CN104024363A - Optical member adhesive composition, adhesive sheet using same, optical member provided with adhesive layer, and flat panel display - Google Patents

Optical member adhesive composition, adhesive sheet using same, optical member provided with adhesive layer, and flat panel display Download PDF

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Publication number
CN104024363A
CN104024363A CN201280065245.1A CN201280065245A CN104024363A CN 104024363 A CN104024363 A CN 104024363A CN 201280065245 A CN201280065245 A CN 201280065245A CN 104024363 A CN104024363 A CN 104024363A
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Prior art keywords
methyl
acrylate
adhesive composition
vinylformic acid
ester
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CN104024363B (en
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小山雄司
室井佐知
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Soken Kagaku KK
Soken Chemical and Engineering Co Ltd
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Soken Chemical and Engineering Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • 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
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polarising Elements (AREA)
  • Adhesive Tapes (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The objective of the present invention is to provide an optical member adhesive composition that has superior dimensional stability and that exerts superior light leak prevention performance and durability even in hot, humid environments. The optical member adhesive composition is characterized by containing a specific amount of: a (meth)acrylic copolymer (A) obtained by the copolymerization of specific monomer components (a-1 to a-4) at specific proportions; and a cross-linking agent (B).

Description

Used for optical part adhesive composition, bonding sheet, optics and indicating meter
Technical field
The present invention relates to used for optical part adhesive composition and use its bonding sheet, with optics and the flat-panel monitor thereof of adhesive layer, described used for optical part adhesive composition has good dimensional stability and damp and hot weather resistance, can under hot and humid environment, effectively prevent light leak or peel off.
Background technology
For the binding agent towards flat-panel monitor (FPD) field, be accompanied by the maximization of indicating meter and popularizing of LED mode, it is more and more higher that the requirement of high image quality, high durability is just becoming.
For example, the subclass liquid-crystal display (LCD) in FPD is comprised of liquid crystal panel, backlight and peripheral circuit.This liquid crystal panel consists of each layers such as Polarizer, the glass substrate with transparency electrode, colored filters conventionally, thereby obtains the structure of above-mentioned glass substrate holding liquid crystal.
Above-mentioned Polarizer consists of the multilayered structure of differing materials, each material has respectively different physics, chemical property, therefore especially under high temperature, high humidity environment, due to pucker & bloat, the degree of the dimensional change of each layer is different, and these different degree are also very large.Therefore, the integral body of Polarizer lacks dimensional stability.
Due to this dimensional change, to the various performances that light leak and weather resistance be representative of take of Polarizer integral body, can produce many and diverse influences.And known, the kind of the binding agent using in the bonding between each optical thin film of Polarizer etc. or the bonding of glass substrate and Polarizer can exert an influence to above-mentioned light leak and weather resistance.
Under this present situation, by Polarizer kind-binding agent kind is combined, deal with the performance of various requirements such as above-mentioned light leak and weather resistance, the performance of its requirement as previously mentioned, is to be accompanied by the universal of large screen, LED mode and the requirement of the higher degree of higher image quality of coming, high-durability and so on.
Here, kind for above-mentioned binding agent, peeling off under the light leak causing for the dimensional change solving due to Polarizer, hot and humid environment, can be conceived to form the various characteristicses such as the hardness property of polymkeric substance of binding agent or optical characteristics, in order to find that good light leakage performance and realization guarantee high-durability and are studied.
For example, be conceived to the binding agent of hardness property, owing to being also not easy distortion and foaming etc. under hygrothermal environment, therefore proof stress and the weather resistance when Polarizer shrinks is good, easily obtains reasonable light leakage characteristic and weather resistance.Yet, if carry out the maximization of FPD, under former size, not that the light leak of problem and the foaming of a little also can become obvious, therefore become problem.Therefore,, for this High Level that requires characteristic, utilize binding agent in the past not tackle fully.
As this binding agent, for example patent documentation 1 discloses a kind of adhesive composition, contain (methyl) acrylic copolymer (A) and ionic compound (B) and linking agent (C), described (methyl) acrylic copolymer (A) is formed by specific (methyl) acrylate (A-1), unsaturated monomer (A-3) copolymerization that has the unsaturated monomer (A-2) of aromatic nucleus and have a polar functional group.
For example, can in the bonding of Polarizer, use said composition, example as above-mentioned (A-1), can enumerate n-butyl acrylate, as the example of (A-2), (methyl) vinylformic acid 2-phenoxy ethyl can be enumerated, as the example of above-mentioned (A-3), vinylformic acid or (methyl) vinylformic acid 2-hydroxy methacrylate can be enumerated.
In addition, patent documentation 2 discloses the Polarizer with the tack coat consisting of binding agent, described binding agent contains (methyl) acrylic copolymer (A) and can form the multi-functional compound (B) of crosslinking structure, and described (methyl) acrylic copolymer (A) is by (methyl) acrylate monomer (a of not enough-30 ℃ of the Tg of homopolymer 1), the Tg of homopolymer is at more than-30 ℃ compound (a with vinyl 2) and contain specific monomer (a 3) form.
As above-mentioned (a 1) example can enumerate n-butylacrylate, as above-mentioned (a 2) example vinylformic acid tertiary butyl ester, as above-mentioned (a 3) example can enumerate (methyl) vinylformic acid or (methyl) vinylformic acid 2-hydroxy methacrylate.
Yet disclosed binding agent in these documents, as mentioned above, can not tackle the characteristic of the height of existing requirement.
Prior art document
Patent documentation
Patent documentation 1: JP 2010-66755 communique
Patent documentation 2: JP 2006-301572 communique
Summary of the invention
The problem to be solved in the present invention
The object of the present invention is to provide a kind of used for optical part adhesive composition, the excellent in dimensional stability of described adhesive composition, even if also can bring into play excellent light leakage performance and weather resistance under hygrothermal environment.
The method of dealing with problems
The inventor, is conceived to hardness property and the optical compensation function of binding agent and is cross-linked, and adhesive composition is studied.Found to give polymkeric substance and used according to specific ratio with the monomer of flexibility and the monomer used in the adjusting of the hardness of polymkeric substance, thereby the hardness property of polymkeric substance has been set in to suitable scope; In addition, can give polymkeric substance with the monomer of optical compensation function and can give polymkeric substance and use and can obtain a kind of (methyl) acrylic acid series co-polymer according to specific ratio with the monomer of bridging property, by being set to suitable degree of crosslinking, above-mentioned (methyl) acrylic acid series co-polymer is cross-linked, can provide dimensional stability and damp and hot weather resistance good, under hot and humid environment, also can effectively prevent light leak and the used for optical part adhesive composition peeling off.
That is, used for optical part adhesive composition of the present invention is characterised in that and contains:
(A): according to following ratio, following (a-1)～(a-4) carried out to (methyl) acrylic acid series co-polymer that copolymerization obtains:
(a-1) second-order transition temperature of homopolymer is-40 ℃ of (methyl) acrylate 40～94.9 % by weight following, that there is no aromatic nucleus;
(a-2) second-order transition temperature of homopolymer is more than 0 ℃, there is no (methyl) acrylate 0.1～50 % by weight of aromatic nucleus;
(a-3) there is (methyl) acrylate 0.1～25 % by weight of aromatic nucleus;
(a-4) there is (methyl) acrylic monomer of polar functional group of more than two kinds and/or two or more has (methyl) different, a kind of polar functional group acrylic monomer 0.1～6 % by weight;
(wherein, (a-2) and (a-3) add up to 5～59.9 % by weight; Above-mentioned polar functional group is selected from carboxyl, hydroxyl, amino, amide group and epoxy group(ing);
(a-1)～(a-4) add up to 100 % by weight)
(B): relatively above-mentioned (methyl) acrylic copolymer (A) 100 weight parts, the linking agent of 0.01～3 weight part.
The copolymerization ratio of above-mentioned (methyl) acrylate (a-2) is 10～40 % by weight preferably.
At least one in above-mentioned (methyl) acrylate (a-2) group that preferably freely (methyl) methyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate and (methyl) isobornyl acrylate form.
Above-mentioned (methyl) acrylate (a-2) is (methyl) tert-butyl acrylate preferably.
