance of the durability caused by relative quantity of the acrylic acid series copolymer B maintaining high molecular side.
Wherein, as containing ratio A/B, due to above-mentioned same reason, more preferably the scope of 65/35～75/25.
In above-mentioned, as the compound mode of the acrylic acid series copolymer A in the present invention Yu acrylic acid series copolymer B, it is preferred to following (1) the 1st mode～(3) the 3rd mode.That is,
(1) the 1st mode:
Construction unit that acrylic acid series copolymer A comprises the Arrcostab from (methyl) acrylic acid carbon number 1～4, from (methyl) acrylic acid construction unit and from the construction unit of " monomer of the homopolymer of the glass transition temperature that absolute value is 30～90 DEG C of the difference of the glass transition temperature of the polymer having and make the Arrcostab homopolymerization of above-mentioned (methyl) acrylic acid carbon number 1～4 and obtain can be formed "
Acrylic acid series copolymer B comprises the construction unit of the Arrcostab from (methyl) acrylic acid carbon number 1～8, from (methyl) acrylic acid construction unit and the construction unit from (methyl) hydroxyalkyl acrylates.
(2) the 2nd modes:
Acrylic acid series copolymer A comprise the construction unit from n-butyl acrylate, from have carboxyl (methyl) acrylic monomer construction unit and from the construction unit of acrylic acid methyl ester. and/or tert-butyl acrylate,
Acrylic acid series copolymer B comprise the construction unit from n-butyl acrylate, from have carboxyl (methyl) acrylic monomer construction unit and from the construction unit of (methyl) hydroxyalkyl acrylates.
(3) the 3rd modes:
Acrylic acid series copolymer A comprises the construction unit from n-butyl acrylate, from (methyl) acrylic acid construction unit and acrylic acid methyl ester. and/or tert-butyl acrylate,
Acrylic acid series copolymer B comprises the construction unit from n-butyl acrylate, from (methyl) acrylic acid construction unit and the construction unit from (methyl) hydroxyalkyl acrylates.
The polymerization of the acrylic acid series copolymer in the present invention has no particular limits, it is possible to the methods such as solution application polymerization, emulsion polymerization, suspension polymerisation.Fairly simple from the viewpoint for the treatment of process and can carry out at short notice, it is preferred to polymerisation in solution.
Polymerisation in solution is usually the chain-transferring agent loading the organic solvent of regulation, monomer, polymerization initiator in polymerization tank and using as required, in nitrogen stream or under the backflow of organic solvent, stirs reacting by heating a few hours.As above-mentioned polymerization initiator, it does not have limit especially, for instance Azo can be used.
The weight average molecular weight (Mw) of acrylic acid series copolymer can be adjusted to required molecular weight by adjusting reaction temperature, time, quantity of solvent, the kind of catalyst or amount.
In this specification, the weight average molecular weight (Mw) of acrylic acid series copolymer is the value measured by following method.That is, it is measured by following (1)～(3).
(1) acrylic acid series copolymer solution is coated on releasing sheet (releasing sheet), make it dry 2 minutes at 100 DEG C, obtain membranaceous acrylic acid series copolymer.
(2) with oxolane, the membranaceous acrylic acid series copolymer obtained in above-mentioned (1) is dissolved as solid constituent 0.2 mass %.
(3) gel permeation chromatography (GPC) is used to measure the weight average molecular weight (Mw) of (methyl) acrylic acid series copolymer by following condition.
<condition>
GPC:HLC-8220GPC (TOSOH Co., Ltd. system)
Chromatographic column: TSK-GELGMHXL (uses 4)
Mobile phase solvent: oxolane
Standard specimen: polystyrene standard
Flow velocity: 0.6ml/min
Column temperature: 40 DEG C
-isocyanate-based cross-linking agent-
The polarization plates adhesive composite of the present invention contains at least one in isocyanate-based cross-linking agent.This cross-linking agent is the compound with polarity, when comprising the composition of this cross-linking agent, obtains the effect (prevent irregular colour (especially white macula) and improve durability) of the present invention further.
As isocyanate-based cross-linking agent, it is preferable that first phenylene diisocyanate based compound can be enumerated.As first phenylene diisocyanate based compound, it is possible to use the dimer of isocyanates or trimer, or the various toluene from isocyanates such as the adduct of isocyanates and trimethylolpropane polyhydric alcohol support diisocyanate cpds.
First phenylene diisocyanate based compound can use the commercially available product of listing, as the example of commercially available product, it is possible to uses " CORONATEL " (trade name) of Nippon Polyurethane Industry Co., Ltd. etc. well.
