CN104024363B - Adhesive composition used for optical part, bonding sheet, optics and display - Google Patents

Adhesive composition used for optical part, bonding sheet, optics and display Download PDF

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Publication number
CN104024363B
CN104024363B CN201280065245.1A CN201280065245A CN104024363B CN 104024363 B CN104024363 B CN 104024363B CN 201280065245 A CN201280065245 A CN 201280065245A CN 104024363 B CN104024363 B CN 104024363B
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methyl
acrylate
acrylic acid
adhesive composition
optical part
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CN104024363A (en
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小山雄司
室井佐知
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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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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (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

It is an object of the invention to provide a kind of adhesive composition used for optical part, it has excellent dimensional stability, even if also can play excellent light leakage performance and durability under hygrothermal environment.The adhesive composition used for optical part that the present invention relates to is characterised by, (methyl) acrylic acid series copolymer (A) containing certain content and cross-linking agent (B), described (methyl) acrylic acid series copolymer (A) is by obtaining the specific monomer composition of special ratios (a 1)～(a 4) copolymerization.

Description

Adhesive composition used for optical part, bonding sheet, optics and display
Technical field
The present invention relates to adhesive composition used for optical part and use its bonding sheet, with the light of adhesive layer Department of the Chinese Academy of Sciences's part and flat faced display thereof, described adhesive composition used for optical part have excellent dimensional stability and Wet heat durability, it is possible to be effectively prevented light leak or peeling under hot and humid environment.
Background technology
For the binding agent towards flat faced display (FPD) field, along with maximization and the LED of display Popularizing of mode, high image quality, the requirement of high durability are just becoming more and more higher.
Such as, the subclass liquid crystal display (LCD) in FPD is made up of liquid crystal panel, backlight and peripheral circuit. This liquid crystal panel generally by Polarizer, there is each layers such as the glass substrate of transparency electrode, colored filter constitute, Thus obtain the structure of above-mentioned glass substrate clamping liquid crystal.
Above-mentioned Polarizer is made up of the multiple structure of different materials, and each material is respectively provided with different physics, change Learn characteristic, therefore especially under high temperature, high humidity environment, owing to shrinking and expanding, the journey of the change in size of each layer Degree difference, and these different degree are the biggest.Therefore, the overall of Polarizer lacks dimensional stability.
Due to this change in size, with light leak and the durability various performances as representative overall to Polarizer can be produced Raw many and diverse influences.And it is known that the bonding between each optical thin film of Polarizer etc. or glass substrate With the kind of the binding agent used in the bonding of Polarizer, above-mentioned light leak and durability can be produced impact.
Under this present situation, by by Polarizer kind-binding agent category combinations, tackle above-mentioned light leak and resistance to The performance of various requirements such as long property, its performance required is as it was previously stated, be accompanied by large screen, LED The requirement of the higher degree of the universal and next higher image quality of mode, high-durability etc.
Here, for the kind of above-mentioned binding agent, in order to solve the leakage caused due to the change in size of Polarizer Peeling under light, hot and humid environment, can be conceived to constitute the hardness property of the polymer of binding agent or optics is special The various characteristics such as property, in order to find that good light leakage performance and realization guarantee that high-durability is studied.
Such as, it is conceived to the binding agent of hardness property, owing to being also not easy deformation and foaming etc. under hygrothermal environment, Therefore the resistance to stress when Polarizer shrinks and excellent durability, be readily obtained reasonable light leakage characteristic and Durability.But, if carried out the maximization of FPD, under former size be not the light leak of problem and a bit The foaming of point also can become obvious, therefore becomes problem.Therefore, for this High Level requiring characteristic, profit Can not sufficiently tackle with conventional binding agent.
As this binding agent, such as, patent document 1 discloses that a kind of adhesive composition, containing (methyl) Acrylic copolymer (A) and ionic compound (B) and cross-linking agent (C), described (methyl) acrylic acid Unsaturated monomer (A-2) that based copolymer (A) by specific (methyl) acrylate (A-1), has aromatic rings, And unsaturated monomer (A-3) copolymerization with polar functional group forms.