The copolymerization ratio of above-mentioned (methyl) acrylate (a-1) is preferably 50～90 % by weight.
Above-mentioned (methyl) acrylate (a-1) is selected from least one in the group that following compound forms: n-butyl acrylate, vinylformic acid n-pentyl ester, vinylformic acid isopentyl ester, Ethyl acrylate, vinylformic acid heptyl ester, vinylformic acid isopentene ester, 2-EHA, vinylformic acid n-octyl, Isooctyl acrylate monomer, vinylformic acid ester in the positive ninth of the ten Heavenly Stems, vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, (methyl) isodecyl acrylate, methacrylic acid dodecyl ester, (methyl) vinylformic acid n-tridecane base ester, vinylformic acid methoxyl group ethyl ester, vinylformic acid methoxy poly (ethylene glycol) ester and vinylformic acid ethoxy ethoxy ethyl ester.
At least one in the group that the freely following compound of above-mentioned (methyl) acrylate (a-3) choosing forms: phenoxy group ethyl (methyl) esters of acrylic acid and derivative thereof that (methyl) vinylformic acid benzyl ester, following general formula (I) represent
In formula (1), R 0for hydrogen or methyl; R 1for (CH 2cH 2o) nthe group (integer that n is 1～20) representing, the integer that m is 1～5, R 2for hydrogen, the carbonatoms alkyl that is 1～9, aryl that carbonatoms is 6～10 or the carbonatoms aralkyl that is 7～11, m is 2 when above, a plurality of R of existence 2can be identical also can be different.
The copolymerization ratio of above-mentioned (methyl) acrylic monomer (a-4) is preferably 1～6 % by weight.
When above-mentioned used for optical part adhesive composition is carried out to following small creep test, preferably the ratio of 60 ℃ of measured value/23 ℃ measured values is 1.05～2.00.
Small creep test
On the polyester film that has carried out lift-off processing, be coated with and make it dry above-mentioned used for optical part adhesive composition, preparation has the bonding sheet of the adhesive layer of thickness 25 μ m.
With this bonding sheet and the Polarizer that formed by TAC (cellulosetri-acetate)-PVA (polyvinyl alcohol)-TAC, with above-mentioned adhesive layer, contact with above-mentioned Polarizer and make it fit to make to evaluate by bonding and process Polarizer.
This evaluation is cut into wide 10mm * long 100mm with bonding processing Polarizer, the alkaline purification of peeling off through the polyester film of above-mentioned lift-off processing is on glass, by above-mentioned adhesive layer and above-mentioned glass contact, and according to the bond area of 10mm * 10mm, make it bonding, as evaluating with bonding processing Polarizer test film.
To this evaluation with bonding processing Polarizer test film carry out autoclave (50 ℃, 50atm) process, under the environment of 23 ℃/50%RH standing 24 hours;
Then the fixing length 15mm place by chuck part in the cavity BOX of small creep tstr arranges above-mentioned test film;
To in above-mentioned cavity BOX, be heated to measure temperature, measuring at temperature after standing 40 minutes, with stretching loading 800g, stretching time 1000 seconds, parallel and along the stretch bonding processing Polarizer for above-mentioned evaluation of above-mentioned test film of the length direction of Polarizer according to the contact surface of Polarizer and above-mentioned glass;
Measure the distance (mm) of skew of the fitting part of above-mentioned glass in above-mentioned test film and Polarizer.
Used for optical part adhesive composition of the present invention, with respect to 100 weight parts above-mentioned (methyl) acrylic copolymers (A), further preferably contains 0.01～0.5 weight part silane coupling agent.
In addition, above-mentioned composition, with respect to 100 weight parts above-mentioned (methyl) acrylic copolymers (A), further preferably contains 0.01～3 weight part static inhibitor.
Be used as the used for optical part adhesive composition of the present invention of the composition of adhesive layer, the adhesive layer that can obtain forming and the bonding sheet that forms on base material film.
In addition, the optics that has adhered to this adhesive layer is also contained in scope of the present invention, it is the optics of adhesive layer that formed adhering to of adhesive layer at least one side of optics, and above-mentioned adhesive layer is to contain used for optical part adhesive composition of the present invention as feature.
Flat-panel monitor of the present invention take that to have the optics that has adhered to above-mentioned adhesive layer be feature.
The effect of invention
The invention provides dimensional stability and damp and hot weather resistance is good, the used for optical part adhesive composition that can effectively prevent light leak or peel off under hot and humid environment, relates to simultaneously and uses the bonding sheet of said composition, the optics that adheres to adhesive layer and FPD.
Accompanying drawing explanation
In the mensuration of Fig. 1 light leak size in an embodiment, shown the mode chart that the distance d at angle partly occurs from light leak.
Fig. 2 has shown the mode chart of the measuring method of photoelastic coefficient in an embodiment.
Embodiment
Next coming in order illustrate used for optical part adhesive composition of the present invention (hereinafter referred to as " composition of the present invention ") and use its bonding sheet, the optics that has adhered to adhesive layer and flat-panel monitor.And in this manual, (methyl) vinylformic acid refers to methacrylic acid and vinylformic acid, (methyl) acrylate refers to methacrylic ester or acrylate.
[used for optical part adhesive composition]
(A) (methyl) acrylic copolymer
(methyl) acrylic copolymer (A) of the constituent of composition of the present invention is by above-mentioned specific monomer component (a-1)～(a-4) obtain with specific ratio copolymerization.These monomers are below described respectively.
The second-order transition temperature of < (a-1) homopolymer is at (methyl) esters of acrylic acid > that there is no aromatic nucleus below-40 ℃
(methyl) acrylate (a-1) using in the present invention, the second-order transition temperature of its homopolymer (hereinafter to be referred as Tg) is below-40 ℃.
Above-mentioned Tg in this manual, apart from specified otherwise, refers to by the test film (homopolymer) of measuring Tg at N 2environment under, in the scope of-60 ℃ to 180 ℃, with the ratios of 10 ℃/minute, it is heated up, with DSC (Rigaku company manufactures, differential scanning calorimetry DSC8230), carry out calorimetric measurement and try to achieve.In addition, measure and carry out according to JIS (Japanese Industrial Standards) K7121 (the transition temperature measuring methods of plastics).
If only in order to improve hardness property, used for optical part adhesive composition of the present invention is cross-linked and obtains in crosslinked due to inappropriate situations such as the sticky close sense deficiencies of meeting generation, therefore use the Tg of homopolymer at (methyl) esters of acrylic acid (a-1)-40 ℃ below, can give (methyl) acrylic copolymer (A) thus appropriate flexibility averages out.
In addition, above-mentioned (methyl) acrylate (a-1) does not have aromatic nucleus.If there is aromatic nucleus, can not give (methyl) acrylic copolymer (A) flexibility, when carrying out the balance of adjusting of optical compensation function by (methyl) acrylate (a-3), also can produce inappropriate situation in addition.
In the present invention, above-mentioned aromatic nucleus is to form by circular permutation structure with π-electron and atom, and it meets Huckel's rule, and above-mentioned π-electron is the ring that non-localization and above-mentioned ring refer to planar configuration.
As this (methyl) acrylate (a-1), can enumerate: n-butyl acrylate, vinylformic acid n-pentyl ester, vinylformic acid isopentyl ester (Isopentyl acrylate), Ethyl acrylate, vinylformic acid heptyl ester, vinylformic acid isopentene ester (Isoamyl acrylate), 2-ethylhexyl acrylate, vinylformic acid n-octyl, Isooctyl acrylate monomer, vinylformic acid ester in the positive ninth of the ten Heavenly Stems, vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, (methyl) isodecyl acrylate, methacrylic acid dodecyl ester, (methyl) vinylformic acid n-tridecane base ester, vinylformic acid methoxyl group ethyl ester, vinylformic acid methoxy poly (ethylene glycol) ester and vinylformic acid ethoxy ethoxy ethyl ester etc.
In these compounds, from obtaining the balance of hardness property and flexibility and realizing the viewpoint of good proof stress, preferably n-butyl acrylate and 2-EHA.
(methyl) described above acrylate (a-1), may be used alone or in combination of two or more kinds.
