CN103168083A - Adhesive composition for optical components, adhesive for optical components, optical component with adhesive layer, and image display device - Google Patents

Adhesive composition for optical components, adhesive for optical components, optical component with adhesive layer, and image display device Download PDF

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Publication number
CN103168083A
CN103168083A CN2011800495954A CN201180049595A CN103168083A CN 103168083 A CN103168083 A CN 103168083A CN 2011800495954 A CN2011800495954 A CN 2011800495954A CN 201180049595 A CN201180049595 A CN 201180049595A CN 103168083 A CN103168083 A CN 103168083A
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China
Prior art keywords
optical component
methyl
monomer
binder layer
weight
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CN2011800495954A
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CN103168083B (en
Inventor
池端晃
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Mitsubishi Kasei Corp
Sumitomo Chemical Co Ltd
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Nippon Synthetic Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • 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
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers

Abstract

The present invention provides an adhesive composition for optical components that is capable of achieving both reworkability and durability and that is capable of inhibiting unevenness in color and light leakage when applied to image display devices such as liquid crystal display panels. The present invention relates to an adhesive composition for optical components that contains an acrylic resin (A) obtained by copolymerizing a copolymerization component [I] containing, as the principal component thereof, an alkyl (meth)acrylate ester monomer (a1), wherein the adhesive composition is characterized by containing a N-(alkoxyalkyl)(meth)acrylamide monomer (a2) as the copolymerization component [I].

Description

Optical component with binder composition, optical component with tackiness agent, with optical component and the image display device of binder layer
Technical field
The present invention relates to optical component with binder composition, optical component with tackiness agent, with optical component and the image display device of binder layer.specifically, relate to and be suitable for liquid crystal indicator, organic EL display, PDP(plasma display panel) optical thin film (polarizing film of image display device such as, phase-contrast film, optical compensating film, film adds lustre to) etc. optical component, more specifically, relate to the optical component binder composition for the glass substrate of bonding optical laminate by the protective films such as cellulosetri-acetate class film covering polarizing film and liquid crystal cells, the optical component tackiness agent that this binder composition cross-links forms, be formed with and comprise this optical component with the optical component with binder layer of the binder layer of tackiness agent, especially with the Polarizer of binder layer, and then contain this with the image display device of the optical component of binder layer.
Background technology
Up to now; carried out on the surface with the liquid crystal cells of the stacked liquid crystal composition that is to have between two sheet glass orientation of Polarizer; thereby make the research of LCD panel; described Polarizer covers the polaroids such as polyvinyl alcohol film given polarity etc. with protective membranes such as cellulose family films two sides forms, to the stacked binder layer by will be arranged at the Polarizer surface usually of this liquid crystal cells face with the surperficial butt of above-mentioned liquid crystal cells and press to carry out.
For the tackiness agent that forms this binder layer, require because of the error that adds man-hour, impurity sneak into optical components such as causing Polarizer when peeling off from liquid crystal cells, can be without cull and the re-workability of easily peeling off (releasable).In addition, when exposing to the open air for a long time, produce sometimes tackiness agent causes peel off, bubble under the environment of the harshnesses such as high temperature, high humidity, the tackiness agent for forming described binder layer also requires weather resistance.And then, because of Polarizer through the time when producing dimensional change, the dimensional change of following Polarizer due to described binder layer produces distortion, polymer moieties ground in binder layer is orientated, double refraction occurs thus, and the peripheral part that causes occuring LCD panel is brighter or more secretly wait irregular colour, light leakage phenomena than central authorities.Therefore, for the tackiness agent that forms this binder layer, also requirement can suppress irregular colour, the light leakage phenomena that the stress because of the dimensional change that is accompanied by the optical components such as Polarizer produces.
To address the above problem as purpose, disclose a kind of adhesive of optical film composition that makes (methyl) acrylic polymers that tertiary-amino-containing monomer (with reference to acrylate, the acrylamide of the 0036th section record of same document) copolymerization forms that contains in patent documentation 1, disclose a kind of adhesion type Polarizer that is laminated with the acrylic adhesives layer that contains specific silane coupling agent in patent documentation 2.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2009-215528 communique
Patent documentation 2: Japanese kokai publication hei 9-288214 communique
Summary of the invention
The problem that invention will solve
Yet, for patent documentation 1, the prior aries such as 2, be difficult to reach taking into account of weather resistance when exposing to the open air for a long time to re-workability with under high temperature, high humidity, weather resistance variation when existing re-workability to improve, the such problem of re-workability variation when weather resistance improves on the other hand also have the space of further improving.
The present invention In view of the foregoing makes, and its purpose is to provide the optical component binder composition of taking into account and can suppress when being applied to the image display devices such as LCD panel irregular colour, light leakage phenomena that can reach re-workability and weather resistance; The optical component tackiness agent that this binder composition cross-links forms; Be formed with and comprise this optical component with the optical component with binder layer of the binder layer of tackiness agent; Contain this with the image display device of the optical component of binder layer.
For the scheme of dealing with problems
The inventor conducts in-depth research in view of above-mentioned practical situation, found that by using with the N-(alkoxyalkyl) (methyl) acrylamide monomers is as the acrylic resin of copolymer composition, can reach taking into account re-workability and weather resistance, and can suppress irregular colour, light leakage phenomena when being applied to image display device, thereby completed the present invention, wherein, described N-(alkoxyalkyl) (methyl) acrylamide monomers is (methyl) acrylamide monomers, and is bonded to the alkyl chain alkoxy replacement of the nitrogen-atoms of amido linkage.
Namely, main idea of the present invention relates to the optical component binder composition, it is characterized in that, it is to contain the acrylic resin (A) that copolymer composition [I] copolymerization take (methyl) alkyl-acrylates monomer (a1) as main component is obtained to form, and contains the N-(alkoxyalkyl) (methyl) acrylamide monomers (a2) is as copolymer composition [I].
And then, also relate to optical component that above-mentioned optical component forms with binder composition cross-links with tackiness agent, comprise described optical component with the formed optical component with binder layer of the binder layer of tackiness agent, contain the image display device of described optical component with binder layer.
The present invention comprises following embodiment.
[1] a kind of optical component binder composition, it is characterized in that, it is to contain the copolymer composition [I] take (methyl) alkyl-acrylates monomer (a1) as main component is carried out the acrylic resin (A) that copolymerization obtains to form, and contains the N-(alkoxyalkyl) (methyl) acrylamide monomers (a2) is as copolymer composition [I].
[2] optical component binder composition described according to [1], is characterized in that, it contains to be selected from and contains aromatic nucleus monomer (a3) and contain at least a as copolymer composition [I] of carboxylic monomer (a4).
[3] optical component binder composition described according to [1] or [2], is characterized in that, it contains linking agent (B) and forms.
[4] according to the described optical component binder composition of any one in [1]～[3], it is characterized in that, it contains silane coupling agent (C) and forms.