Content in the polarization plates adhesive composite of isocyanate-based cross-linking agent is set to the scope of below 20 mass parts relative to total amount 100 mass parts of acrylic acid series copolymer.If the content of isocyanate-based cross-linking agent is more than 20 mass parts; then cohesiveness becomes too much; be exposed to hot and humid under time and polarization plates (cellulose triacetate (TAC) especially as its protection sheet material) between zygosity easily decline, it is impossible to suppress peel off generation.Content as isocyanate-based cross-linking agent, it is preferred to the scope of 8～20 mass parts, more preferably the scope of 10～15 mass parts.When the content of isocyanate-based cross-linking agent is more than 8 mass parts, the shrinkage stress of the polarization plates after suppressing laminating bond layer is shown good cohesiveness, more efficiently suppresses the generation of white macula.
-epoxy cross-linking agent-
The polarization plates adhesive composite of the present invention comprises epoxy cross-linking agent while preferably comprising above-mentioned isocyanate-based cross-linking agent.When polarization plates adhesive composite comprises epoxy cross-linking agent, it is easy to adjust cohesiveness, also can suppress abnormal appearance under hot and humid.
Example as epoxy cross-linking agent, it is possible to enumerate 1,3-double; two (N, N-glycidyl aminomethyl) hexamethylene, N, N, N ', N '-four glycidyl group m-xylene diamine etc..
Additionally, epoxy cross-linking agent can use the commercially available product of listing, as the example of commercially available product, it is possible to use " TETRAD-X " of Mitsubishi Gas Chemical Co., Ltd, " TETRAD-C " (trade name) etc. well.
As the content in the polarization plates adhesive composite of epoxy cross-linking agent, relative to the total amount of acrylic acid series copolymer A and acrylic acid series copolymer B, it is preferred to the scope of 0.001～0.1 mass %.If the content of epoxy cross-linking agent is in above-mentioned scope, then can adjust the cohesiveness of bond layer, the stripping that can suppress in durability (humidity resistance) generation in consider to be advantageous for.
-silane coupler-
The polarization plates adhesive composite of the present invention preferably comprises silane coupler.When polarization plates adhesive composite comprises silane coupler, the display device (such as liquid crystal indicator) of polarization plates is installed if exposed to, under hot and humid environment, being not susceptible to peel off between bond layer and polarization plates or liquid crystal cells.The polarization plates adhesive composite of the present invention is thought of as preferably from the aspect of the engaging force that smooth glass display is good.
As silane coupler, for instance, it is possible to enumerate the silane compound containing polymerism unsaturated group such as vinyltrimethoxy silane, VTES and 3-methacryloxypropyl trimethoxy silane；The silane based compound containing sulfydryl such as 3-mercaptopropyi trimethoxy silane, 3-Mercaptopropyltriethoxysilane and 3-mercaptopropyi dimethoxymethylsilane；And 3-glycidoxypropyltrime,hoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane etc. have the silane compound of epoxy construction；The silane compound containing amino such as 3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane and N-(2-aminoethyl)-3-aminopropyltriethoxy dimethoxysilane；And three-(3-trimethoxy-silylpropyl) isocyanuric acid esters etc..They can be used alone one, it is also possible to combination uses two or more.
Silane coupler can use the commercially available product of listing, as the example of commercially available product, it is possible to uses " KBM-403 " (trade name) of Shin-Etsu Chemial Co., Ltd etc. well.
As the content in the polarization plates adhesive composite of silane coupler, total amount 100 mass parts relative to acrylic acid series copolymer A and acrylic acid series copolymer B, it is preferred to the scope of 0.01～2.0 mass %.If the content of silane coupler is in above-mentioned scope, then can improve the zygosity of bond layer further.
The polarization plates adhesive composite of the present invention is except mentioned component, it is possible to various additives or the solvents etc. such as further suitably combined with ultraviolet radiation absorbent.
< is with the polarization plates > of bonding agent
The polarization plates with bonding agent of the present invention is formed at the bond layer on polaroid at least provided with polaroid and by giving the polarization plates adhesive composite of the already described present invention and constitutes.
As polaroid, generally use such as polyvinyl alcohol (PVA) film etc..Polaroid such as can serve as the polarization plates such as constituted between protection sheet materials such as being maintained at cellulose triacetate (TAC) with 3-tier architecture (such as TAC/ polaroid/TAC).