Such as, said composition can be used in the bonding of Polarizer, as the example of above-mentioned (A-1), can arrange Lifting n-butyl acrylate, the example as (A-2) can enumerate (methyl) acrylic acid 2-phenoxy ethyl, makees Example for above-mentioned (A-3) can enumerate acrylic acid or (methyl) acrylic acid 2-hydroxy methacrylate.
It addition, patent document 2 discloses that the Polarizer with the tack coat being made up of binding agent, described binding agent Contain (methyl) acrylic acid series copolymer (A) and the multi-functional compound (B) of cross-linked structure can be formed, Described (methyl) acrylic acid series copolymer (A) is by (methyl) acrylic acid of not enough-30 DEG C of the Tg of homopolymer Ester monomer (a1), the Tg of the homopolymer compound (a with vinyl more than-30 DEG C2) and contain Specific monomer (a3) constitute.
As above-mentioned (a1) example can enumerate n-butylacrylate, as above-mentioned (a2) example propylene Acid tertiary butyl ester, as above-mentioned (a3) example can enumerate (methyl) acrylic acid or (methyl) acrylic acid 2- Hydroxy methacrylate.
But, the binding agent disclosed in these documents, as mentioned above, it is impossible to tackle the spy of the height of existing requirement Property.
Prior art literature
Patent documentation
Patent documentation 1: JP 2010-66755 publication
Patent documentation 2: JP 2006-301572 publication
Summary of the invention
The problem to be solved in the present invention
It is an object of the invention to provide a kind of adhesive composition used for optical part, described adhesive composition Excellent in dimensional stability, even if also can play light leakage performance and the durability of excellence under hygrothermal environment.
The method of solution problem
The present inventor, is conceived to the hardness property of binding agent and optical compensation function and crosslinking, combines binding agent Thing is studied.It is found that the regulation by the polymer monomer with flexibility and the hardness at polymer can be given Middle monomer uses according to specific ratio, thus the hardness property of polymer is set in suitable scope； It addition, with the monomer of optical compensation function and the polymer monomer with bridging property can be given polymer can be given Use according to specific ratio and can obtain one (methyl) acrylic copolymer compound, by by above-mentioned (first Base) acrylic copolymer compound sets the suitable degree of cross linking and cross-links, it is possible to provide dimensional stability and damp and hot Excellent durability, also can effectively prevent the binding agent used for optical part of light leak and peeling in the environment of hot and humid Compositions.
That is, the adhesive composition used for optical part of the present invention be characterised by containing:
(A): according to following ratio, following (a-1)～(a-4) are carried out (methyl) third that copolymerization obtains Olefin(e) acid system co-polymer:
(a-1) glass transition temperature of homopolymer be less than-40 DEG C, (methyl) third that do not have aromatic rings Olefin(e) acid ester 40～94.9 weight %；
(a-2) glass transition temperature of homopolymer is more than 0 DEG C, does not has (methyl) acrylic acid of aromatic rings Ester 0.1～50 weight %；
(a-3) there is (methyl) acrylate 0.1～25 weight % of aromatic rings；
(a-4) have (methyl) acrylic monomer of polar functional group of more than two kinds and/or two or more There is (methyl) acrylic monomer 0.1～6 weight % different, a kind of polar functional group；
(wherein, (a-2) and (a-3) adds up to 5～59.9 weight %；Above-mentioned polar functional group selected from carboxyl, Hydroxyl, amino, amide groups and epoxy radicals；
(a-1)～(a-4) add up to 100 weight %)
(B): the most above-mentioned (methyl) acrylic acid series copolymer (A) 100 weight portion, 0.01～3 weight The cross-linking agent of part.
Copolymerization ratios preferably 10～40 weight % of above-mentioned (methyl) acrylate (a-2).
Above-mentioned (methyl) acrylate (a-2) preferably is selected from by (methyl) acrylic acid methyl ester., methacrylic acid different Butyl ester, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate and (methyl) isobomyl acrylate At least one in the group that ester is constituted.
Above-mentioned (methyl) acrylate (a-2) preferably (methyl) tert-butyl acrylate.