The vitrifying tansition temperature of the homopolymer of < (a-2) be 0 ℃ above and do not there is (methyl) acrylate > of aromatic nucleus
For (methyl) acrylate (a-2) using in the present invention, the Tg of its homopolymer is more than 0 ℃.Higher (methyl) acrylate (a-2) of Tg of this homopolymer has given (methyl) acrylic copolymer (A) good hardness property, and the high-dimensional stability of used for optical part adhesive composition of the present invention is made contributions.
In addition, (methyl) acrylate (a-2) does not have aromatic nucleus.If there is aromatic nucleus,, when the balance of the adjusting of the optical compensation function by aftermentioned (methyl) acrylate (a-3), can there is inappropriate situation.
This (methyl) acrylate (a-2), can enumerate: (methyl) methyl acrylate, propyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate and (methyl) stearyl acrylate acid esters etc.
In these compounds, from realizing the viewpoint of excellent stiffness characteristic, preferably (methyl) methyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate and (methyl) isobornyl acrylate, particularly preferably (methyl) tert-butyl acrylate.
(methyl) described above acrylate (a-2), may be used alone or in combination of two or more kinds.
< (a-3) has (methyl) acrylate > of aromatic nucleus
(methyl) acrylate (a-3) has aromatic nucleus, by the structural unit being come by it is added in (methyl) acrylic copolymer (A), thereby can suitably control the optical compensation function of above-mentioned multipolymer (A).Through this, with used for optical part adhesive composition of the present invention, carry out cohesion member, even if there is a little light leak under hygrothermal environment, also can suppress this light leak by above-mentioned optical compensation function.
As this (methyl) acrylate (a-3), can enumerate (methyl) vinylformic acid phenoxy ethyl and the derivative thereof of (methyl) vinylformic acid benzyl ester, following general formula (1) expression.
In formula (1), R 0for hydrogen or methyl; R 1for (CH 2cH 2o) nthe group (integer that n is 1～20) representing, the integer that m is 1～5, R 2for hydrogen, the carbonatoms alkyl that is 1～9, aryl that carbonatoms is 6～10 or the carbonatoms aralkyl that is 7～11, m is 2 when above, a plurality of R of existence 2can be identical also can be different.
(methyl) the vinylformic acid phenoxy ethyl representing as general formula (1) and the object lesson of derivative thereof, can enumerate: (methyl) vinylformic acid phenoxy ethyl, (methyl) vinylformic acid phenoxy group binaryglycol ester, (methyl) vinylformic acid phenoxy group (gathering) glycol ester, nonyl phenol EO affixture (methyl) acrylate, ethoxylation o-phenyl phenol (methyl) acrylate etc.
In these compounds, from realizing the viewpoint of good optical compensation function, preferred (methyl) vinylformic acid benzyl ester and (methyl) vinylformic acid phenoxy ethyl.
(methyl) described above acrylate (a-3), may be used alone or in combination of two or more kinds.
< (a-4) has (methyl) acrylic monomer and/or two or more (methyl) different, that have a kind of polar functional group acrylic monomer > of two or more polar functional group
(methyl) acrylic monomer (a-4) using in the present invention has polar functional group, and between linking agent described later (B), crosslinking reaction occurs, thereby realizes the good bonding characteristic of used for optical part adhesive composition of the present invention.Above-mentioned functional group is carboxyl, hydroxyl, amido, amide group and epoxy group(ing).In these groups, from the viewpoint of the good weather resistance hygrothermal environment, preferred hydroxyl.
In addition, (methyl) acrylic monomer (a-4) has two or more polar functional group, can think by there being different various polarity functional groups, crosslinked can suitably the carrying out between (methyl) acrylic copolymer (A), thus realize good degree of crosslinking.
Above-mentioned " having two or more polar functional groups " refers to when (methyl) acrylic monomer (a-4) by a plurality of molecular compositions is treated as a whole, has two or more polar functional group.
Therefore, (methyl) Acrylic Acid Monomer (a-4) is a kind of monomer, in this monomer 1 molecule, can have polar functional group of more than two kinds; (methyl) acrylic monomer (a-4) also can consist of two or more different monomer, and these monomers have respectively a kind of polar functional group.Although and do not comprise it being the monomer of more than two kinds that structure is different in the latter, the situation of the identical polar functional group having.
In (methyl) acrylic copolymer (A), as monomer (a-4), can only use the monomer that has two or more polar functional group in 1 molecule monomer, also can not use this monomer and use the monomer with a kind of polar functional group of more than two kinds, also can both use.
In addition, in this manual, meet any one in (methyl) acrylate (a-1)～(a-3), and meet the monomer of (methyl) acrylic monomer (a-4), be considered as (methyl) acrylic monomer (a-4).
As (methyl) acrylic monomer with two or more polar functional group described above, can enumerate: hydroxyethyl acrylamide and N-tert-butyl acrylamide sulfonic acid etc.
In addition, as (methyl) acrylic monomer with a kind of polar functional group described above, can enumerate following monomer:
(i) there is (methyl) acrylic monomer of carboxyl: (methyl) vinylformic acid, (methyl) propenoic acid beta-carboxyl ethyl ester;
(ii) there is (methyl) acrylic monomer of hydroxyl: (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid monoglyceride, (methyl) vinylformic acid (gathering) ethylene glycol ester, (methyl) vinylformic acid (gathering) propylene glycol monoester;
(iii) there is (methyl) acrylic monomer of amido: (methyl) vinylformic acid amido ethyl ester, (methyl) vinylformic acid N, N dimethyl amido ethyl ester, (methyl) vinylformic acid tertiary butyl amido ethyl ester;
(iv) there is (methyl) acrylic monomer of amide group: (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-butyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxymethyl-propane (methyl) acrylamide;
(v) there is (methyl) acrylic monomer of epoxy group(ing): (methyl) glycidyl acrylate, (methyl) vinylformic acid 4-hydroxyl butyl ester glycidyl ether.
Other monomers of < >
In the present invention, in not damaging effective scope of the present invention, in order to regulate various characteristics, in (methyl) acrylic copolymer (A), can contain except the structural unit from other monomers above-mentioned monomer component (a-1)～(a-4).
As the example of these other monomer, can enumerate: vinylbenzene, alpha-methyl styrene, vinyl-acetic ester, propionate, ethyl propenoate, isobutyl acrylate, 2-Ethylhexyl Methacrylate, lauryl acrylate etc.
The manufacture method > of < (methyl) acrylic copolymer (A)
(the copolymerization ratio of each monomer)
(methyl) acrylic copolymer (A) of the moiety of used for optical part adhesive composition of the present invention, obtains according to the specified proportion copolymerization monomer component described above (a-1) of following explanation～(a-4) and other monomers as required.
The copolymerization ratio of above-mentioned (methyl) acrylate (a-1) in (methyl) acrylic copolymer (A), from the viewpoint of the balance of hardness property and flexibility, is 40～94.9% % by weight, preferably 50～90 % by weight.
The copolymerization ratio of above-mentioned (methyl) acrylate (a-2) in (methyl) acrylic copolymer (A), viewpoint from hardness property, be 0.1～50% % by weight, preferred 10～40 % by weight, further preferred 10～25 % by weight.
The copolymerization ratio of above-mentioned (methyl) acrylate (a-3) in (methyl) acrylic copolymer (A), from the viewpoint of optical compensation function, is 0.1～25% % by weight, preferably 5～20 % by weight.
The copolymerization ratio of above-mentioned (methyl) acrylate (a-4) in (methyl) acrylic copolymer (A), from the viewpoint of suitable degree of crosslinking, is 0.1～6% % by weight, preferably 1～6 % by weight.
And, the copolymerization ratio of each monomer component (a-1)～(a-4) add up to 100 % by weight.
In addition, for hardness property and optical compensation function are side by side set in to suitable region and effectively prevent light leak, (methyl) acrylate (a-2) and copolymerization ratio (a-3) add up to 5～59.9 % by weight, preferably 10～50 % by weight.
Further, with respect to monomer (a-1)～(a-4), add up to 100 weight parts, the copolymerization ratio of above-mentioned other monomers is generally 0～5 weight part.