At least one side by the polarization plates adhesive composite of the already described present invention gives the polarization plates to the such as 3-tier architecture of TAC/ polaroid/TAC is upper and arranges bond layer, thus making the polarization plates with bonding agent.In this case, it is also possible to compositions is given to polarization plates, but it is preferred that give to strippable protection sheet material (releasing sheet) when using.The imparting of polarization plates adhesive composite can be well carried out by employing the coating processes such as the infusion process of polarization plates adhesive composite of liquid, rubbing method, ink-jet method.Wherein, it is preferred to rubbing method.
Specifically; the polarization plates adhesive composite of the present invention is coated on protection sheet material (releasing sheet) so that it is dry, after protection sheet material forms bond layer; this bond layer is transferred in polarization plates and carries out ripening, thus making the polarization plates with bonding agent.
Give and the conditions at 70～120 DEG C to dry about 1～3 minute such as air drier are preferably used to the adhesive composite on protection sheet material (releasing sheet) and are dried.
And then, from the view point of the contact surface that protection is to bonded object, it is preferable that the exposed surface at the adhesive linkage being arranged in polarization plates is snugly arranged to the protection sheet material (releasing sheet) of protection exposed surface.As this protection sheet material, in order to easily carry out the stripping between adhesive linkage, it is preferred to use implemented, with releasing agents such as fluorine resin, paraffin, organosilicons, the synthetic resin sheet material such as polyester that the demoulding processes.When being attached at the glass plate etc. of display floater, protection sheet material is peeled off, makes the surface of the layer of adhesive material exposed be sealed at glass substrate etc..
Additionally, the surface (exposed surface) of the side at the bond layer being not provided with polarization plates can arrange the surface-protective sheet protecting this surface further.Surface-protective sheet is preferably used the bond processing protecting film etc. to the one side of PET film.
Thickness as bond layer, it does not have limit especially, with dried thickness gauge, it is preferred to 1～100 μm, more preferably 5～50 μm, more preferably 15～30 μm.
The polarization plates with bonding agent of the present invention is being sized to more than 19 inches wide (260mm × 415mm) and also can apply of liquid crystal cells of lamination.If liquid crystal cells be sized to more than 19 inches wide (260mm × 415mm), then the heat of polarization plates, humidity the caused expansion of impact, shrink and become big.Therefore, the conventional polarization plates with bonding agent 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., it is impossible to suppress the generation of " white macula " that produce at frame (ベ セ Le) periphery.On the other hand, the polarization plates with bonding agent of the present invention becomes the kind of the resin design so that copolymer and cross-linking agent and the composition that amount is suitable, therefore under hot and humid, stress is also fully suppressed, it is also suitable for the liquid crystal cells of the size of more than 19 inches wide (260mm × 415mm), in addition, even if being applied to be suppressed by the stress retentivity of appropriateness the generation of white macula less than the compact display apparatus (liquid crystal indicator) of 19 inches (and then, less than 10 inches).
< display device >
The display device of the present invention arranges the display floater of display image and is arranged at the constituting with the polarization plates of bonding agent of the already described present invention of at least one side of display floater.
As display floater, it is possible to enumerate and be sealed with the display panels of liquid-crystal compounds, organic EL display panel etc..
Example as the display device of the present invention, the liquid crystal indicator possessing following structure can be enumerated: the polarization plates with bonding agent of the present invention is configured at by bond layer in the way of each face contacts with the surface of display panels (surface of such as glass substrate) two sides 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, it is shown that the polarization plates adhesive composite of the present invention, with the polarization plates of bonding agent and display device and their optimal way.
< 1 > polarization plates adhesive composite, wherein, containing acrylic acid series copolymer A, acrylic acid series copolymer B and isocyanate-based cross-linking agent, aforesaid propylene acid based copolymer A comprises the construction unit from (methyl) alkyl acrylate and the construction unit from the monomer with carboxyl, and weight average molecular weight is 300000～700000；Aforesaid propylene acid based copolymer B comprise the construction unit from (methyl) alkyl acrylate, from have carboxyl monomer construction unit and from the construction unit of the monomer with hydroxyl, and weight average molecular weight is 1000000～2000000；The above-mentioned isocyanate-based cross-linking agent scope that content is below 20 mass parts relative to aforesaid propylene acid based copolymer A and total amount 100 mass parts of aforesaid propylene acid based copolymer B, the glass transition temperature (TgA) of the aforesaid propylene acid based copolymer A glass transition temperature (TgB) be more than or equal to aforesaid propylene acid based copolymer B.