The copolymerization ratios of above-mentioned (methyl) acrylate (a-1) is preferably 50～90 weight %.
Above-mentioned (methyl) acrylate (a-1) at least one in the group that following compound is constituted: propylene Acid N-butyl, acrylic acid n-pentyl ester, isoamyl acrylate, Hexyl 2-propenoate, heptylacrylate, acrylic acid are different Amylene ester, 2-EHA, n-octyl, Isooctyl acrylate monomer, acrylic acid positive nonyl ester, third Olefin(e) acid different nonyl ester, (methyl) acrylic acid ester in the positive last of the ten Heavenly stems, (methyl) isodecyl acrylate, methacrylic acid positive ten Dialkyl, (methyl) acrylic acid n-tridecane base ester, methoxyethyl acrylate, methoxyethyl are poly- Glycol ester and ethioxy ethoxyethyl group ester.
At least one in above-mentioned (methyl) acrylate (a-3) choosing group that freely following compound is constituted: (first Base) Phenoxyethyl (methyl) esters of acrylic acid that represents of benzyl acrylate, following logical formula (I) and spreading out Biology,
In formula (1), R0For hydrogen or methyl；R1For (CH2CH2O)n(n is 1～20 to the group represented Integer), m is the integer of 1～5, R2For alkyl that hydrogen, carbon number are 1～9, carbon number be 6～ The aryl of 10 or the aralkyl that carbon number is 7～11, when m is more than 2, the multiple R existed2Can be identical Also can be different.
The copolymerization ratios of above-mentioned (methyl) acrylic monomer (a-4) is preferably 1～6 weight %.
When above-mentioned adhesive composition used for optical part is carried out following small creep test, preferably 60 DEG C measured values The ratio of/23 DEG C of measured values is 1.05～2.00.
Small creep test
Above-mentioned adhesive composition used for optical part is coated with on the mylar carrying out lift-off processing and makes it Being dried, preparation has the bonding sheet of the adhesive layer of thickness 25 μm.
With this bonding sheet and the polarisation that is made up of TAC (Triafol T)-PVA (polyvinyl alcohol)-TAC Plate, contacts with above-mentioned Polarizer with above-mentioned adhesive layer and makes it fit to make evaluation bonding processing Polarizer.
This evaluation bonding processing Polarizer is cut into wide 10mm × long 100mm, will be at above-mentioned stripping The alkali that the mylar of reason is peeled off processes on glass, by above-mentioned adhesive layer and above-mentioned glass contact, and according to The bond area of 10mm × 10mm makes it bond, as evaluating with bonding processing Polarizer test film.
To this evaluation bonding processing Polarizer test film carry out autoclave (50 DEG C, 50atm) process, 24 hours are stood in the environment of 23 DEG C/50%RH；
Then come at length 15mm of the fixing chuck section in the cavity BOX of small creep tester Above-mentioned test film is set；
Temperature is measured, after standing 40 minutes at a temperature of measuring, with stretching by being heated in above-mentioned cavity BOX Loading 800g, stretching time 1000 seconds, parallel with the contact surface of above-mentioned glass and along polarisation according to Polarizer The length direction of plate stretches the above-mentioned evaluation bonding processing Polarizer of above-mentioned test film；
Measure the distance (mm) of the skew of the fitting part of the above-mentioned glass in above-mentioned test film and Polarizer.
The adhesive composition used for optical part of the present invention, above-mentioned relative to 100 weight portions (methyl) acrylic acid Based copolymer (A), further preferably containing 0.01～0.5 weight portion silane coupler.
It addition, above-mentioned composition, above-mentioned relative to 100 weight portions (methyl) acrylic acid series copolymer (A), Further preferably containing 0.01～3 weight portion antistatic additive.
Use the adhesive composition used for optical part of the present invention of the composition as adhesive layer, can get at base The adhesive layer that formed on material thin film and the bonding sheet that constitutes.
It addition, the optics being attached to this adhesive layer is also contained in the scope of the present invention, it is at optics The optics being attached to adhesive layer of adhesive layer, above-mentioned adhesive layer is defined at least one side of parts It is using the adhesive composition used for optical part containing the present invention as feature.