(manufacture method of (methyl) acrylic copolymer (A))
(methyl) acrylic copolymer (A) can be by solution polymerization process, block polymerization, emulsion polymerization method, be suspended the known polymerization such as polymerization carries out polymerization manufacture by other monomers of each monomer component (a-1)～(a-4) and as required and obtains.In these methods, for the molecular weight of easy telomerized polymer, and the impurity that makes to sneak in reaction system is few, preferably uses solution polymerization process.
In solution polymerization process, using organic solvent as reaction solvent, in this reaction solvent, dissolve or disperse to form each monomer component of above-mentioned (methyl) acrylic copolymer (A), under agitation add polymerization starter, thereby implement copolyreaction.
As above-mentioned organic solvent, can enumerate such as ester series solvents such as ethyl acetate the ketone series solvents such as methylethylketone, formaldehyde and acetaldehyde, the ether series solvents such as dimethyl ether, the aromatic series series solvent of toluene and dimethylbenzene; The alicyclic series solvent such as hexanaphthene; And the aliphatics series solvent such as hexane and octane.
Also can be used alone in these solvents a kind, also can use two or more mixed solvents.
In addition, as above-mentioned polymerization starter, can enumerate 2,2 '-azobis isobutyronitrile (AIBN), 2,2 ' azo two (4-methoxyl group-2,4-methyl pentane nitrile), 2,2 '-azo is two-2,4-methyl pentane nitrile, 1, the azo-compounds such as 1 '-azo bis cyclohexane-1-formonitrile HCN; Peroxidation isobutyryl, α; α-bis-(the new decanoyl of peroxidation) diisopropylbenzene(DIPB), peroxidation neodecanoic acid isopropyl phenyl ester, peroxy dicarbonate di-n-propyl ester, di-isopropyl peroxydicarbonate, peroxy dicarbonate diisobutyl ester, peroxidation neodecanoic acid 1; 1; 3,3-tetramethyl-butyl ester, two (the 4-butyl cyclohexyl) esters of peroxy dicarbonate, benzoyl peroxide (benjoyl peroxide), peroxidation di tert butyl carbonate, lauroyl peroxide and the caproic acid tertiary butyl-oxygen base-2-ethyl ester etc.These compounds can be used alone or in combination.
In solution polymerization process, use the temperature of reaction of the copolyreaction of these reaction solvents and polymerization starter to be generally 50～90 ℃, preferably in the scope of 60～85 ℃; Reaction times is generally 1～10 hour, preferably 2～8 hours; Reaction pressure is generally normal pressure～0.5MPa.
< (A) methacrylic acid based copolymer >
Hardness property and the optical compensation function good crosslinked of (methyl) acrylic copolymer (A) for being cross-linked to form by use aftermentioned linking agent (B), if therefore use used for optical part adhesive composition of the present invention, can realize good dimensional stability, leakproof photosensitiveness and the weather resistance under hygrothermal environment.
The average molecular weight Mw of above-mentioned (methyl) acrylic copolymer (A) by gpc measurement is generally 500,000～2,000,000, and preferably 800,000～1,800,000, this multipolymer (A) has good cohesive force.
In addition, the second-order transition temperature of (methyl) acrylic copolymer (A) is preferably below 0 ℃, below more preferably-10 ℃, and particularly preferably-15～-60 ℃.If second-order transition temperature is higher than 0 ℃, resulting binding agent reduces for the stopping property of material to be bonded and the pliability of adhesive layer, can occur from the separated or floating situation of sticking up of material to be bonded.In addition, the second-order transition temperature of (methyl) acrylic copolymer (A) is the value of calculating by following FOX formula.
(FOX formula)
1/Tg＝Wa/Tga+Wb/Tgb+…
Tg:(methyl) second-order transition temperature of acrylic copolymer (A);
Tga, Tgb ...: monomer a, monomer b ... the second-order transition temperature of homopolymer separately;
Wa, Wb ...: the weight fraction of the structural unit from each monomer of monomer a, monomer b in (methyl) acrylic copolymer (A);
* (methyl) acrylic monomer (a-1)～(a-4) and other monomers, can be assigned as arbitrarily monomer a, monomer b ...
Above-mentioned (methyl) acrylic copolymer (A) can be the random copolymers of above-mentioned each monomer component, also can be segmented copolymer.
In addition, in the present invention, (methyl) acrylic copolymer (A) can be used alone a kind, also can be used in combination.
[(B) linking agent]
Used for optical part adhesive composition of the present invention except (methyl) described above acrylic copolymer (A), also contains linking agent (B) simultaneously.
As long as can there is crosslinking reaction with (methyl) acrylic copolymer (A) in linking agent (B), there is no particular limitation, can enumerate as an example: isocyanate-based linking agent, metal-chelating system linking agent and epoxy are linking agent.
As the object lesson of above-mentioned isocyanate-based linking agent, can enumerate: the isocyanate-monomers such as tolylene diisocyanate, chlorobenzene vulcabond, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, Xylene Diisocyanate, diphenylmethanediisocyanate, hydrogenated diphenyl methane diisocyanate; The isocyanate compound that these several isocyanate-monomer additions are formed on trihydroxy methyl propane etc.; Tricarbimide ester cpds; Biuret type compound; Carry out the isocyanic ester of the urethanum prepolymer type that addition reaction obtains with known polyether polyols or polyester polyalcohols, vinylformic acid polyalcohols (acryl polyol), polyhutadiene polyalcohols, polyisoprene polyalcohols etc.
As above-mentioned metal-chelating system linking agent, can be set forth in the coordination compound that on the polyvalent metals such as aluminium, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium or zirconium, coordination Virahol, methyl ethyl diketone or methyl aceto acetate etc. obtain.
As concrete example, can enumerate: aluminum isopropylate, diisopropanol bis-acetylacetonate titanium and tri ethylacetoacetate aluminium.
Above-mentioned epoxy is the object lesson of linking agent, can enumerate: hexylene glycol glycidyl ethers, polyoxyethylene glycol diepoxy propyl ether, glycerine diepoxy propyl ether, glycerine three glycidyl ethers, 1, two (the N of 3-, N-diepoxy propyl group aminomethyl) hexanaphthene, N, N, N ', a N '-tetra-epoxypropyl-hexichol two methylene amine, N, N, N ', N '-tetra-epoxypropyl aminocarbonyl phenyl methane, triglycidyl isocyanurate, a N, N-diepoxy propyl group aminocarbonyl phenyl glycidyl ethers, N, N-diepoxy propyltoluene amine, N, N-diepoxy propyl group aniline.
Linking agent described above (B), can be used alone a kind, but also two or more is used in combination.
In used for optical part adhesive composition of the present invention, with respect to (methyl) acrylic copolymer (A) 100 weight parts, this linking agent (B) that contains 0.01～3 weight part.
By containing a certain amount of like this linking agent (B), can realize suitable degree of crosslinking, and can realize good cohesiveness, dimensional stability and light leakage performance and weather resistance under hygrothermal environment.From these points of view, the content of above-mentioned linking agent, with respect to (methyl) acrylic copolymer (A) 100 weight parts, preferably 0.03～2.5 weight part.
[other compositions]
In used for optical part adhesive composition of the present invention, can contain as required other compositions such as silane coupling agent, static inhibitor, antioxidant, UV light absorber, tinting material, pigment, dyestuff, tackifying resin, surface lubricant, flow agent (leveling agent), tenderizer, anti-aging agent, photostabilizer, light trigger, stopper, weighting agent, organic filler, inorganic particulate or fluidizer.Further, composition of the present invention also can contain other solvents beyond the solvent that uses in the method for manufacture (methyl) acrylic copolymer (A).Above-mentioned silane coupling agent and static inhibitor are below described.
< silane coupling agent >
As above-mentioned silane coupling agent, can enumerate: the silicon compound that ethene Trimethoxy silane, vinyl triethoxysilane and methacryloxypropyl trimethoxy silane etc. contain polymerizability unsaturated group; The silicon compound with epoxy construction of 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane and 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane; 3-aminocarbonyl propyl Trimethoxy silane, N-(2-amido ethyl) 3-aminocarbonyl propyl Trimethoxy silane and the N-silicon compound that (2-amido ethyl)-3-aminocarbonyl propyl methyl dimethoxysilane etc. contains amido; With 3-r-chloropropyl trimethoxyl silane; Oligomer type silane coupling agent etc.