[5] a kind of optical component tackiness agent, is characterized in that, it is that the described optical component of any one in [1]～[4] forms with binder composition cross-links.
[6] optical component tackiness agent described according to [5], is characterized in that, optical component is Polarizer.
[7] a kind of optical component with binder layer, is characterized in that, it comprises the stepped construction of binder layer and optical component, and described binder layer comprises [5] or [6] described optical component tackiness agent.
[8] a kind of image display device, is characterized in that, it contains [7] described optical component with binder layer.
[9] optical component with binder layer described according to [7], is characterized in that, optical component is Polarizer.
The effect of invention
The optical component that optical component of the present invention obtains with binder composition cross-links is excellent with the re-workability of tackiness agent, therefore because of the error that adds man-hour, impurity sneak into optical components such as causing Polarizer when peeling off from liquid crystal cells etc., can be without cull and easily peel off.In addition, excellent in te pins of durability when tackiness agent of the present invention exposes to the open air under high temperature, high humidity for a long time, even therefore under the environment of high temperature, high humidity and under the environmental change of repetition low temperature～high temperature, can obtain being difficult between excellent in adhesion, binder layer between optical laminate, particularly Polarizer and glass substrate and glass substrate the image display device that produces foaming, peel off.And then, for be formed with the binder layer that comprises tackiness agent of the present invention with for the optical component of binder layer, even because of optical component through the time when producing dimensional change, due to the double refraction that can make binder layer near 0, therefore for containing this image display device with the optical component of binder layer, can suppress irregular colour, light leakage phenomena.
Embodiment
Below the present invention is described in detail, an example of desirable embodiment is shown.Need to prove, in the present invention, (methyl) vinylformic acid refers to acrylic or methacrylic acid, and (methyl) acryl refers to acryl or methacryloyl, and (methyl) acrylate refers to acrylate or methacrylic ester.
[optical component binder composition]
At first, describe with binder composition (below, also referred to as " binder composition ") about optical component of the present invention.
Binder composition of the present invention is to contain the composition that acrylic resin (A) forms.
In the present invention, acrylic resin (A) used is take (methyl) alkyl-acrylates monomer (a1) as main component, and then containing the N-(alkoxyalkyl) (methyl) acrylamide monomers (a2) is as essential component, the copolymer composition [I] that preferably, will contain aromatic nucleus monomer (a3) and/or contain carboxylic monomer (a4) carries out the material that copolymerization forms.
as this (methyl) alkyl-acrylates monomer (a1), the carbonatoms of alkyl is preferably 1～20 usually, be particularly preferably 1～12, , more preferably 1～8, , especially be preferably 4～8, particularly can list (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid n-propyl, the just own ester of (methyl) vinylformic acid, (methyl) ethyl acrylate, (methyl) vinylformic acid n-octyl, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) vinylformic acid cetyl, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate etc.These can be used alone or be used in combination of two or more.
Be somebody's turn to do in (methyl) alkyl-acrylates monomer (a1), from copolymerizable, bonding physical property, easily process and viewpoint that raw material easily obtains, preferred (methyl) n-butyl acrylate, (methyl) ethyl acrylate of using, from the viewpoint of excellent in te pins of durability, further preferably use (methyl) n-butyl acrylate.
Refer to take (methyl) alkyl-acrylates monomer (a1) " as main component ", overall with respect to copolymer composition [I], contain above (methyl) alkyl-acrylates monomer (a1) of 50 % by weight.Should (methyl) alkyl-acrylates monomer (a1) ratio is preferably 50～97 % by weight, is particularly preferably 60～95 % by weight, 80～93 % by weight more preferably with respect to overall the containing of copolymer composition [I].
Should (methyl) alkyl-acrylates monomer (a1) contain ratio when very few, bonding hypodynamic tendency is arranged when using as tackiness agent making binder composition cross-links.
as the N-(alkoxyalkyl) (methyl) acrylamide monomers (a2), the carbonatoms of alkoxyl group is preferably 1～10 usually, be particularly preferably 1～8, , more preferably 1～6, especially be preferably 1～4, the carbonatoms of alkyl is preferably 1～6 usually, be particularly preferably 1～4, more preferably 1～2, especially be preferably 1, particularly, for example can list the N-(methoxymethyl) (methyl) acrylamide, N-(n-butoxy methyl) (methyl) acrylamide, N-(isobutoxy methyl) (methyl) acrylamide, N-(n-butoxy ethyl) (methyl) acrylamide etc., from weather resistance, the viewpoint of the balance excellence of re-workability is considered, the preferred N-(n-butoxy methyl that uses in these) acrylamide, the N-(methoxymethyl) acrylamide, N-(isobutoxy methyl) acrylamide.These can be used alone or be used in combination of two or more.
This N-(alkoxyalkyl) ratio is preferably 0.1～3 % by weight, is particularly preferably 0.3～2 % by weight (methyl) acrylamide monomers (a2), 0.3～1 % by weight more preferably with respect to overall the containing of copolymer composition [I].
This N-(alkoxyalkyl) (methyl) acrylamide monomers (a2) contain ratio when very few, the tendency that causes weather resistance and re-workability to descend because force of cohesion is not enough is arranged, have viscosity to uprise in the time of too much or the tendency of the stability decreases of resin.
As containing aromatic nucleus monomer (a3), such as listing (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) vinylformic acid phenoxy ethyl, the adjacent phenyl phenyl ester of ethoxyquin (methyl) vinylformic acid, (methyl) vinylformic acid diethylamino phenyl diol ester, (methyl) vinylformic acid-2-hydroxyl-3-phenoxy group propylene, vinylbenzene, alpha-methyl styrene etc., among these, consider preferred vinylformic acid diethylamino phenyl diol ester, the vinylformic acid phenoxy ethyl used from the viewpoint of anti-light leak excellence.These can be used alone or be used in combination of two or more.
Ratio is preferably 3～20 % by weight, is particularly preferably 3～15 % by weight, 5～15 % by weight more preferably with respect to overall the containing of copolymer composition [I] to contain aromatic nucleus monomer (a3).
What contain aromatic nucleus monomer (a3) contains ratio when very few, and the tendency that has anti-light leak (performance that suppresses light leak) easily to descend has the bonding physical property variation of anti-light leak decline, acrylic resin or the tendency that polymerization stability descends in the time of too much.
As containing carboxylic monomer (a4), such as listing (methyl) vinylformic acid, acrylic acid dimer, β-crotonic acid, toxilic acid, maleic anhydride, fumaric acid, citraconic acid, propene dicarboxylic acid, methylene-succinic acid, acrylamide-N-glycolic acid, TRANSCINNAMIC ACID etc., wherein preferably use (methyl) vinylformic acid.These can be used alone or be used in combination of two or more.