The flat faced display of the present invention is characterized to have the optics being attached to above-mentioned adhesive layer.
The effect of invention
The invention provides dimensional stability and wet heat durability is excellent, can the most anti-leak-stopping under hot and humid environment Light or the adhesive composition used for optical part of peeling, be directed to use with the bonding sheet of said composition simultaneously, adhere to and glue The optics of knot oxidant layer and FPD.
Accompanying drawing explanation
In the mensuration of Fig. 1 light leak size in an embodiment, it is shown that distance d at the angle of part occurs from light leak Ideograph.
Fig. 2 shows the ideograph of the assay method of photoelastic coefficient in an embodiment.
Detailed description of the invention
The adhesive composition used for optical part (hereinafter referred to as " compositions of the present invention ") of the next coming in order explanation present invention And use its bonding sheet, the optics being attached to adhesive layer and flat faced display.And, in this theory In bright book, (methyl) acrylic acid refers to methacrylic acid and acrylic acid, and (methyl) acrylate refers to Methacrylate or acrylate.
[adhesive composition used for optical part]
(A) (methyl) acrylic acid series copolymer
(methyl) acrylic acid series copolymer (A) of the constituent of the compositions of the present invention is by above-mentioned Specific monomer component (a-1)～(a-4) obtain with specific ratio copolymerization.Illustrate that these are single individually below Body.
< the glass transition temperature of (a-1) homopolymer (methyl) propylene not having aromatic rings below-40 DEG C Esters of gallic acid >
(methyl) acrylate (a-1) used in the present invention, the glass transition temperature of its homopolymer (with Lower abbreviation Tg) it is less than-40 DEG C.
Above-mentioned Tg in this manual, except there being specified otherwise, refers to by the test film (homopolymer) measuring Tg At N2In the environment of, in the range of-60 DEG C to 180 DEG C, make it heat up with the ratio of 10 DEG C/minute, use DSC (Rigaku company manufactures, differential scanning calorimetry DSC8230) carries out calorimetry and tries to achieve.It addition, survey Determine to carry out according to JIS (Japanese Industrial Standards) K7121 (the transition temperature assay methods of plastics).
If only for improving hardness property, making the adhesive composition used for optical part of the present invention be handed over Due to inappropriate situation such as viscous close sense can be occurred not enough in conjuncted, therefore use the Tg of homopolymer-40 DEG C with Under (methyl) esters of acrylic acid (a-1), can give (methyl) acrylic acid series copolymer (A) appropriateness Flexibility thus obtain balance.
It addition, above-mentioned (methyl) acrylate (a-1) does not have aromatic rings.If there is aromatic rings, it is impossible to Give (methyl) acrylic acid series copolymer (A) flexibility, additionally by (methyl) acrylate (a-3) During the balance of the regulation carrying out optical compensation function, also can produce inappropriate situation.
In the present invention, above-mentioned aromatic rings is to form by annular arrangement structure with pi-electron and atom, and it meets Huckel's rule, above-mentioned pi-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, acrylic acid n-pentyl ester, Isoamyl acrylate (Isopentyl acrylate), Hexyl 2-propenoate, heptylacrylate, acrylic acid isopentenyl ester (Isoamyl acrylate), 2-ethylhexyl acrylate, n-octyl, Isooctyl acrylate monomer, third Olefin(e) acid positive nonyl ester, acrylic acid different nonyl ester, (methyl) acrylic acid ester in the positive last of the ten Heavenly stems, (methyl) isodecyl acrylate, Methacrylic acid dodecyl ester, (methyl) acrylic acid n-tridecane base ester, methoxyethyl acrylate, Methoxyethyl macrogol ester and ethioxy ethoxyethyl group ester etc..
In these compounds, from obtaining the balance of hardness property and flexibility and realizing excellent resistance to stress From the point of view of viewpoint, preferably n-butyl acrylate and 2-EHA.
(methyl) described above acrylate (a-1), can be used alone a kind or two or more combination made With.