< 2 > such as polarization plates adhesive composite described in above-mentioned < 1 >, wherein, the glass transition temperature (TgB) of aforesaid propylene acid based copolymer B is-50 DEG C～-40 DEG C.
Polarization plates adhesive composite described in < 3 > such as above-mentioned < 1 > or above-mentioned < 2 >, wherein, the ratio (MwA/MwB) of the weight average molecular weight (MwA) of the aforesaid propylene acid based copolymer A weight average molecular weight (MwB) relative to aforesaid propylene acid based copolymer B is less than 0.5.
Polarization plates adhesive composite according to any one of < 4 > such as above-mentioned < 1 >～above-mentioned < 3 >, wherein, the aforesaid propylene acid based copolymer A ratio (A/B) that contains relative to aforesaid propylene acid based copolymer B is calculated as 60/40～80/20 with quality criteria.
Polarization plates adhesive composite according to any one of < 5 > such as above-mentioned < 1 >～above-mentioned < 4 >, wherein, aforesaid propylene acid based copolymer A comprises the construction unit of the Arrcostab from (methyl) acrylic acid carbon number 1～4, from (methyl) acrylic acid construction unit, and the construction unit from the monomer that can form homopolymer, the absolute value of the glass transition temperature that this homopolymer has and the difference of the glass transition temperature of the polymer making the Arrcostab homopolymerization of above-mentioned (methyl) acrylic acid carbon number 1～4 and obtain is 30 DEG C～90 DEG C,
Aforesaid propylene acid based copolymer B comprises the construction unit of the Arrcostab from (methyl) acrylic acid carbon number 1～8, from (methyl) acrylic acid construction unit and the construction unit from (methyl) hydroxyalkyl acrylates.
< 6 > polarization plates with bonding agent, wherein, there is polaroid and be formed at the bond layer on above-mentioned polaroid by the polarization plates adhesive composite according to any one of imparting above-mentioned < 1 >～above-mentioned < 5 >.
< 7 > display device, wherein, the polarization plates with bonding agent described in above-mentioned < 6 > of the display floater possessing display image and at least one side being configured at display floater.
Embodiment
Hereinafter, specifically described the present invention further by embodiment, as long as but the present invention is then not limited to following example not past its purport.Should illustrating, unless otherwise specified then " part " is quality criteria.
(manufacturing example A1)
Add in the reactor possessing thermometer, blender, nitrogen ingress pipe and reflux cooling pipe n-butyl acrylate (BA) 79.0 mass parts, acrylic acid methyl ester. (MA) 20.0 mass parts, acrylic acid (AA) 1.0 mass parts, double; two methyl pentane nitrile (ABVN) 0.1 mass parts of ethyl acetate (EAc) 110 mass parts and azo and after mixing, to carrying 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, it is adjusted to solid constituent 37.0 mass % with diluted ethyl acetate reactant mixture.So, the solution (acrylic acid series copolymer A) of BA/MA/AA copolymer A 1 is obtained.
For the BA/MA/AA copolymer A 1 of gained, carried out the mensuration of weight average molecular weight (Mw) and the calculating of glass transition temperature (Tg) by method shown below.Result is shown in table 1 below.
Weight average molecular weight is to be measured with TSK-GELGMHXL (the styrenic filler of TOSOH) for chromatographic column by gel permeation chromatography (GPC) according to already described method, carries out polystyrene conversion and obtains.
Tg uses the calculating formula of already described glass transition temperature (Tg) and mole average glass transition temperature that calculates.
(manufacturing example A2～A11)
It is changed to as described in Table 1 by manufacturing the ratio being used for the n-butyl acrylate (BA) of synthesis of BA/MA/AA copolymer A 1, acrylic acid methyl ester. (MA) and acrylic acid (AA) in example A1, simultaneously by adjusting quantity of solvent or catalytic amount, it is as described in Table 1 by molecular-weight adjusting, in addition, the solution (acrylic acid series copolymer A) of BA/MA/AA copolymer A 2～A11 is obtained in the same manner as manufacturing example A1.
Additionally, for each copolymer, carry out the mensuration of Mw and the calculating of Tg in the same manner as manufacturing the copolymer A 1 of example A1.Result is shown in table 1 below.
(manufacturing example A12～A14)
It is changed to the composition monomer shown in table 2 below by manufacturing the n-butyl acrylate (BA), acrylic acid methyl ester. (MA) and the acrylic acid (AA) that are used for synthesizing in example A1 and synthesizes, obtained the solution (acrylic acid series copolymer A) of copolymer A 12～A11 by the method same with manufacturing example A1.