Contain carboxylic monomer (a4) with respect to copolymer composition [I] overall contain ratio be preferably 1.5 % by weight following, be particularly preferably 0.05～1 % by weight, 0.05～0.6 % by weight more preferably.
What contain carboxylic monomer (a4) contains ratio when very few, and the tendency that has the force of cohesion deficiency to cause endurance quality to descend has viscosity to uprise in the time of too much or the tendency of the bad stability of resin.
Acrylic resin (A) used in the present invention can also be with other co-polymerized monomers (a5) as copolymer composition [I] on the basis of the monomer of above-mentioned (a1)～(a4).As these other co-polymerized monomers (a5); such as listing hydroxyl monomer, emulsion stability, contain acetoacetyl (acetoacetyl) monomer, contain isocyanate-monomer, containing glycidyl monomer etc.; among these; consider from the viewpoint that can carry out efficiently crosslinking reaction, preferably use the hydroxyl monomer.
as the hydroxyl monomer, for example can list (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-4-hydroxyl butyl ester, (methyl) vinylformic acid-5-hydroxyl pentyl ester, (methyl) vinylformic acid-own ester of 6-hydroxyl, (methyl) vinylformic acid-vinylformic acid hydroxyalkyl acrylates such as 8-hydroxyl monooctyl ester, the caprolactone modification monomers such as caprolactone modification (methyl) 2-Hydroxy ethyl acrylate, Diethylene Glycol (methyl) acrylate, the oxyalkylene modified monomers such as polyoxyethylene glycol (methyl) acrylate, and 2-acryloxy ethyl-2-hydroxyethyl phthalic acid, N-methylol (methyl) acrylamide etc. contains primary hydroxy monomers, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-2-hydroxyl butyl ester, (methyl) vinylformic acid-2-hydroxyl-3-phenoxy group propyl ester, (methyl) vinylformic acid-3-chlorine-2-hydroxyl propyl ester, (methyl) vinylformic acid-2-hydroxyl-3-phenoxy group propyl ester etc. contains the secondary hydroxyl monomer, (methyl) vinylformic acid-2, and 2-dimethyl-2-hydroxy methacrylate etc. contains the tert-hydroxyl monomer.
Among the hydroxyl monomer, from considering with the reactive excellent viewpoint of linking agent, preferably contain primary hydroxy monomers.And then viewpoint few from impurity such as two (methyl) acrylate and that be easy to make is considered, particularly preferably uses 2-Hydroxy ethyl acrylate, vinylformic acid-4-hydroxyl butyl ester.
In addition, as the hydroxyl monomer that uses in the present invention, preferred use is the following material of 0.5 % by weight as the ratio that contains of two (methyl) acrylate of impurity, more preferably below 0.2 % by weight, especially be preferably below 0.1 % by weight, particularly, preferably use 2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, vinylformic acid-4-hydroxyl butyl ester.
As emulsion stability, such as listing (methyl) vinylformic acid tertiary butyl amino ethyl ester, (methyl) vinylformic acid ethylamino ethyl ester, (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester etc.
As containing the acetoacetyl monomer, such as listing (methyl) vinylformic acid-2-(acetoacetoxy groups) ethyl ester, acetoacetic acid allyl ester etc.
As containing the isocyanate group monomer, such as listing 2-acrylyl oxy-ethyl isocyanic ester, 2-methylacryoyloxyethyl isocyanic ester, their oxyalkylene affixture etc.
As containing the glycidyl monomer, such as listing (methyl) glycidyl acrylate, (methyl) vinylformic acid allyl glycidyl etc.
other examples as other co-polymerized monomers (a5), can list (methyl) vinylformic acid-2-methoxyl group ethyl ester, (methyl) vinylformic acid-2-ethoxy ethyl ester, (methyl) vinylformic acid-3-methoxyl group butyl ester, (methyl) vinylformic acid-2-butoxyethyl, (methyl) vinylformic acid-2-butoxy binaryglycol ester, methoxyl group Diethylene Glycol (methyl) acrylate, methoxyl group triethylene glycol (methyl) acrylate, oxyethyl group Diethylene Glycol (methyl) acrylate, methoxyl group dipropylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, octyloxy polyethylene glycol-propylene glycol-list (methyl) acrylate, bay oxygen base polyethyleneglycol (methyl) acrylate, stearic oxygen base polyethyleneglycol (methyl) acrylate etc. contains the monomer of alkoxyl group and oxyalkylene group,
Vinyl cyanide, methacrylonitrile, vinyl-acetic ester, propionate, stearic acid vinyl ester, vinylchlorid, vinylidene chloride, alkyl vinyl ether, Vinyl toluene, vinyl pyridine, vinyl pyrrolidone, methylene-succinic acid dialkyl, dialkyl fumarate, vinyl carbinol, acrylate chloride, methyl vinyl ketone, N acrylamide methyl trimethoxy ammonium chloride, allyl group trimethyl ammonium chloride, dimethyl-allyl vinyl ketone etc.
Other co-polymerized monomers (a5) with respect to copolymer composition [I] overall contain ratio be preferably 5 % by weight following, be particularly preferably 0.5～3 % by weight, 0.4～1.6 % by weight more preferably.
Other co-polymerized monomers (a5) contain ratio when too much, having becomes is difficult to obtain the tendency of effect of the present invention.
For the present invention, as other co-polymerized monomers (a5), can also be used in combination the N-(alkoxyalkyl in the scope of not damaging effect of the present invention) (methyl) acrylamide monomers (a2) amides monomer (the amides monomer that does not namely have alkoxyalkyl, such as (methyl) acryloyl morpholine, dimethyl (methyl) acrylamide, diethyl (methyl) acrylamide, dimethylamino (methyl) acrylamide, dimethylaminopropyl (methyl) acrylamide etc.) in addition is as copolymer composition [I].
In addition, be used in combination the N-(alkoxyalkyl) in (methyl) acrylamide monomers (a2) situation of amides monomer as above-mentioned co-polymerized monomer (a5) in addition, its content totally is generally 0.1～2 % by weight, is preferably that 0.3～1 % by weight is following to be got final product with respect to copolymer composition [I], perhaps with respect to the N-(alkoxyalkyl) (methyl) acrylamide monomers (a2) is 0～100 % by weight, be preferably 0～50 % by weight, be particularly preferably 0～20 % by weight gets final product.
In addition, N-(alkoxyalkyl) (methyl) acrylamide monomers (a2) and contain carboxylic monomer (a4) always contain ratio with respect to copolymer composition [I] totally be preferably 4 % by weight following, be particularly preferably 0.3～2 % by weight, 0.4～1.6 % by weight more preferably.
Should (a2) and (a4) always contain ratio when too much, have the viscosity tendency of stability decreases of too high or resin that becomes.
When turning to purpose with the high molecular of the acrylic resin (A) that used in the present invention, can be used in combination ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, Vinylstyrene etc. and have compound of 2 above ethylenically unsaturated groups etc.