< glass transition temperature of the homopolymer of (a-2) is more than 0 DEG C and does not have (methyl) of aromatic rings Acrylate >
For (methyl) acrylate (a-2) used in the present invention, the Tg of its homopolymer is more than 0 DEG C. (methyl) acrylate (a-2) higher for Tg of this homopolymer imparts (methyl) acrylic copolymer The hardness property that thing (A) is excellent, and the high dimensionally stable of the adhesive composition used for optical part to the present invention Property is made contributions.
It addition, (methyl) acrylate (a-2) does not have aromatic rings.If there is aromatic rings, then passing through During the balance of the regulation of the optical compensation function of aftermentioned (methyl) acrylate (a-3), it may occur that inappropriate Situation.
This (methyl) acrylate (a-2), can enumerate: (methyl) acrylic acid methyl ester., methacrylic acid Propyl ester, n-BMA, isobutyl methacrylate, (methyl) tert-butyl acrylate, (methyl) Cyclohexyl acrylate, (methyl) isobornyl acrylate and (methyl) stearyl acrylate acid esters etc..
In these compounds, from the viewpoint of realizing excellent stiffness characteristic, preferably (methyl) acrylic acid first Ester, isobutyl methacrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate and (first Base) isobornyl acrylate, particularly preferably (methyl) tert-butyl acrylate.
(methyl) described above acrylate (a-2), can be used alone a kind or two or more combination made With.
(methyl) acrylate of aromatic rings<(a-3) have>
(methyl) acrylate (a-3) has aromatic rings, by the construction unit come by it is added on (first Base) in acrylic acid series copolymer (A), thus can suitably control the optical compensation merit of above-mentioned copolymer (A) Energy.Through this, the adhesive composition used for optical part of the present invention is used to bond chemical components, even if damp and hot Occur a little light leak also can suppress this light leak by above-mentioned optical compensation function under environment.
As this (methyl) acrylate (a-3), (methyl) benzyl acrylate, following logical can be enumerated (methyl) acrylate that formula (1) represents and derivant thereof.
In formula (1), R0For hydrogen or methyl；R1For (CH2CH2O)n(n is 1～20 to the group represented Integer), m is the integer of 1～5, R2For alkyl that hydrogen, carbon number are 1～9, carbon number be 6～ The aryl of 10 or the aralkyl that carbon number is 7～11, when m is more than 2, the multiple R existed2Can be identical Also can be different.
(methyl) acrylate represented as formula (1) and the object lesson of derivant thereof, Can enumerate: (methyl) acrylate, (methyl) acrylic acid phenoxy group binaryglycol ester, (first Base) acrylic acid phenoxy group (gathering) glycol ester, nonyl phenol EO addition product (methyl) acrylate, Ethoxylation o-phenyl phenol (methyl) acrylate etc..
In these compounds, from the viewpoint of realizing excellent optical compensation function, preferably (methyl) third Olefin(e) acid benzyl ester and (methyl) acrylate.
(methyl) described above acrylate (a-3), can be used alone a kind or two or more combination made With.
< (a-4) have (methyl) acrylic monomer of two or more polar functional group and/or two or more not Same, there is a kind of polar functional group (methyl) acrylic monomer >
(methyl) acrylic monomer (a-4) used in the present invention has polar functional group, with friendship described later Crosslink reaction between connection agent (B), thus realize the excellent of the adhesive composition used for optical part of the present invention Good bonding characteristic.Above-mentioned functional group is carboxyl, hydroxyl, amido, amide groups and epoxy radicals.At these groups In, from the viewpoint of the good durability hygrothermal environment, preferably hydroxyl.
It addition, (methyl) acrylic monomer (a-4) has two or more polar functional group, it is believed that pass through There is different various polarity functional groups, the crosslinking between (methyl) acrylic acid series copolymer (A) can be suitably Carry out, thus realize the good degree of cross linking.
Above-mentioned " having two or more polar functional group " refers to by by (methyl) propylene of multiple molecular compositions Acid is monomer (a-4) when treating as entirety, there is two or more polar functional group.