In these compounds, if use have with (methyl) acrylic copolymer (A) in the silane coupling agent of functional group of contained functional group reactions, under hygrothermal environment, be difficult for producing peeling phenomenon, this point is very desirable.
The use level of the silane coupling agent in used for optical part adhesive composition of the present invention, with respect to (methyl) acrylic copolymer (A) 100 weight parts, is generally 0.01～0.5 weight part, preferably 0.05～0.3 weight part.
< static inhibitor >
In order to reduce the sheet resistance value of used for optical part adhesive composition of the present invention, use static inhibitor.In the present invention, can use known static inhibitor, this static inhibitor can be divided into (i) tensio-active agent, (ii) ionic compound and (iii) electric conductive polymer haply.
(i) as above-mentioned tensio-active agent, can use following compound: quaternary ammonium salt, amide group quaternary ammonium salt, pyridine salt, there is the cationic surfactant of the cationic groups such as primary amine groups～tertiary amine groups.
The anionic surfactant with anionic property groups such as sulphonate-base, sulfuric ester alkali, phosphoric acid ester alkali.
The amphotericses such as alkyl betaine class, alkyl imidazole betaines, oxidation of alkyl amine, amino acid sulfuric acid ester.
The nonionic surfactants such as glycerol fatty acid ester class, Span class, polyoxyethylene alkyl amine class, polyoxyethylene alkyl amine fatty acid ester, N-hydroxyethyl-N-2-hydroxyalkyl amine, alkyl diglycollic amide base class.
In addition, as tensio-active agent, also can enumerate the reactive emulsifier with polymerizable group, can use the monomer component polymer of above-mentioned tensio-active agent or reactive emulsifier is quantized to the polymer system tensio-active agent obtaining.
(ii) above-mentioned ionic compound is to consist of cationic moiety and anionicsite, at room temperature (23 ℃ of 50%RH) its can be solid state, also can be liquid.
Above-mentioned cationic moiety can be any one or two kinds in inorganic cation or organic system positively charged ion.
As above-mentioned inorganic cation, preferred as alkali ion and alkaline-earth metal ion, the Li more preferably having excellent antistatic properties +, Na +and K +.
As above-mentioned organic system positively charged ion, can enumerate: pyridinium salt positively charged ion, piperidinium salt positively charged ion, pyrrolidinium cation, pyrroline positively charged ion, pyrroles's positively charged ion, glyoxaline cation, tetrahydropyrimidine positively charged ion, dihydro-pyrimidin positively charged ion, pyrazoles positively charged ion, pyrazoline positively charged ion, tetraalkylammonium cation, trialkyl sulfonium cation, Si Wan Ji phosphonium cation etc. and derivative thereof.
On the other hand, as the anionicsite that forms ionic compound, so long as can carry out ionic bonding with above-mentioned positively charged ion, form the material of ionic compound, be not particularly limited.Particularly, can enumerate: F -, Cl -, Br -, I -, AlCl 4 -, Al 2cl 7 -, BF 4 -, PF 6 -, SCN -, ClO 4 -, NO 3 -, CH 3cOO -, CF 3cOO -, CH 3sO 3 -, CF 3sO 3 -, (CF 3sO 2) 2n -, (F 2sO 2) 2n -, (CF 3sO 2) 3c -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, F (HF) n -, (CN) 2n -, C 4f 9sO 3 -, (C 2f 5sO 2) 2n -, C 3f 7cOO-and (CF 3sO 2) (CF 3cO) N -deng.In these ions, contain the negatively charged ion of the contain fluorine atoms of the ionic compound that low melting point preferably can be provided, more preferably (F 2sO 2) 2n -(CF 3sO 2) 2n -.
The ionic compound using as the static inhibitor in the present invention, preferred: two (trifluoromethane sulfonyl group) imidization lithium, two (two fluorosulfonyls) imidization lithium, lithium three (trifluoromethane sulfonyl group) methane, two (trifluoromethane sulfonyl group) imidization potassium, two (two fluorosulfonyls) imidization potassium, phosphofluoric acid 1-ethylpyridine, phosphofluoric acid 1-butyl-pyridinium, phosphofluoric acid 1-hexyl-4-picoline, phosphofluoric acid 1-octyl group-4-picoline, two (fluorosulfonyl) imines of 1-octyl group-4-picoline, Tetrafluoroboric acid (N, N-diethyl-N-methyl-N-(2-methoxy ethyl) ammonium), N, two (trifluoromethane sulfonyl group) imines of N-diethyl-N-methyl-N-(2 methoxy ethyl) ammonium, fluorine sulfonium imines 1-octyl group pyridine, 1-octyl group 3-picoline and trifluoro sulfonium imines etc.
(iii), as above-mentioned electric conductive polymer, can enumerate Polythiophene, polyaniline, polypyrrole and derivative thereof etc.
In used for optical part adhesive composition of the present invention, the use level of static inhibitor, with respect to (methyl) acrylic copolymer (A) 100 weight parts, is generally 0.01～3 weight part, preferably 0.05～2.5 weight part.
[used for optical part adhesive composition]
It is neccessary composition that used for optical part adhesive composition of the present invention be take above-mentioned (methyl) acrylic copolymer (A) and linking agent (B), can contain other above-mentioned one-tenth arbitrarily and grade.
Then in above-mentioned (methyl) acrylic copolymer (A), by by (methyl) acrylate (a-2) with (a-3) with specified proportion copolymerization, excellent stiffness characteristic and optical compensation function have been had both, and due to copolymerization together with (methyl) vinylformic acid (a-1), not only merely strengthened hardness property, also can in (methyl) acrylic copolymer (A), introduce suitable flexibility, thereby realize good dimensional stability.
Further, in (methyl) acrylic copolymer (A), copolymerization (methyl) acrylic monomer (a-4), because there is crosslinking reaction with a certain amount of linking agent coordinating (B) in it, produce the crosslinked of appropriateness, thereby realized good cohesiveness, good dimensional stability and weather resistance under hygrothermal environment.
Because dimensional stability and the weather resistance of composition of the present invention under hygrothermal environment is good, therefore, even in hygrothermal environment, be out of shape also considerably lessly, and be difficult to occur the phenomenon of the reduction values of the product such as foaming.
For example, while carrying out small creep test with composition of the present invention by following declaration condition, the measured value of implementing at 60 ℃ is generally 1.05～2.00 with the ratio (60 ℃ of measured value/23 ℃ measured values) of the measured value of implementing at 23 ℃, and preferably 1.05～1.95.
Small creep test
Used for optical part adhesive composition of the present invention is coated on the polyester film of lift-off processing and is dried, make and there is the bonding sheet that thickness is the adhesive layer of 25 μ m.
By this bonding sheet and the Polarizer (plano-polarized light plate) being formed by TAC (cellulosetri-acetate)-PVA (polyvinyl alcohol)-TAC, with above-mentioned adhesive layer, fit with the mode that above-mentioned Polarizer contacts, make and evaluate with bonding processing Polarizer.
The evaluation of making is cut into wide 10mm * long 100mm with bonding processing Polarizer, peels the above-mentioned polyester film through lift-off processing, on glass by adhesive layer and above-mentioned glass contact in alkaline purification, and fitting by 10mm * 10mm fitting area.
Then, the evaluation with above-mentioned glass gluing is carried out to autoclave processing (50 ℃, 5atm) with bonding processing Polarizer, under 23 ℃/50%RH environment standing 24 hours, and using it as small creep test sample.
In the cavity BOX of small creep test machine, the long 15mm place of fixing chuck part carries out the setting of sample for above-mentioned test, will in cavity BOX, be heated to measure temperature (23 ℃ or 60 ℃).Measuring at temperature after standing 40 minutes, with stretching loading 800g, stretching time 1000 seconds, on and the length direction at above-mentioned Polarizer parallel at the contact surface with this Polarizer and above-mentioned glass, above-mentioned test is stretched with bonding processing Polarizer with the above-mentioned evaluation in sample.
After stretching, the distance (mm) of the skew of the fitting part of mensuration glass and Polarizer, as the test-results (measured value) of small creep.