For the present invention, by will contain at least above-mentioned (a1) and monomer (a2), further contain the monomer that is preferably (a3), (a4), as required the copolymer composition [I] of monomer of (a5) carries out copolymerization, thereby make acrylic resin (A), this copolymerization can be undertaken by the existing known method such as solution free radical polymerization, suspension polymerization, mass polymerization, letex polymerization.For example, mix in the organic solvent or drip (methyl) alkyl-acrylates monomer (a1), N-(alkoxyalkyl) (methyl) acrylamide monomers (a2), contain aromatic nucleus monomer (a3), contain carboxylic monomer (a4), polymerizable monomer, the polymerization starter such as other co-polymerized monomers (a5), and with reflux state or 50～90 ℃ of lower polymerizations 2～20 hours.
As the organic solvent that uses in this polymerization, can list toluene, dimethylbenzene etc. aromatic hydrocarbon based; The ester such as ethyl acetate, butylacetate class, the aliphatics alcohols such as n-propyl alcohol, Virahol; The ketones such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone etc.
As the polymerization starter in this free-radical polymerized middle use, can list peroxide polymerization starters such as azo polymerization starter, benzoyl peroxide, lauroyl peroxide, ditertiary butyl peroxide, isopropyl benzene hydroperoxide such as Diisopropyl azodicarboxylate as common radical polymerization initiator, the two methyl pentane nitriles of azo etc. as concrete example.
The weight-average molecular weight (Mw) of acrylic resin (A) is generally 400,000～2,000,000, is preferably 450,000～1,900,000, is particularly preferably 500,000～1,800,000.When weight-average molecular weight was too small, the tendency that has endurance quality to reduce had the Macrodilution of needs solvent, is not preferred tendency from coating, cost aspect consideration when excessive.
In addition, the dispersity of acrylic resin (A) (weight-average molecular weight (Mw)/number-average molecular weight (Mn)) is preferably below 20, is particularly preferably below 15, more preferably below 10, especially is preferably below 7.When this dispersity is too high, have the endurance quality reduction of binder layer, the tendency that becomes and easily bubble.Wherein, the lower limit of dispersity is generally 2 from the viewpoint of manufacturing limit.
And then the second-order transition temperature of acrylic resin (A) is preferably-80～-20 ℃, is particularly preferably-75～-30 ℃, more preferably-60～-40 ℃, when second-order transition temperature was too high, the tendency of meeting toughness deficiency had the tendency that thermotolerance reduces when too low.
Wherein, above-mentioned weight-average molecular weight (Mw) is the weight-average molecular weight that converts based on the polystyrene standard molecular weight, is at high performance liquid chromatography (Japanese Waters company make " Waters2695(main body) " 3 root chromatogram columns of connecting with use in " Waters2414(detector) ": Shodex GPC KF-806L(exclusion limit molecular weight: 2 * 10 7, separating ranges: 100～2 * 10 7, theoretical plate number: 10000 sections/, filler material: styrene diethylene benzene copoly mer, packing material size: 10 μ m) measure and the value that obtains, number-average molecular weight (Mn) also can make and use the same method.Dispersity can be tried to achieve by weight-average molecular weight and number-average molecular weight in addition.In addition, second-order transition temperature is calculated by following Fox formula.
[mathematical expression 1]
1 Tg = Wa Tga + Wb Tgb + · · · + Wn Tgn
Tg: the second-order transition temperature of multipolymer (K).
Tga: the second-order transition temperature of the homopolymer of monomer A (K) Wa: the weight fraction of monomer A
Tgb: the second-order transition temperature of the homopolymer of monomers B (K) Wb: the weight fraction of monomers B
Tgn: the second-order transition temperature of the homopolymer of monomer N (K) Wn: the weight fraction of monomer N
（Wa+Wb+…+Wn=1）
The invention provides and contain the tackiness agent that aforesaid propylene acid resin (A) forms with binder composition cross-links as the optical component of essential component, preferred optical component also contains linking agent (B) with binder composition, is by utilizing linking agent that the crosslinked tackiness agent that obtains occurs.
As this linking agent (B), for example can list isocyanates linking agent, epoxies linking agent, aziridines linking agent, melamine class linking agent, aldehydes linking agent, amine linking agent, metallo-chelate class linking agent.Among these, from improving with the viewpoint of the adaptation of base material, considering with reactive viewpoint of base polymer, preferably use the isocyanates linking agent.
as above-mentioned isocyanates linking agent, for example can list 2, the 4-tolylene diisocyanate, 2, the 6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1, the 3-Xylene Diisocyanate, 1, the 4-Xylene Diisocyanate, hexamethylene diisocyanate, ditan-4, 4 '-vulcabond, isophorone diisocyanate, 1, two (isocyanato-methyl) hexanaphthenes of 3-, tetramethylxylene diisocyanate, 1, the 5-naphthalene diisocyanate, the adducts of the polyol compounds such as triphenylmethane triisocyanate and these polyisocyanate compounds and TriMethylolPropane(TMP), the biuret body of these polyisocyanate compounds, isocyanuric acid ester body etc.
As above-mentioned epoxies linking agent, for example can list epoxy resin, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, glycerin diglycidyl ether, the T 55,1 of dihydroxyphenyl propane-Epicholorohydrin type, 6-hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, Sorbitol Powder polyglycidyl ether, Polyglycerine polyglycidyl ether, tetramethylolmethane polyglycidyl ether, two glycerine polyglycidyl ethers etc.
As above-mentioned aziridines linking agent, for example can list tetramethylol methane-three-β-'-aziridino propionic ester, TriMethylolPropane(TMP)-three-β-'-aziridino propionic ester, N, N '-ditan-4,4 '-two (1-aziridine methane amides), N, N '-hexa-methylene-1,6-two (1-aziridine methane amide) etc.
As above-mentioned melamine class linking agent, such as listing HMMM, six ethoxyl methyl trimeric cyanamides, six propoxy-methyl melamines, six butoxymethyl trimeric cyanamides, six pentyloxy methyl melamines, six hexyloxy methyl melamines, melamine resin etc.
As above-mentioned aldehydes linking agent, such as can list oxalic dialdehyde, mda, suceinic aldehyde, maleic dialdehyde, glutaraldehyde, formaldehyde, acetaldehyde, phenyl aldehyde etc.
As above-mentioned amine linking agent, such as listing hexamethylene-diamine, triethyl diamines, polymine, vulkacit H, diethylenetriamine, trientine, isophorone diamine, aminoresin, polymeric amide etc.
As above-mentioned metallo-chelate class linking agent, can list methyl ethyl diketone, acetylacetic ester coordination compound of the polyvalent metals such as aluminium, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium etc.
In addition, these linking agents (B) can use separately, also can be used in combination of two or more.