Additionally, for each copolymer, carry out the mensuration of Mw and the calculating of Tg in the same manner as manufacturing the copolymer A 1 of example A1.Result is shown in table 2 below.
(manufacturing example B1)
Add in the reactor possessing thermometer, blender, nitrogen ingress pipe and reflux cooling pipe n-butyl acrylate (BA) 89.0 mass parts, acrylic acid methyl ester. (MA) 9.5 mass parts, acrylic acid (AA) 1.0 mass parts, acrylic acid 2-hydroxy methacrylate (2HEA) 0.5 mass parts, double; two methyl pentane nitrile (ABVN) 0.03 mass parts of ethyl acetate (EAc) 90 mass parts and azo and after mixing, to carrying 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, it is adjusted to solid constituent 17.0 mass % with diluted ethyl acetate reactant mixture.So, the solution (acrylic acid series copolymer B) of BA/MA/AA/2HEA copolymer B1 is obtained.
Additionally, for copolymer B1, carry out the mensuration of Mw and the calculating of Tg in the same manner as manufacturing the copolymer A 1 of example A1.Result is shown in table 1 below.
(manufacturing example B2～B5, B7～B9)
It is changed to as described in Table 1 by manufacturing the ratio being used for the n-butyl acrylate (BA) of synthesis of BA/MA/AA/2HEA copolymer B1, acrylic acid methyl ester. (MA), acrylic acid (AA) and acrylic acid 2-hydroxy methacrylate (2HEA) in example B1, simultaneously by adjusting quantity of solvent or catalytic amount, it is as described in Table 1 by molecular-weight adjusting, in addition, the solution (acrylic acid series copolymer B) of BA/MA/AA/2HEA copolymer B2～B5, B7～B9 is obtained in the same manner as manufacturing example B1.
Additionally, for each copolymer, carry out the mensuration of Mw and the calculating of Tg in the same manner as manufacturing the copolymer B1 of example B1.Result is shown in table 1 below.
(manufacturing example B6)
It is changed to as described in Table 1 by manufacturing the ratio being used for the n-butyl acrylate (BA) of synthesis of BA/MA/AA/2HEA copolymer B1, acrylic acid (AA) and acrylic acid 2-hydroxy methacrylate (2HEA) in example B1, and acrylic acid methyl ester. (MA) 9.5 parts is replaced with 2-EHA (2EHA) 15 parts, simultaneously by adjusting quantity of solvent or catalytic amount, it is as described in Table 1 by molecular-weight adjusting, in addition, the solution (acrylic acid series copolymer B) of BA/2EHA/AA/2HEA copolymer B6 is obtained in the same manner as manufacturing example B1.
Additionally, for each copolymer, carry out the mensuration of Mw and the calculating of Tg in the same manner as manufacturing the copolymer B1 of example B1.Result is shown in table 1 below.
(manufacturing example B10～B13)
It is changed to the composition monomer shown in table 2 below by manufacturing the n-butyl acrylate (BA), acrylic acid methyl ester. (MA), acrylic acid (AA) and acrylic acid 2-hydroxy methacrylate (2HEA) that are used for synthesizing in example B1 and synthesizes, obtained the solution (acrylic acid series copolymer B) of copolymer B10～B13 by the method same with manufacturing example B1.
Additionally, for each copolymer, carry out the mensuration of Mw and the calculating of Tg in the same manner as manufacturing the copolymer B1 of example B1.Result is shown in table 2 below.
(embodiment 1)
-preparation of adhesive composite-
nullUsing the solution (solid constituent of BA/MA/AA copolymer: 70.0 mass parts) as the BA/MA/AA copolymer obtained in the above-mentioned manufacture example A1 of acrylic acid series copolymer A of 189.2 mass parts、176.5 the solution as the BA/MA/AA/2HEA copolymer B1 obtained in the above-mentioned manufacture example B1 of acrylic acid series copolymer B of mass parts (solid constituent of BA/MA/AA/2HEA copolymer: 30.0 mass parts)、CORONATEL as isocyanate compound (the isocyanates based compound of Japanese polyurethane industrial group of 20 mass parts，Effective ingredient: 15 mass parts)、The TETRAD-X as epoxide of the 0.02 mass parts (epoxide of Rhizoma Sparganii gas chemical company，Effective ingredient: 0.02 mass parts)、And 0.1 KBM-403 (silane coupler of chemical industrial company of SHIN-ETSU HANTOTAI as silane compound (SC agent) of mass parts，Effective ingredient: 0.1 mass parts) fully stirring be obtained by mixing adhesive composite.