The measured value of 23 ℃ in small creep test is generally 0.05～1.00mm, preferably 0.08～0.50mm, more preferably 0.10～0.30mm;
The measured value of 60 ℃ in small creep test is preferably 0.15～1.00mm, more preferably 0.15～0.50mm.
That is,, even if composition of the present invention is difficult to distortion and excellent size stability under hygrothermal environment, in addition, the degree of the distortion that the variation of Yin Wendu causes is almost constant.
Measured value in these small creep tests, is mainly to stipulate by the hardness property of composition of the present invention, and by this characteristic is adjusted, measured value also can change.Generally, if raising hardness property, improve the copolymerization ratio of (methyl) acrylate (a-2) in (methyl) acrylic copolymer (A), improve the copolymerization ratio of (methyl) acrylic monomer (a-4) with polar functional group, increase the usage quantity of linking agent (B), said determination value trend diminishes.In addition, if reduce the copolymerization ratio of (methyl) acrylate (a-2) in (methyl) acrylic copolymer (A), the copolymerization ratio that reduction has (methyl) acrylic monomer (a-4) of polar functional group, the usage quantity that reduces linking agent (B), it is large that said determination value tends to become.
Because the distortion of this kind in hygrothermal environment is very little, therefore the optics when the composition of the present invention of having fitted under hygrothermal environment, present contractions, float stick up, distortion etc. is when be out of shape, composition of the present invention has represented its proof stress, can prevent well above-mentioned distortion.
Consequently prevented well the light leak causing due to above-mentioned distortion.And, even if can not prevent light leak completely, also can, by the optical compensation function from above-mentioned (methyl) acrylic copolymer (A), suppress these small light leaks.
[bonding sheet]
Used for optical part adhesive composition of the present invention is when binding agent is used, if form adhesive layer as bonding sheet on base material film, simple to operate and convenient.
If the operability of considering while using above-mentioned bonding sheet in the manufacturing process of flat-panel monitor etc., the preferred stripping film of above-mentioned base material film; As its material, can enumerate: for example polyester, polyolefine, polyethers.
For example can be by the masking liquid that coating contains used for optical part adhesive composition of the present invention on base material film, and dry make the gasifications such as solvent that contain in masking liquid, the adhesive layer that forms desired thickness is made bonding sheet of the present invention.The thickness of above-mentioned adhesive layer is not particularly limited, preferably the scope of 5～100 μ m, the more preferably scope of 10～50 μ m.If the thickness deficiency of this adhesive layer 5 μ m, there will be the situation that can not bring into play fixed performance (damp and hot weather resistance etc.), if surpass 100 μ m, thereby easily there is binding agent when severing bonding sheet, overflow the situation that causes processibility to reduce.
In addition, in bonding sheet of the present invention, with stripping film, cover the face not contacting with above-mentioned base material film of above-mentioned bonding basic unit, during use, above-mentioned stripping film can be peeled.
[optics that adheres to adhesive layer]
By the adhesive layer that contains used for optical part adhesive composition of the present invention being formed on at least one side of optics, above, can obtain the above-mentioned optics that adheres to adhesive layer of realizing good light leakage performance and weather resistance under hygrothermal environment.
As the optics in the present invention; be not particularly limited; can enumerate the optical thin film that is applicable to flat-panel monitor; for example Polarizer, polarizer, elliptical polarization plate, optical compensating film, briliancy promote film, infrared resistant/hertzian wave film, use antireflective film, surface protective film above, and the stacked film of these films etc.
And in these films Polarizer particularly, because the deformation extent of the structural sheet under hygrothermal environment is different, therefore produce warp or physical distortion and multiple bending occur.This multiple bending is the reason that light leak occurs, and then causes serious problem.Composition of the present invention, because its hardness property can suppress the distortion of Polarizer, thereby thereby the distortion that can suppress optics suppress light leak, and the weather resistance that its inhibition is peeled off etc. is also very good.In addition,, even from producing warp slightly, also can suppress this point of light leak by optical compensation function, be applicable to being very much applied to Polarizer and sheet glass laminating.
In addition, this that can suppress Polarizer distortion because of its hardness property put, and composition of the present invention is applicable to the liquid crystal panel of more large-sized TV purposes.Be particularly suitable for being applied to the Polarizer in liquid crystal panel and glass substrate laminating for VA pattern.
< adheres to the making method > of the optics of adhesive layer
The optics that adheres to adhesive layer, for example, can make by the method for following (1)～(3).
(1) by known method (die coating method, cutter formula coating method etc.), the masking liquid that contains used for optical part adhesive composition of the present invention is coated on the peel ply of stripping film, by heated drying, the solvent containing in masking liquid is gasified, formation has the adhesive layer of desired thickness, and by itself and optical member adhering.
(2) by known method (die coating method, cutter formula coating method etc.), the masking liquid that contains used for optical part adhesive composition of the present invention is coated on optics, by heated drying, the solvent containing in masking liquid is gasified, formation has the adhesive layer of desired thickness, and by the peel ply laminating of itself and stripping film.
(3) by known method (die coating method, cutter formula coating method etc.), the masking liquid that contains used for optical part adhesive composition of the present invention is coated on the peel ply of the 1st stripping film, by heated drying, the solvent containing in masking liquid is gasified, formation has the adhesive layer of desired thickness, and by itself and the 2nd in peel ply (conventionally low than the peeling force of the stripping film in the 1st) laminating of stripping film, make non-carrier adhesive film.Then, peel the 2nd stripping film and optical member adhering.
Used for optical part adhesive composition of the present invention is after above-mentioned adhesive layer forms, at room temperature (23 ℃ of 50%RH) is lower is cross-linked 3～7 days, or under heating promotion condition, (40 ℃ of 90%RH) is cross-linked 2～5 days, can be attached on the structural sheet of flat-panel monitor described later.
In addition, there is no particular limitation for the thickness of the adhesive layer in the optics that adheres to adhesive layer obtaining, preferably the scope of 5～100 μ m, the more preferably scope of 10～50 μ m.If the thickness deficiency of this adhesive layer 5 μ m, there will be the situation that can not bring into play fixed performance (damp and hot weather resistance etc.), if surpass 100 μ m, thereby easily there is binding agent when severing bonding sheet, overflow the situation that causes processibility to reduce.
Further, while using composition of the present invention in the manufacture of FPD, form the structural sheet that the adhesive layer consisting of said composition is used as FPD.The crosslinked that contains (methyl) acrylic copolymer (A) with optical compensation function in adhesive layer, therefore the photoelastic coefficient of above-mentioned adhesive layer is preferably-320～0 (* 10 -12m 2/ N).About the measuring method of photoelastic coefficient, in embodiment part, illustrate.
[flat-panel monitor]
Can at least with a slice optics that adheres to adhesive layer of the present invention, manufacture flat-panel monitor, the FPD so manufacturing is also contained in scope of the present invention.
As FPD, can enumerate liquid-crystal display (LCD), plasma display (PDP) and field emission escope (FED) etc.
LCD generally forms by having the laminate structure of following setting: by having the glass substrate of transparency electrode, carry out clamping liquid crystal layer, between this glass substrate and liquid crystal layer, be provided with alignment film or colored filter, on the face of the close liquid crystal layer of glass substrate and the back side, Polarizer be set further.
PDP generally forms by having the laminate structure of following setting: between relative glass substrate, have luminescent coating, be provided with various conductor layers or electrode, other functional layers on the face of the close above-mentioned luminescent coating of above-mentioned glass substrate.
FED generally forms by having the glass substrate laminate structure of following setting: glass substrate, the anode electrode (anode) forming on this substrate, be formed on luminescent coating on this electrode, vacuum space and across this space cathode electrode relative with luminescent coating (cathode).
The optics that adheres to adhesive layer of the present invention forms a part for the structural sheet of these FPD.In addition, can use bonding sheet of the present invention, at least a portion of FPD structural sheet is stacked gradually.
Embodiment
The present invention is described in detail by the following examples.
The Production Example > of the acrylic copolymer using in < embodiment 1～13 and comparative example 1～8
In being equipped with the reaction unit of stirrer, reflux cooler, thermometer and nitrogen ingress pipe, according to the proportioning shown in table 1～3 (weight part), add the acrylate shown in table 1～3 (a-1)～(a-3) and acrylic monomer (a-4), then by the use level of monomer concentration 50 % by weight, add ethyl acetate.