The content of above-mentioned linking agent (B) is preferably 0.01～10 weight part with respect to 100 parts by weight of acrylic acid resinoids (A), and more preferably 0.05～5 weight part, be particularly preferably 0.1～2.5 weight part.When linking agent (B) is very few, have the force of cohesion deficiency, can't obtain the tendency of sufficient weather resistance, have flexibility and bonding force in the time of too much and reduce, weather resistance reduces, and becomes and easily peels off, and therefore is difficult to the tendency of using as optical component.
In the present invention, also contain silane coupling agent (C) as optical component with the constituent of binder composition, from improving, the viewpoint of the adaptation of optical component is considered it is preferred.
As this silane coupling agent (C), contain epoxy silane coupling such as listing, contain (methyl) acryloxy silane coupling agent, contain mercaptosilane coupling agents, hydroxyl silane coupling agent, contain the carboxyl silane coupling agent, contain amino silicane coupling agent, the amide-containing silane coupling agent, contain isocyanato silanes coupling agent etc.These can use separately, also can be used in combination of two or more.Among these, preferred use contains epoxy silane coupling, contains mercaptosilane coupling agents, and from improving damp and hot weather resistance and excessively not improving the viewpoint of bounding force, also preferably combination is used and contained epoxy silane coupling and contain mercaptosilane coupling agents.
as the above-mentioned object lesson that contains epoxy silane coupling, for example can list γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, γ-glycidoxy propyl group methyldiethoxysilane, γ-glycidoxy propyl group methyl dimethoxysilane, methyl three (glycidyl) silane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc., wherein, γ-glycidoxypropyltrime,hoxysilane preferably, γ-glycidoxy propyl-triethoxysilicane, γ-glycidoxy propyl group methyldiethoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane.
As the object lesson of above-mentioned thiol containing type silane coupling agent, such as listing γ mercaptopropyitrimethoxy silane, γ-sulfydryl propyl-triethoxysilicane, γ-sulfydryl propyl group dimethoxy-methyl silane etc.
As the content of silane coupling agent (C), with respect to 100 parts by weight of acrylic acid resinoids (A), be generally 0.001～10 weight part, be preferably 0.01～1 weight part, be particularly preferably 0.03～0.8 weight part.When the content of this silane coupling agent (C) is very few, have the tendency that can not get additive effect, have the tendency that can not get bonding force, force of cohesion with the consistency reduction of acrylic resin (A) in the time of too much.
In the present invention, can also contain compound (D) and the polymerization starter (E) of unsaturated group, and by active energy beam and/or heat (active energy beam irradiation and/or heating) with the optical component binder composition cross-links.
In the situation that above-mentioned crosslinked by active energy beam and/or heat (active energy beam irradiation and/or heating), use and contain the compound (D) of unsaturated group and the optical component binder composition of polymerization starter (E).So, by the compound (D) that contains unsaturated group, thereby can adjust crosslinkedly, and can realize being suitable for the bonding physical property of optical component purposes.In addition, by containing above-mentioned polymerization starter (E), the stable reaction in the time of can making active energy beam when irradiation and/or heating.
Above-mentioned when crosslinked, the compound (D) that contains unsaturated group is by active energy beam and/or warm and crosslinked (physical crosslinking) with acrylic resin (A) carried out in polymerization (high molecular).In the situation that acrylic resin (A) is for containing the acrylic resin of unsaturated group, be not limited to the high molecular of active energy beam and/or the compound that contains unsaturated group (D) that causes of heat, also can be accompanied by high molecular etc. crosslinked of the acrylic resin (A) that contains unsaturated group and the compound (D) that contains unsaturated group.
As the above-mentioned compound (D) that contains unsaturated group, can be have in 1 molecule 1 unsaturated group simple function contain the unsaturated group compound, it can be also the polyfunctional unsaturated group compound that contains that has 2 above unsaturated groups in 1 molecule, but what preferably have 2 above unsaturated groups contains the unsaturated group compound, what more preferably have 3 above unsaturated groups contains the unsaturated group compound, and the viewpoint of the solidified nature when this shines from active energy beam is preferred.
As the above-mentioned structure that contains unsaturated group compound (D), such as can use the ethylenically unsaturated monomer that contains 1 above ethylenically unsaturated group in carbamate (methyl) acrylic ester compound, epoxy (methyl) acrylic ester compound, polyester (methyl) acrylic ester compound, 1 molecule, such as monofunctional monomer, two functional monomers, monomer etc. more than trifunctional.Among these, use carbamate (methyl) acrylic ester compound (d1), ethylenically unsaturated monomer (d2), consider it is preferred from curing speed, the viewpoint that arrives the excellent in stability of physical property.
Above-mentioned carbamate (methyl) acrylic ester compound (d1) is (methyl) acrylic ester compound that has amino-formate bond in molecule, use makes (methyl) acrylic compounds that contains hydroxyl and polyisocyanate compound (as required by known usual way, multicomponent alcoholics compound) reaction and the material that obtains gets final product, as its weight-average molecular weight, usually can use 300～4000 weight-average molecular weight.
As the ethylenically unsaturated monomer that uses in the present invention (d2), can use the above monomer of known general monofunctional monomer, two functional monomers, trifunctional etc.
As the above-mentioned content that contains the compound (D) of unsaturated group, with respect to 100 parts by weight of acrylic acid resinoids (A), be preferably 0.5～99 weight part, more preferably 1～50 weight part, 8～30 weight parts more preferably.When the content of the above-mentioned compound (D) that contains unsaturated group is too much, can be observed and the consistency of resin descends, filming, the tendency of albefaction occurs have the cross-linking density of tackiness agent to become when very few tendency that insufficient, anti-light leak, weather resistance reduce.
As aforementioned polymerization starter (E), such as using the various polymerization starters such as Photoepolymerizationinitiater initiater (e1), thermal polymerization (e2), from considering by the viewpoint that crosslinked (curing) is carried out in the ultraviolet isoreactivity energy-ray irradiation of utmost point short period of time, particularly preferably use Photoepolymerizationinitiater initiater (e1).
In addition, when using above-mentioned Photoepolymerizationinitiater initiater (e1), make the optical component binder composition cross-links by active energy beam, when using thermal polymerization (e2), make the optical component binder composition cross-links by heating, as required, also preferably will both be used in combination.
Be not particularly limited for above-mentioned Photoepolymerizationinitiater initiater (e1) and above-mentioned thermal polymerization (e2), can use known general Photoepolymerizationinitiater initiater, thermal polymerization.