Now, the molecular weight ratio (MwA/MwB) of the weight average molecular weight (MwB) of the weight average molecular weight (MwA) of BA/MA/AA copolymer A 1 (acrylic acid series copolymer A) and BA/MA/AA/2HEA copolymer (acrylic acid series copolymer B) is 0.33, for Tg, acrylic copolymer A is higher than acrylic acid series copolymer B.
-making of optical film sample-
By adhesive composite with dried coating weight for 25g/cm2Mode coat with silicon-type releasing agent carried out surface treatment stripping film releasing agent process face.Then, use hot air circulation type drying machine to make it dry 90 seconds at 100 DEG C, stripping film is formed bond layer.It follows that polarisation basement membrane (is pressed on cellulose triacetate (TAC) rete the two sides of the polaroid based on polyvinyl alcohol (PVA) film and has the polarisation basement membrane of the laminar structure of TAC film/PVA film/TAC film；About 190 μm) back side laminating overlapping with the surface of above-mentioned bond layer, by niproll and the pressing of pressurizeing.After pressing, 23 DEG C, ripening 10 days under the environmental condition of 65%RH, make the polarizing coating of the laminar structure with stripping film/bond layer/polarisation basement membrane as optical film sample.
-evaluate-
Use the polarizing coating of above-mentioned making, carry out following evaluation.Evaluation result is shown in table 1 below.
(1) cohesiveness
By with the JISZ0237 method being benchmark, measuring the value (angle=30 ° of hang plate) of tilting Rolling Ball Tack, it is 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) durability
(2-1) 4.3 inches (dry (Dry), wet (Wet))
Preparation by the polarizing coating made in above-mentioned " making of optical film sample " relative to the test film (4.3 inches) absorbing 54mm × 96mm (long limit) that the mode that the long limit of axle is 45 ° is cut, stripping film is peeled off from this test film.The surface of the layer of adhesive material by exposing due to stripping is closely sealed with the one side of the alkali-free glass plate (#1737, CORNING company system) of 0.7mm, and test film is overlapped on glass plate, uses laminating machine to carry out attaching and making layered product.Then, this layered product execution autoclave is processed (50 DEG C, 5kg/cm2, 20 minutes), 23 DEG C, 65%RH when place 24 hours.Thereafter, under wet (WET) environment (60 DEG C, 90%RH) of dry (Dry) environment (80 DEG C, 0%RH) of high temperature low humidity conditions and hot and humid condition, 500 hours are placed respectively.After standing time, the state being foamed by visualization, peeling off, it is evaluated according to following metewand.
<metewand>
A: do not observe foaming completely, peel off.
B: be barely perceivable foaming, peel off.
C: observe some foaming, stripping.
D: observe obvious foaming, stripping.
(2-2) 19 inches (dry (Dry), wet (Wet))
The dimension modifying of the test film except being obtained by cutting polarizing coating in above-mentioned " (2-1) 4.3 inches (dry (Dry); wet (Wet)) " is beyond 240mm × 427mm (19 inches), by being evaluated with " (2) durability (4.3 inches: dry (Dry), wet (Wet)) " same method.
(3) irregular colour
(3-1) white macula 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 polarizing coating of same size, alkali-free glass plate (the #1737 of 0.7mm it is attached in the mutually perpendicular mode of polarizing axis, CORNING company system) two sides, make test specimen.Then, this test specimen execution autoclave is processed (50 DEG C, 5kg/m2, 20 minutes), 23 DEG C, 50%RH when place 24 hours.Thereafter, place 500 hours under dry environment (70 DEG C, 0%RH).After placement, 23 DEG C, 50%RH when be respectively placed on the backlight of liquid crystal display, with the state of visualization white macula.
<metewand>
A: do not observe white macula completely.
B: be barely perceivable white macula.
C: observe some white maculas.
D: observe a lot of white macula.
(3-2) white macula phenomenon (7 inches)
The dimension modifying of the test film except being obtained by cutting polarizing coating in above-mentioned " (3-1) white macula phenomenon (4.3 inches) " is evaluated with the method same with " (3-1) white macula phenomenon (4.3 inches) " except being 88mm × 156mm (7.0 inches).