Therefore, (methyl) acrylic monomers (a-4) is a kind of monomer, can have 2 in this monomer 1 molecule Plant above polar functional group；(methyl) acrylic monomer (a-4) can also be by two or more different list Body is constituted, and these monomers are respectively provided with a kind of polar functional group.Although and the most do not include be structure not Same monomer of more than two kinds, but the situation of the identical polar functional group having.
In (methyl) acrylic acid series copolymer (A), as monomer (a-4), can only use 1 molecule monomer The monomer of middle two or more polar functional group of existence, it is possible to do not use this monomer and use and of more than two kinds have The monomer of a kind of polar functional group, it is possible to both use.
Additionally, in this manual, meet any one of (methyl) acrylate (a-1)～(a-3), And meet the monomer of (methyl) acrylic monomer (a-4), then it is 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 tert-butyl acrylamide sulfonate etc..
It addition, as (methyl) acrylic monomer with a kind of polar functional group described above, can arrange Lift following monomer:
I () has (methyl) acrylic monomer of carboxyl: (methyl) acrylic acid, (methyl) acrylic acid β-carboxyethyl；
(ii) there is (methyl) acrylic monomer of hydroxyl: (methyl) acrylic acid 2-hydroxy methacrylate, (first Base) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxybutyl, (methyl) acrylic acid monoglyceride, (methyl) acrylic acid (gathering) ethylene glycol ester, (methyl) acrylic acid (gathering) propylene glycol monoester；
(iii) there is (methyl) acrylic monomer of amido: (methyl) acrylic acid aminoethyl, (first Base) acrylic acid N, N dimethyl aminoethyl, (methyl) acrylic acid tert-butyl group aminoethyl；
(iv) there is (methyl) acrylic monomer of amide group: (methyl) acrylamide, N, N-bis- Methyl (methyl) acrylamide, N-butyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxymethyl-propane (methyl) acrylamide；
V () has (methyl) acrylic monomer of epoxy radicals: (methyl) glycidyl acrylate, (methyl) acrylic acid 4-hydroxybutyl glycidyl ether.
<other monomers>
In the present invention, in the effective scope not damaging the present invention, in order to regulate various characteristic, (methyl) In acrylic acid series copolymer (A) can containing in addition to above-mentioned monomer component (a-1)～(a-4) from other The construction unit of monomer.
As the example of these other monomer, can enumerate: styrene, α-methyl styrene, vinyl acetate, Propionate, ethyl acrylate, Isobutyl 2-propenoate, 2-Ethylhexyl Methacrylate, lauryl Ester etc..
<manufacture method of (methyl) acrylic acid series copolymer (A)>
(copolymerization ratios of each monomer)
(methyl) acrylic copolymer (A) of the constituent of the adhesive composition used for optical part of the present invention, Special ratios copolymerization monomer component described above (a-1)～(a-4) and as required according to following description Other monomers obtain.
Above-mentioned (methyl) acrylate (a-1) copolymerization ratio in (methyl) acrylic acid series copolymer (A) Example, from the viewpoint of the balance of hardness property and flexibility, is 40～94.9% weight %, preferably 50～90 Weight %.
Above-mentioned (methyl) acrylate (a-2) copolymerization ratio in (methyl) acrylic acid series copolymer (A) Example, from the viewpoint of hardness property, is 0.1～50% weight %, preferably 10～40 weight %, further Preferably 10～25 weight %.
Above-mentioned (methyl) acrylate (a-3) copolymerization ratio in (methyl) acrylic acid series copolymer (A) Example, from the viewpoint of optical compensation function, is 0.1～25% weight %, preferably 5～20 weight %.
Above-mentioned (methyl) acrylate (a-4) copolymerization ratio in (methyl) acrylic acid series copolymer (A) Example, from the viewpoint of the suitable degree of cross linking, is 0.1～6% weight %, preferably 1～6 weight %.
And, the copolymerization ratios of each monomer component (a-1)～(a-4) add up to 100 weight %.
It addition, in order to hardness property and optical compensation function being simultaneously set in suitable region and effectively preventing Leak-stopping light, the copolymerization ratios of (methyl) acrylate (a-2) and (a-3) adds up to 5～59.9 weight %, Preferably 10～50 weight %.