About above-mentioned polymerization starter (E), be preferably 0.01～10 weight part with respect to the 100 aforementioned acrylic resins of weight part (A), be particularly preferably 0.1～7 weight part, more preferably 0.3～3 weight part.When the content of above-mentioned polymerization starter (E) is very few, can be observed and lack solidified nature and the physical property unsettled tendency that becomes, can be observed the tendency that can not get better effect in the time of too much.
in addition, optical component of the present invention is with in binder composition, in the scope that does not undermine effect of the present invention, also further compounding static inhibitor, acrylic resin (A) other tackiness agents such as acrylic adhesives in addition, urethane resin, rosin, rosin ester, hydrogenated wood rosin glycerol ester, resol, the aromatic series modified terpene resin, the aliphatic category petroleum resin, alicyclic ring same clan petroleum resin, styrene resin, the tackifiers such as xylene resin, tinting material, weighting agent, antiaging agent, UV light absorber, functional pigmented grade is known additive in the past, produce the compound of colour developing or variable color by ultraviolet ray or radiation exposure.
In addition, except above-mentioned additive, also can contain on a small quantity optical component with the contained impurity such as the manufacturing raw material of the constituent of binder composition etc.
As above-mentioned static inhibitor, such as the cationic static inhibitor that can list the quaternary ammonium salts such as imidazole salts (imidazolium), tetra-allkylammonium sulfonate; The anionic antistatic agent such as aliphatic sulfonate, higher alcohol sulfate salt, higher alcohols oxyalkylene affixture sulfuric acid, high alcohol phosphate salt, higher alcohols oxyalkylene affixture phosphate ester salt; An alkali metal salt, alkaline earth salt, higher alcohols oxyalkylene affixture, the polyalkylene glycol fatty acid esters etc. such as two (fluorosulfonyl) imide potassium, two (three fluorosulfonyls) imide li, lithium chloride.
In addition, in the present invention, optical component is with the preferred composition take acrylic resin (A) as main component of binder composition, " being main component " refers to respect to optical component binder composition total amount herein, usually contain the above aforesaid propylene acid resin (A) of 50 % by weight, more than preferably containing 60 % by weight, more than more preferably containing 70 % by weight.In addition, the upper limit of acrylic resin (A) content is generally 99.9 % by weight.
So can obtain optical component binder composition used in the present invention, and this described optical component occurs with binder composition and becomes optical component tackiness agent of the present invention crosslinked.
[optical component tackiness agent]
In the present invention, from the very excellent viewpoint of balance of the anti-light leak of endurance quality, the crosslinked optical component that forms occurs with binder composition and is preferably 60～95%, is particularly preferably 65～90%, more preferably 70～85% with the gel fraction of tackiness agent in above-mentioned optical component.Have easy generation when gel fraction is too low and result from the tendency of weather resistance deficiency of force of cohesion deficiency, have when gel fraction is too high that force of cohesion excessively rises and the tendency peeled off in endurance test.
In addition, when the gel fraction of tackiness agent is adjusted into above-mentioned scope, can reach by such as the hydroxyl in the kind of adjusting linking agent and amount, adjustment composition and the ratio of components of carboxyl etc.In addition, therefore the ratio between this linking agent and sense base unit weight need to average out respectively because interaction separately causes gel fraction to change.
Above-mentioned gel fraction is the standard of degree of crosslinking, for example calculates with following method.Namely, will the high molecular sheet of base material (such as pet film etc.) is upper to be formed the adhesive sheet (barrier film is not set) that binder layer forms and wraps up with 200 purpose SUS wire nettings processed consisting of, dipping is 23 ℃ * 24 hours in toluene, with undissolved binder constituents residual in wire netting with respect to the weight percent that impregnated in the binder layer before toluene as gel fraction.Wherein, deduct in advance the weight of base material.
Optical component of the present invention can be used for the conceptual optical component that comprises indicating meter, consists of its optics with tackiness agent.As indicating meter, can list the various indicating meters such as word processor, computer, mobile phone, TV, as optics, can list Polarizer, optical laminate based on this etc.Optical component of the present invention except the optical component with binder layer described later, also has various application with tackiness agent.Especially optical component of the present invention due to re-workability and excellent in te pins of durability, is also useful as the tackiness agent for the protection of the screening glass of the display frames such as LCD screen with tackiness agent.In addition, optical component of the present invention also can use with tackiness agent, concavo-convex tracing ability tackiness agent with tackiness agent, cosmetic sheet with tackiness agent, the sheet that is used for toy with tackiness agent, common label with tackiness agent, medical adhesive, surface protection with tackiness agent, double sticky tape as the temporary transient surface protection of electric substrate etc. with tackiness agent.
[with the optical component of binder layer]
In the present invention, comprise above-mentioned optical component with the binder layer of tackiness agent by the single or double stratification at optical component (for example, optical laminate), can obtain the optical component with binder layer.
In above-mentioned optical component with binder layer, preferably also be provided with release sheet at the face (exposing face) opposite with the face of optical component one side of binder layer.
In addition, with the optics of binder layer for when the practicality, peel off above-mentioned release sheet and use.And, as above-mentioned release sheet, preferably use silicon class release sheet.
In addition, making is during with the optical component of binder layer, as making optical component with the method for binder composition cross-links, can list: [1] after coating, dry optical component on optical component were with binder composition, the applying release sheet also carried out the method for maturation process; [2] after coating, dry optical component on release sheet are with binder composition, the applying optical component also carries out the method for maturation process.Among these, never damage viewpoint, operability, the stable viewpoint of making of optical component and consider, the method for preferred [2].
Above-mentioned maturation process is carried out for the balance that obtains bonding physical property, condition as slaking, temperature is generally room temperature～70 ℃, time and is generally 1 day～and 30 days, particularly, such as 23 ℃ lower 1 day～20 days, 23 ℃ lower 3 days～10 days, lower 1 day～7 days etc. implement to get final product under condition at 40 ℃.
At the above-mentioned optical component of coating when using binder composition, preferably described optical component is diluted in solvent with binder composition and is coated with, as weaker concn, be preferably 5～60 % by weight, be particularly preferably 10～30 % by weight.In addition, as long as above-mentioned solvent, optical component just is not particularly limited with the binder composition dissolving, such as using the esters solvents such as methyl acetate, ethyl acetate, methyl acetoacetate, methyl aceto acetate; The ketones solvents such as acetone, methylethylketone, mibk; The aromatic series such as toluene, dimethylbenzene kind solvent; The alcoholic solvents such as methyl alcohol, ethanol, propyl alcohol.Among these, from viewpoints such as solvability, drying property, prices, can use aptly ethyl acetate, methylethylketone.
In addition, about the coating of above-mentioned optical component with binder composition, can utilize rolling method, mould to be coated with the customary ways such as method, intaglio plate coating method, comma coating method, silk screen printing and carry out.
In addition, the thickness with the binder layer of the optics of binder layer of gained is preferably 5～300 μ m usually, is particularly preferably 10～50 μ m, more preferably 12～30 μ m.The thickness of this binder layer is crossed has bonding physical property to be difficult for stable tendency when thin, and the blocked up tendency of thickness of optics integral body is arranged when blocked up.
About the optical component with binder layer of the present invention, after the optical component with release sheet is peeled off release sheet, the tackiness agent aspect is fitted in for example glass substrate of liquid crystal cells, in liquid crystal indicator.