(3-3) white macula phenomenon (19 inches)
The dimension modifying of the test film except being obtained by cutting polarizing coating in above-mentioned " (3-1) white macula phenomenon (4.3 inches) " is evaluated with the method same with " (3-1) white macula phenomenon (4.3 inches) " except being 240mm × 427mm (19 inches).
(embodiment 2～21, comparative example 1～6)
Except by the monomer composition of acrylic acid series copolymer in embodiment 1 or physical property (Tg, Mw), weight average molecular weight, being changed to containing ratio, cross-linked dosage as shown in table 1 below～table 2 of acrylic acid series copolymer A, B, prepare adhesive composite similarly to Example 1, make polarizing coating, be evaluated simultaneously.
[table 1]
[table 2]
As the above Table 1 to Table 2, in embodiment, unrelated with DRY environment and wet (WET) environment, foaming or the generation peeled off can be suppressed, good durability can be obtained.Additionally, unrelated with the size of size, it is possible to effectively suppress the generation of white macula.Additionally, there is no being involved in of the bubble easily produced when laminating, it is shown that good cohesiveness.
Full content disclosed in Japanese publication 2012-128291 is incorporated by reference into the present specification.
Situation equal extent ground with being concrete by referring to each document of introducing, patent application and technical standard and be each described, is incorporated by reference into the present specification whole documents, patent application and the technical standard recorded in this specification.

Claims (7)

1. a polarization plates adhesive composite, wherein, contains:
Acrylic acid series copolymer A, it comprises the construction unit from (methyl) alkyl acrylate and the construction unit from the monomer with carboxyl, and weight average molecular weight is 300000～700000；
Acrylic acid series copolymer B, its comprise the construction unit from (methyl) alkyl acrylate, from have carboxyl monomer construction unit and from the construction unit of the monomer with hydroxyl, and weight average molecular weight is 1000000～2000000；And
Isocyanate-based cross-linking agent, the scope that content is below 20 mass parts of its total amount 100 mass parts relative to described acrylic acid series copolymer A and described acrylic acid series copolymer B,
The glass transition temperature Tg A of described acrylic acid series copolymer A is be more than or equal to the glass transition temperature Tg B of described acrylic acid series copolymer B.
2. polarization plates adhesive composite as claimed in claim 1, wherein, the glass transition temperature Tg B of described acrylic acid series 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 the described acrylic acid series copolymer A ratio MwA/MwB relative to the weight average molecular weight MwB of described acrylic acid series copolymer B is less than 0.5.
4. polarization plates adhesive composite as claimed in claim 1 or 2, wherein, described acrylic acid series copolymer A is calculated as 60/40～80/20 relative to the ratio A/B that contains of described acrylic acid series copolymer B with quality criteria.
5. polarization plates adhesive composite as claimed in claim 1 or 2, wherein,
Described acrylic acid series copolymer A comprises the construction unit of the Arrcostab from (methyl) acrylic acid carbon number 1～4, from (methyl) acrylic acid construction unit and the construction unit from the monomer that can form homopolymer, the absolute value of the difference of the glass transition temperature of the polymer that the glass transition temperature that this homopolymer has carries out homopolymerization with the Arrcostab making described (methyl) acrylic acid carbon number 1～4 and obtains is 30 DEG C～90 DEG C
Described acrylic acid series copolymer B comprises the construction unit of the Arrcostab from (methyl) acrylic acid carbon number 1～8, from (methyl) acrylic acid construction unit and the construction unit from (methyl) hydroxyalkyl acrylates.
6. with a polarization plates for bonding agent, wherein, there is polaroid and require that the polarization plates adhesive composite according to any one of 1～5 is formed at the bond layer on described polaroid by entitle.
7. a display device, wherein, possesses the display floater demonstrating image and is configured at the polarization plates with bonding agent described in claim 6 at least simultaneously of display floater.