Then, relatively acrylate (a-1)～(a-3) and total 100 weight parts of acrylic monomer (a-4), add 2 of 0.1 weight part, 2 '-Diisopropyl azodicarboxylate, on one side with the air in nitrogen replacement reaction unit, stir and be warming up to 60 ℃ on one side, then under pressure 1atm, react 4 hours.After reaction terminating, the acrylic copolymer obtaining is diluted by ethyl acetate, obtain acrylic copolymer solution.
< evaluates the making > with bonding processing Polarizer
The acrylic copolymer solution that use obtains by Production Example, the use level of according to the form below 1～3 is added each composition, obtains the solution of adhesive composition.On the surface of the polyester film through lift-off processing, and make it dry obtain thering is the bonding sheet that thickness is the adhesive layer of 25 μ m this adhesive composition solution coat.This bonding sheet is attached to the one side of polarizing film of the layer structure of TAC-PVA-TAC, then slaking 7 days under the dark room conditions of 23 ℃/50%RH, obtains evaluating with bonding processing Polarizer.
For each, evaluate with bonding processing Polarizer, carry out table 1～shown in 3 about small creep, light leak, floatingly stick up, evaluation that bubble, crack peel off.
Table 1
Table 2
Table 3
Abbreviation in table 1～3 etc. thes contents are as follows:
BA-n-butyl acrylate
T-BA: tert-butyl acrylate
POA: vinylformic acid phenoxy ethyl
HEA: vinylformic acid 2-hydroxy methacrylate
MA: methyl acrylate
CHA: cyclohexyl acrylate
IBOA: isobornyl acrylate
AA: vinylformic acid
TD:XDI is isocyanate compound (TD-75: Zong Yan chemical company manufactures)
L:TDI affixture type isocyanate compound (CORONATE L: Japanese polyurethane company manufactures)
KBM-403:3-glycidyl propyl trimethoxy silicane (manufacture of chemical industrial company of SHIN-ETSU HANTOTAI)
Static inhibitor: 1-octyl group-4-picoline-bis-(fluorosulfonyl) imide
[Tg mensuration]
Carry out table 1 in such a way～the various Acrylic Acid Monomers (a-1) shown in 3～mensuration of the Tg of homopolymer (a-3).
By solution polymerization, prepare the various homopolymer shown in table 4 as test film.
At N 2environment under, test film ratio with 10 ℃/min in the scope of-60 ℃ to 180 ℃ is heated up, with DSC (the differential scanning calorimetry DSC8230 that Rigaku company manufactures), according to JIS (Japanese Industrial Standards) K7121 (the transition temperature measuring methods of plastics), carry out calorimetric measurement.
Table 4
Example) Mw PDI(Mw/Mn) Tg(℃)
Bn 500000 5.2 -54
t-BA 500000 5.6 41
POA 500000 4.9 -22
MA 500000 5.3 7
CHA 500000 5.5 15
IBOA 500000 5.2 94
HEA 100000 4.2 15
AA 80000 3.6 106
[Mw, PDI measure]
For the acrylic copolymer of preparing according to embodiment and comparative example, according to following GPC condition determination, measure weight-average molecular weight (Mw), number-average molecular weight (Mn), try to achieve heterogeneity index (PDI=Mw/Mn).
<GPC condition determination >
Determinator: HLC-8120GPC (manufacture of Dong Cao company)
GPC tubular column structure: following 5 series connection tubing strings (manufacture of Cao Jun Shidong company)
(1) TSK-GEL HXL-H (protection tubing string)
(2)TSK-GEL?G7000HXL
(3)TSK-GEL?GMHXL
(4)TSK-GEL?GMHXL
(5)TSK-GEL?G2500HXL
Sample concentration: be diluted to 1.0mg/cm with tetrahydrofuran (THF) 3.
Mobile phase solvent: tetrahydrofuran (THF)
Flow: 1ml/min
Tubing string temperature: 40 ℃
[each evaluation method]
By method shown below, undertaken table 1～the various evaluations shown in 3.
The small creep > of <
Be cut into wide 10mm * long 100mm, and on glass in alkaline purification, to having peeled the bonding processing Polarizer for evaluation of the polyester film of crossing through lift-off processing, by adhesive layer and above-mentioned glass contact, and fit with the fitting area of 10mm * 10mm, carry out after autoclave processing (50 ℃, 5atm) under the environment of 23 ℃/50%RH standing 24 hours.Using it as small creep test sample.At small creep testing machine, (the great smart machine (strain) of English company manufactures, machine name: the setting with sample is tested at the length 15mm place of the fixing catch disc portion in cavity BOX TA.TX.PLUS).
Temperature will be heated to measure in cavity BOX, measuring at temperature after standing 40 minutes, with stretching loading 800g, stretching time 1000 seconds, parallel and along the length direction of above-mentioned Polarizer, bonding processing Polarizer for the evaluation of the above-mentioned test film that stretches according to the contact surface of Polarizer and above-mentioned glass.The distance (mm) of the skew of the above-mentioned glass after confirmation (mensuration) stretches and the fitting part of Polarizer is as the test-results of small creep.
[light leak]
At the VA type liquid crystal panels of 19 inches big or small, (IO DATA company manufactures, model: the panel taking out from LCD-A191EW), to having peeled the bonding processing plate for evaluation of the polyester film of crossing through lift-off processing, adhesive layer is contacted with above-mentioned liquid crystal panel, and above-mentioned evaluation is fitted according to the mode of cross-polarized light (crossed-Nicol) with bonding processing Polarizer and above-mentioned liquid crystal panel, under the environment of 80 ℃, place after 240 hours, under the environment of 23 ℃/50%RH, place 2 hours.
Then, the VA type liquid crystal panel of the above-mentioned Polarizer of having fitted is connected on computer in darkroom and its full frame blank screen is shown.The display monitor that this full frame blank screen is shown, with brightness photometer (Hi-Land company manufacture RISA-COLOR/CD8), be determined at the briliancy (Lcenter) in the diameter 1cm region of briliancy (La, Lb, Lc, Ld) in the region of the diameter 1cm each corner near and watch-dog middle body, and calculate light leak (Δ L) by following formula.Δ L is less to be meaned (from backlight), and light leak is fewer, if common less than 2.0 can be used as liquid-crystal display and uses with panel.
ΔL＝(La+Lb+Lc+Ld)/4-Lcenter
Light leak size is under the state showing at above-mentioned full frame blank screen, and the part of Visual Confirmation generation light leak as shown in Figure 1, is measured from there is the distance d at the angle of light leak part.If distance, below 30mm, can be used as liquid-crystal display and uses with panel.
And, for comparative example 1 and 3～6, under the environment of 80 ℃, place after 240 hours and confirm display monitor, there is foaming, the bad order causing because of adhesive layer, the mensuration that cannot carry out light leak test such as peeled off.
The damp and hot weather resistance > of <
The evaluation of having peeled off through the polyester film of lift-off processing is being become to 15 inches of sizes (233mm * 309mm) with the severing of bonding processing Polarizer, in the one side of the non-alkali glass that is 0.5mm at thickness, adhesive layer is contacted with above-mentioned sheet glass, and make its attaching with stacking-up machine roll extrusion.After attaching, in autoclave (the former making manufacturing of chestnut) under 0.5MPa, the condition of 50 ℃, 20 minutes pressure treatment, obtain test plate.
The test so obtaining is placed 500 hours with plate under the condition of 60 ℃/90%RH.After off-test, test is taken out from testing circumstance with plate, under the environment of 23 ℃/50%RH standing 2 hours, the foaming of visual observation adhesive layer, peel off with crack and by following standard and evaluate.