As of the present invention with the optical component in the optical component of binder layer, be not particularly limited, can list the optical thin film that can be aptly be used for the image display devices such as liquid crystal indicator, such as Polarizer, polarizer, elliptical polarization plate, optical compensating film, the optical laminate etc. that adds lustre to film and be laminated with them.Wherein, the present invention is effective especially as Polarizer.
The Polarizer that uses in the present invention normally is laminated with the Polarizer as the cellulosetri-acetate class film of protective film on the two sides of polarizing film; as above-mentioned polarizing film; the film that use will be formed by the polyvinyl alcohol resin of 85～100 % by mole of mean polymerisation degree 1500～10000, saponification deg carries out hyperchromatic single axle drawn membrane (common 2～10 times, the stretching ratio of preferred 3～7 times of left and right) as reel film, the aqueous solution or dichroic dye by IKI.
As above-mentioned polyvinyl alcohol resin, usually the polyvinyl acetate saponification that vinyl-acetic ester is polymerized is made, also can contain a small amount of unsaturated carboxylic acid (comprising its salt, ester, acid amides, nitrile etc.), olefines, vinyl ethers, unsaturated sulfonic acid salt etc. can with the composition of vinyl acetate copolymerization.In addition, can list so-called polyvinyl acetal resin and the polyvinyl alcohol derivatives such as bunching butyral resin, vinyl-formal resin that polyvinyl alcohol obtains with the aldehydes reaction under the existence of acid.
[image display device]
Optical component with binder layer of the present invention can suitably be used for the image display devices such as liquid crystal indicator, organic EL display, PDP, Electronic Paper, LED panel.Even the image display device that contains the optical component with binder layer of the present invention also is difficult for producing between binder layer and image display device and bubbles, peels off under the environment of high temperature, high humidity and repeating under the environmental change of low temperature～high temperature.In addition, can suppress the irregular colour that the stress because of the dimensional change that is accompanied by the optical components such as Polarizer produces, the generation of light leakage phenomena.Therefore, can keep the display quality of image display device.
Embodiment
Below enumerate embodiment the present invention further is specifically described, as long as but be no more than main idea of the present invention, just be not limited to following embodiment.Wherein, " part " in example, " % " all represent weight basis in case of no particular description.
At first, prepare in the following manner various acrylic resins (A).Wherein, about the weight-average molecular weight of acrylic resin (A) and the mensuration of number-average molecular weight, measure according to aforesaid method.
[preparation of acrylic resin (A)]
For embodiment 1～13, to possess that reflux exchanger, agitator, nitrogen are blown into mouthful and the four-hole round-bottomed flask of thermometer in each monomer (a1)～(a5), 80 parts of ethyl acetate, 40 parts of acetone of amount of input table 1 record, add 0.03 part of Diisopropyl azodicarboxylate as polymerization starter after the beginning reflux, after reacting 3 hours at the ethyl acetate backflow temperature, dilute with ethyl acetate, obtain respectively acrylic resin (A) solution.
for embodiment 14, to possessing reflux exchanger, agitator, nitrogen be blown into mouthful and the four-hole round-bottomed flask of thermometer in 120 parts of ethyl acetate of input, warming while stirring, when interior temperature reaches 75 ℃, 0.05 part of azobis isobutyronitrile (polymerization starter) being dissolved in the solution that 5 parts of ethyl acetate form all adds, then interior temperature is remained on 74～76 ℃, with 90.4 parts of butyl acrylates (a1), 8 parts of phenoxy group Diethylene Glycol acrylate (a3), 1 part of 2-Hydroxy ethyl acrylate (a5), 0.5 part N-(n-butoxy methyl) acrylamide (a2), 0.4 the mixing solutions of part vinylformic acid (a4) was added drop-wise in reaction system through 2 hours.Under interior temperature 74～76 ℃ make polymerization carry out 5 hour after add ethyl acetate, thereby obtain acrylic resin (A) solution thereafter.
In addition, for comparative example 1～3, add in table 1 other co-polymerized monomers (acid amides or amine compound) of the amount of record (a5) to replace the N-(alkoxyalkyl) (methyl) acrylamide monomers (a2), for comparative example 4, do not add monomer (a2), in addition, operate equally with embodiment 1～13, obtain respectively acrylic resin (A) solution.
Weight-average molecular weight, the number-average molecular weight of above-mentioned resulting each acrylic resin (A) solution are shown in table 1.
Shown in the symbol of table 1, monomer is as described below.
BA: butyl acrylate
MA: methyl acrylate
BMAA:N-(n-butoxy methyl) acrylamide
The MMAA:N-(methoxymethyl) acrylamide
IBMAA:N-(isobutoxy methyl) acrylamide
PEA2: diethylamino phenyl glycol acrylate (Kyoeisha Chemical Co., Ltd. makes, trade(brand)name " Light acrylate P2HA ")
PEA: vinylformic acid phenoxy ethyl
AAc: vinylformic acid
β-CEA: vinylformic acid carboxyl ethyl ester (mixture)
HEA: 2-Hydroxy ethyl acrylate
DMAA: dimethylamino acrylamide
DMAPAA: dimethylaminopropyl acrylamide
DMAEA: vinylformic acid dimethylamino ethyl ester
[linking agent (B)]
Prepare following material as linking agent (B).
55% ethyl acetate solution of the tolylene diisocyanate affixture of TriMethylolPropane(TMP) (Nippon Polyurethane Industry Co., Ltd. makes, " Coronate L-55E ") (KL-55E)
[silane coupling agent (C)]
Prepare following material as silane coupling agent (C).
γ-glycidoxypropyltrime,hoxysilane (Shin-Etsu Chemial Co., Ltd makes, " X-41-1805 ")
[static inhibitor]
Prepare two (fluorosulfonyl) imide potassium (KFSI) as static inhibitor.
[embodiment 1～14, comparative example 1～4]
With each compounding composition of preparing as described above, preparing with the compounding of ratio shown in table 1, preparation becomes the binder composition that the used for optical part tackiness agent forms material thus, with methylethylketone with its dilution (viscosity [500～1000mPas(25 ℃)]), make binder composition solution.
Then, with above-mentioned binder composition solution coat on the polyester stripping film, making dried thickness is 25 μ m, under 90 ℃ after dry 3 minutes, after being transferred to formed adhesive composition layer side on polyethylene terephthalate (PET) film (thickness 38 μ m), slaking is 10 days under the condition of 23 ℃ * relative humidity of temperature 65%, obtains the PET film with binder layer.
Gel fraction, surface resistivity are measured and estimated to the PET film with binder layer that uses operation like this to obtain according to the whole bag of tricks shown in following.These the results are shown in table 2.