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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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015151173A1 (en) * 2014-03-31 2015-10-08 株式会社寺岡製作所 Adhesive composition, and adhesive tape using same
JP6484484B2 (en) * 2015-03-30 2019-03-13 日本カーバイド工業株式会社 Adhesive composition and adhesive sheet
JP6511659B2 (en) * 2015-06-08 2019-05-15 藤森工業株式会社 Pressure-sensitive adhesive layer for optical film, and pressure-sensitive adhesive film for optical film
TWI745316B (en) 2015-11-25 2021-11-11 日商理研科技股份有限公司 Door
WO2017141449A1 (en) 2016-02-19 2017-08-24 リケンテクノス株式会社 Pressure-sensitive adhesive and articles including same
JP6497476B1 (en) * 2018-09-20 2019-04-10 東洋インキＳｃホールディングス株式会社 Adhesive and adhesive sheet
JP7402769B2 (en) * 2020-09-07 2023-12-21 日本カーバイド工業株式会社 Adhesive composition for vehicle protection film and vehicle protection film
JP7540121B2 (en) 2020-11-19 2024-08-27 アルプスアルパイン株式会社 Display device
JP2022179183A (en) * 2021-05-21 2022-12-02 日東電工株式会社 Adhesive sheet, optical laminate and image display device
CN118055991A (en) * 2021-10-18 2024-05-17 大塚化学株式会社 Adhesive material and adhesive sheet

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010024103A1 (en) * 2008-09-01 2010-03-04 日本カーバイド工業株式会社 Pressure-sensitive adhesive composition, pressure-sensitive adhesive and optical film
CN102108272A (en) * 2009-12-28 2011-06-29 琳得科株式会社 Pressure sensitive adhesive composition, pressure sensitive adhesive and pressure sensitive adhesive sheet
JP2011231190A (en) * 2010-04-26 2011-11-17 Nippon Carbide Ind Co Inc Adhesive composition for polarizing plate, and adhesive-adhered polarizing plate and liquid crystal display device each using the same
WO2012026456A1 (en) * 2010-08-24 2012-03-01 日本カーバイド工業株式会社 Adhesive agent composition

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3594206B2 (en) * 1995-09-14 2004-11-24 日本化薬株式会社 Optical adhesive composition
JP3533589B2 (en) 1997-04-09 2004-05-31 綜研化学株式会社 Pressure-sensitive adhesive composition for polarizing plate and polarizing plate
JP2000109771A (en) * 1998-10-07 2000-04-18 Lintec Corp Adhesive sheet
JP2004323543A (en) * 2003-04-21 2004-11-18 Nitto Denko Corp Pressure-sensitive adhesive composition for optical member, pressure-sensitive adhesive layer for optical member, adherent optical member and image display device
JP4519572B2 (en) * 2004-08-26 2010-08-04 日東電工株式会社 Optical member pressure-sensitive adhesive composition, optical member pressure-sensitive adhesive layer and method for producing the same, pressure-sensitive adhesive layer-attached optical member, and image display device
KR100668943B1 (en) * 2004-04-23 2007-01-12 주식회사 엘지화학 Acrylic Pressure-Sensitive Adhesive Composition for the Polarizing Film
JP5269282B2 (en) * 2004-08-11 2013-08-21 住友化学株式会社 Adhesive
JP2006309114A (en) * 2005-03-30 2006-11-09 Lintec Corp Pressure-sensitive adhesive for polarizing plates, polarizing plate having pressure-sensitive adhesive, and production process for polarizing plate
KR101202518B1 (en) * 2008-01-15 2012-11-16 주식회사 엘지화학 Pressure-sensitive adhesive composition, polarizers and liquid crystal display comprising the same
KR20100059470A (en) * 2008-11-26 2010-06-04 도레이첨단소재 주식회사 Adhesive composition for controlling light-leak phenomena and optical film for display device coated by the same
JP5800363B2 (en) * 2009-03-16 2015-10-28 電気化学工業株式会社 Adhesive and adhesive sheet
JP2011038055A (en) * 2009-08-18 2011-02-24 Nippon Carbide Ind Co Inc Adhesive composition and optical film
JP5465079B2 (en) 2010-04-26 2014-04-09 日本カーバイド工業株式会社 Adhesive composition for polarizing plate, polarizing plate with adhesive and liquid crystal display device using the same
KR101351621B1 (en) * 2010-12-29 2014-01-15 제일모직주식회사 Adhesive Composition and Optical Member Using the Same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010024103A1 (en) * 2008-09-01 2010-03-04 日本カーバイド工業株式会社 Pressure-sensitive adhesive composition, pressure-sensitive adhesive and optical film
CN102108272A (en) * 2009-12-28 2011-06-29 琳得科株式会社 Pressure sensitive adhesive composition, pressure sensitive adhesive and pressure sensitive adhesive sheet
JP2011231190A (en) * 2010-04-26 2011-11-17 Nippon Carbide Ind Co Inc Adhesive composition for polarizing plate, and adhesive-adhered polarizing plate and liquid crystal display device each using the same
WO2012026456A1 (en) * 2010-08-24 2012-03-01 日本カーバイド工業株式会社 Adhesive agent composition

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