Foaming-size)
Zero: cannot see foaming completely
△: foaming diameter is below 1mm
*: foaming diameter is larger than 1mm
Foaming-generating capacity)
Zero: cannot see foaming completely
△: foaming number is below 10
*: foaming number is than more than 10
Crack, peel off-size)
Zero: cannot see to float completely and stick up, peel off
△: it is less than 5% that the floating area that sticks up, peels off is tested with the fitting part all (100%) of plate relatively
*: it is more than 5% that the floating area that sticks up, peels off is tested with the fitting part all (100%) of plate relatively
Crack, peel off-position)
Zero: cannot see defect (float and stick up, peel off) completely
△: only at the position defectiveness from end deficiency 0.5mm
*: at the position defectiveness from more than end 0.5mm
In addition, " end " in crack, in the evaluation of peel off-position refer to by the position that produces crack, peel off move down vertical line to test with on each limit of plate, the shortest vertical line and the intersection point of test with the limit of plate.
In addition, about comparative example 5 and 6, under the condition of 60 ℃/90%RH, place viewing test plate after 500 hours, owing to producing floating that a large amount of adhesive layers cause, stick up, foam, can not evaluate with the situation of peeling off by fracture.
< photoelastic coefficient is measured >
As described below, prepare binding agent test film that 15mm * 50mm * 1mm is thick as working sample.
In the acrylic copolymer solution obtaining in Production Example, according to the ratio shown in table 1-3, add linking agent, silane coupling agent and static inhibitor, as adhesive composition solution.The mode that is 1mm according to the dried thickness of this adhesive composition solution, is coated on the PET of lift-off processing film, and dry.After dry, it is obtained to binding agent test film 12 according to 15mm * 50mm cutting, using it as test sample.
Test sample is arranged on and is measured with device (Japan Spectroscopy Corporation manufactures light splitting Ellipsometer M-220), under the environment of 23 ℃, measure.
In Fig. 2, when sample is stretched along directions X, the stress control producing, in the scope of 0～0.15N, is measured to the wavelength of each stress-the see through relation (* 1) of the phase differential of light.By (* 1), for the phase differential that sees through light of wavelength 600nm, with the relation of phase differential-stress, draw point diagram, and calculate its slope.And then, with slope=(1) * photoelastic coefficient (10 -12m 2/ N) relation is calculated photoelastic coefficient.
Reference numeral
12 binding agent test films
14 samples are fixedly used fixture
16 light sources
18 slits
20 detectors

Claims (14)

1. a used for optical part adhesive composition, is characterized in that, described adhesive composition contains:
(A): according to following ratio, following (a-1)～(a-4) carried out to (methyl) acrylic acid series co-polymer that copolymerization obtains:
(a-1) second-order transition temperature of homopolymer is-40 ℃ of (methyl) acrylate 40～94.9 % by weight following, that there is no aromatic nucleus;
(a-2) second-order transition temperature of homopolymer is more than 0 ℃, there is no (methyl) acrylate 0.1～50 % by weight of aromatic nucleus;
(a-3) there is (methyl) acrylate 0.1～25 % by weight of aromatic nucleus;
(a-4) there is (methyl) acrylic monomer of polar functional group of more than two kinds and/or (methyl) different, a kind of polar functional group acrylic monomer 0.1～6 % by weight that two or more has;
Wherein, (a-2) and (a-3) add up to 5～59.9 % by weight;
Described polar functional group is selected from carboxyl, hydroxyl, amino, amide group and epoxy group(ing);
(a-1)～(a-4) add up to 100 % by weight;
(B): relatively described (methyl) acrylic copolymer (A) 100 weight parts, the linking agent of 0.01～3 weight part.
2. used for optical part adhesive composition according to claim 1, is characterized in that, the copolymerization ratio of described (methyl) acrylate (a-2) is 10～40 % by weight.
3. used for optical part adhesive composition according to claim 1 and 2, it is characterized in that at least one in described (methyl) acrylate (a-2) the choosing group that freely (methyl) methyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate and (methyl) isobornyl acrylate form.
4. used for optical part adhesive composition according to claim 1 and 2, is characterized in that, described (methyl) acrylate (a-2) is (methyl) tert-butyl acrylate.
5. according to the used for optical part adhesive composition described in any one in claim 1～4, it is characterized in that, the copolymerization ratio of described (methyl) acrylate (a-1) is 50～90 % by weight.
6. according to the used for optical part adhesive composition described in any one in claim 1～5, it is characterized in that, described (methyl) acrylate (a-1) is selected from least one in the group that following compound forms: n-butyl acrylate, vinylformic acid n-pentyl ester, vinylformic acid isopentyl ester, Ethyl acrylate, vinylformic acid heptyl ester, vinylformic acid isopentene ester, 2-ethylhexyl acrylate, vinylformic acid n-octyl, Isooctyl acrylate monomer, vinylformic acid ester in the positive ninth of the ten Heavenly Stems, vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, (methyl) isodecyl acrylate, methacrylic acid dodecyl ester, (methyl) vinylformic acid n-tridecane base ester, vinylformic acid methoxyl group ethyl ester, vinylformic acid methoxyl group glycol ester and vinylformic acid ethoxy ethoxy ethyl ester.
7. according to the used for optical part adhesive composition described in any one in claim 1～6, it is characterized in that, at least one in the group that the freely following compound of described (methyl) acrylate (a-3) choosing forms: (methyl) vinylformic acid phenoxy ethyl class and derivative thereof that (methyl) vinylformic acid benzyl ester, general formula (I) represent
In formula (1), R 0for hydrogen or methyl; R 1for (CH 2cH 2o) nthe group representing, the integer that n is 1～20, the integer that m is 1～5; R 2for hydrogen, the carbonatoms alkyl that is 1～9, aryl that carbonatoms is 6～10 or the carbonatoms aralkyl that is 7～11; M is 2 when above, a plurality of R of existence 2can be identical also can be different.
8. according to the used for optical part adhesive composition described in any one in claim 1～7, it is characterized in that, the copolymerization ratio of described (methyl) acrylic monomer (a-4) is 1～6 % by weight.
9. according to the used for optical part adhesive composition described in any one in claim 1～8, it is characterized in that, when described used for optical part adhesive composition is carried out to following small creep test, the ratio of 60 ℃ of measured value/23 ℃ measured values is 1.05～2.00;
On the polyester film that has carried out lift-off processing, be coated with and make it dry described used for optical part adhesive composition, preparation has the bonding sheet of the adhesive layer of thickness 25 μ m;
With this bonding sheet and the Polarizer being formed by TAC-PVA-TAC, with described adhesive layer, contact with described Polarizer and make it fit to make bonding processing Polarizer for evaluation;
This evaluation is cut into wide 10mm * long 100mm with bonding processing Polarizer, peel the polyester film through described lift-off processing, and alkaline purification is on glass, by described adhesive layer and described glass contact, and according to the bond area of 10mm * 10mm, make it bonding, as evaluating with bonding processing polarisation test film;
To this evaluation with bonding processing Polarizer test film carry out autoclave (50 ℃, 50atm) process, under the environment of 23 ℃/50%RH standing 24 hours;
Then the fixing length 15mm place by chuck part in the cavity BOX of small creep tstr arranges described test film;
To in described cavity BOX, be heated to measure temperature, measuring at temperature after standing 40 minutes, with stretching loading 800g, stretching time 1000 seconds, parallel and along the length direction of Polarizer, bonding processing Polarizer for the described evaluation of the described test film that stretches according to the contact surface of Polarizer and described glass;
Measure the distance (mm) of skew of the fitting part of described glass in described test film and Polarizer.
10. according to the used for optical part adhesive composition described in any one in claim 1～9, it is characterized in that, with respect to 100 weight parts above-mentioned (methyl) acrylic copolymers (A), further contain 0.01～0.5 weight part silane coupling agent.
11. according to the used for optical part adhesive composition described in any one in claim 1～10, it is characterized in that, with respect to 100 weight parts above-mentioned (methyl) acrylic copolymers (A), further contains 0.01～3 weight part static inhibitor.
On 12. 1 kinds of base materials, formed the bonding sheet containing the adhesive layer of the used for optical part adhesive composition described in any one in good grounds claim 1～11.
13. 1 kinds of opticses that adhere to adhesive layer, it is characterized in that, it is at least one side of optics, to have formed the optics that adheres to adhesive layer of adhesive layer, and described adhesive layer contains the used for optical part adhesive composition described in any one in claim 1～11.
14. 1 kinds of flat-panel monitors, is characterized in that, it has the optics that adheres to adhesive layer according to claim 13.
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