[measuring method of gel fraction]
After resulting PET film cutting with binder layer is slit into 40 * 40mm size, peels off release sheet and the binder layer side is fitted in the SUS net sheet (200 order) of 50 * 100mm.With respect to SUS net sheet vertically from central part is folding wrap into sample after, the changes in weight when being used in dipping in the sealed vessel that 250g toluene is housed is carried out the mensuration of gel fraction.
[measuring method of surface resistivity]
After resulting PET film cutting with binder layer is slit into 40 * 40mm size, it is placed under the condition of 23 ℃ * relative humidity of temperature 65% carried out damping in 3 hours.For peeling off the binder layer of release sheet after 10～20 seconds, use ohmer (Mitsubishi Chemical Ind's manufacturing, Ha リ レ エ ス タ ー UP) to measure surface resistivity.Wherein, the less expression antistatic property of surface resistivity is higher.
[with the preparation of the Polarizer of binder layer]
With the binder composition solution coat of embodiment 1～14, comparative example 1～4 on the polyester release sheet, making dried thickness is 25 μ m, after under 90 ℃ dry 3 minutes, formed adhesive composition layer is transferred on Polarizer (thickness 190 μ m), then make its slaking 10 days under the condition of 23 ℃ * relative humidity of temperature 65%, thereby obtain the Polarizer with binder layer.
Wherein, above-mentioned Polarizer is cut and uses in the mode at 45 ° with respect to tensile axis.
The Polarizer with binder layer that uses operation like this to obtain is measured, is estimated re-workability, anti-light leak, weather resistance (oven test, hot resistance test, thermal cycling test) according to each method shown in following.These the results are shown in table 2.
[re-workability]
The Polarizer with binder layer of making is cut into width 25mm, peel off release sheet, the binder layer side is pressed on non-alkali glass plate (Corning Incorporated's manufacturing, EagleXG), applying Polarizer and sheet glass.Then, carry out autoclave and process (50 ℃, 0.5MPa, 20 minutes), after placing 48 hours under the environment of 50 ℃, placed 30 minutes under the environment of 23 ℃, then carry out 180 ° of stripping tests.About re-workability, expectation bounding force appropriateness is little, after 48 hours for about 10N/25mm as target.Estimate according to following benchmark.
(metewand)
◎: not enough 10N/25mm
Zero: the above and not enough 15N/25mm of 10N/25mm
Above and the not enough 20N/25mm of △: 15N/25mm
*: more than 20N/25mm
[anti-light leak]
The Polarizer with binder layer that obtains, is made so that Polarizer forms the mode of crossed nicols and is fitted with the light leak observation sample of same sample on surface and two sides, the back side after 1000 hours in placement under 80 ℃.Shine backlight and carry out Visual Confirmation, estimating according to following benchmark.
(metewand)
◎: full confirmation is less than light leak.
Zero: can confirm a small amount of light leak.
△: can confirm the light leak that the degree of obstacle may be arranged in practical.
*: light leak is serious.
[weather resistance]
Peel off the release sheet of resulting Polarizer with binder layer, binder layer one side is pressed on non-alkali glass plate (Corning Incorporated's manufacturing, EagleXG), after applying Polarizer and sheet glass, carry out autoclave and process (50 ℃, 0.5MPa, 20 minutes), the evaluation of bubbling, peel off, floating afterwards in the long duration test (oven test, hot resistance test, thermal cycling test) of following (1)～(3).Wherein, the test film of use is of a size of 20cm * 15cm.
(1) oven test
The long duration test of 90 ℃, 2000 hours
(2) hot resistance test
60 ℃, relative humidity (R.H.) long duration test of 90%, 2000 hour
(3) thermal cycling test
To after placing 30 minutes under-35 ℃, as 1 circulation, carry out the long duration test of 1000 circulations 70 ℃ of operations of placing 30 minutes
[metewand]
(foaming)
◎ is without foaming
Zero does not almost observe foaming
△ can observe slightly and bubble
* can observe a large amount of foamings
(peeling off)
Zero occurs less than the peeling off of 0.5mm, or less than the vestige that floats of 0.5mm
It is above and less than the peeling off of 10mm that 0.5mm appears in △, or 0.5mm is above and less than the vestige that floats of 10mm
* above the peeling off of 10mm appears, or 10mm above float vestige
[table 1]
Figure BDA00003045165000261
[table 2]
Figure BDA00003045165000271
As can be known for containing the N-(alkoxyalkyl) embodiment 1～14 of (methyl) acrylamide monomers (a2) with for the Polarizer of binder layer, all can reach taking into account of weather resistance when exposing to the open air for a long time to re-workability with under high temperature, high humidity.
On the other hand, for the N that has used patent documentation 2 grades to put down in writing, N-dialkyl group (methyl) acrylamide replaces the N-(alkoxyalkyl) comparative example 1 of (methyl) acrylamide monomers (a2), although re-workability is excellent, poor durability.In addition, for the comparative example 2,3 that the tertiary-amino-containing monomer (acrylate, acrylamide) that has used patent documentation 1 grade to put down in writing replaces monomer (a2), re-workability, weather resistance are all poor.And then for the comparative example 4 that does not use monomer (a2), although re-workability is excellent, weather resistance is insufficient.
Describe the present invention in detail and with reference to specific embodiment, but it will be apparent to those skilled in the art that can not break away from the spirit and scope of the present invention ground carries out various changes, correction to the present invention.
The application is incorporated into this with its content as reference based on the Japanese patent application (Patent 2010-229885) of application on October 12nd, 2010.
Utilizability on industry
The optical component binder composition of the application of the invention can obtain the optical component tackiness agent of re-workability and excellent in te pins of durability.And then the optical component tackiness agent of the application of the invention can suppress irregular colour, light leakage phenomena in the image display devices such as LCD panel.

Claims (8)

1. optical component binder composition, it is characterized in that, it is to contain the copolymer composition [I] take (methyl) alkyl-acrylates monomer (a1) as main component is carried out the acrylic resin (A) that copolymerization obtains to form, and contains the N-(alkoxyalkyl) (methyl) acrylamide monomers (a2) is as copolymer composition [I].
2. optical component binder composition according to claim 1, is characterized in that, it contains to be selected from and contains aromatic nucleus monomer (a3) and contain at least a as copolymer composition [I] of carboxylic monomer (a4).
3. optical component binder composition according to claim 1 and 2, is characterized in that, it contains linking agent (B) and forms.
4. the described optical component binder composition of any one according to claim 1～3, is characterized in that, it contains silane coupling agent (C) and forms.
5. an optical component tackiness agent, is characterized in that, it is that the described optical component of any one in claim 1～4 forms with binder composition cross-links.
6. optical component tackiness agent according to claim 5, is characterized in that, optical component is Polarizer.
7. the optical component with binder layer, is characterized in that, it comprises the stepped construction of binder layer and optical component, and described binder layer contains the described optical component tackiness agent of claim 5 or 6.
8. an image display device, is characterized in that, it contains the optical component with binder layer claimed in claim 7.
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