Further, add up to 100 weight portions relative to monomer (a-1)～(a-4), other monomers above-mentioned Copolymerization ratios is usually 0～5 weight portions.
(manufacture method of (methyl) acrylic acid series copolymer (A))
(methyl) acrylic acid series copolymer (A) can pass through solution polymerization process, block polymerization, emulsifying gather The known polymerization such as legal, suspended polymerization is by each monomer component (a-1)～(a-4) and as required Other monomers carry out being polymerized to manufacture obtaining.In these methods, for the molecular weight of easily dimmable polymer, And make the impurity being mixed in reaction system few, solution polymerization process is preferably used.
In solution polymerization process, using organic solvent as reaction dissolvent, dissolve in this reaction dissolvent or disperse shape Become each monomer component of above-mentioned (methyl) acrylic acid series copolymer (A), under agitation add polymerization initiator, Thus implement copolyreaction.
As above-mentioned organic solvent, the ester series solvents such as such as ethyl acetate, butanone, formaldehyde and second can be enumerated The ketone series solvents such as aldehyde, the aromatic series series solvent of ether series solvent, toluene and the dimethylbenzene such as dimethyl ether；Hexamethylene etc. Alicyclic series solvent；And the aliphatic series solvent such as hexane and octane.
Also can be used alone a kind in these solvents, it is possible to use two or more mixed solvents.
It addition, as above-mentioned polymerization initiator, 2 can be enumerated, 2 '-azobis isobutyronitrile (AIBN), 2,2 ' Double-2,4-the methyl pentane nitrile of azo double (4-methoxyl group-2,4-methyl pentane nitrile), 2,2 '-azo, 1,1 '-azo are double The azo-compounds such as hexamethylene-1-formonitrile HCN；Isobutyryl peroxide, α, α-bis-(the new capryl of peroxidating) diisopropyl Benzene, cumyl peroxyneodecanoate, peroxy dicarbonate di-n-propyl ester, di-isopropyl peroxydicarbonate, Double (the 4-of peroxy dicarbonate diisobutyl ester, peroxidating neodecanoic acid 1,1,3,3-tetramethyl butyl ester, peroxy dicarbonate Butylcyclohexyl) ester, benzoyl peroxide (benjoyl peroxide), peroxidating di tert butyl carbonate, peroxidating Lauroyl and the caproic acid tert-butyl group-epoxide-2-ethyl ester etc..These compounds can be used alone or in combination.
In solution polymerization process, the reaction temperature of the copolyreaction of these reaction dissolvents and polymerization initiator is used to lead to It is often 50～90 DEG C, in the range of preferably 60～85 DEG C；Response time is usually 1～10 hour, preferably 2～ 8 hours；Reaction pressure is usually normal pressure～0.5MPa.
<(A) methacrylic acid based copolymer>
(methyl) acrylic acid series copolymer (A) is the hardness by using aftermentioned cross-linking agent (B) to be cross-linked to form Therefore characteristic and the excellent crosslinked of optical compensation function, if using the binding agent group used for optical part of the present invention Compound, then can realize excellent dimensional stability, leakproof photosensitiveness and the durability under hygrothermal environment.
Average molecular weight Mw by above-mentioned (methyl) acrylic acid series copolymer (A) of gpc measurement is usual Being 500,000～2,000,000, preferably 800,000～1,800,000, this copolymer (A) has excellent cohesive force.
It addition, the glass transition temperature of (methyl) acrylic acid series copolymer (A) is preferably less than 0 DEG C, More preferably less than-10 DEG C, particularly preferably-15～-60 DEG C.If glass transition temperature is higher than 0 DEG C, obtained Binding agent the pliability of the sealing of material to be bonded and adhesive layer is reduced, it may occur that divide from material to be bonded From or floating situation about sticking up.It addition, the glass transition temperature of (methyl) acrylic acid series copolymer (A) is logical Cross the value that following FOX formula calculates.
(FOX formula)
1/Tg=Wa/Tga+Wb/Tgb+ ...
Tg:(methyl) glass transition temperature of acrylic acid series copolymer (A)；
Tga, Tgb ...: monomer a, the glass transition temperature of respective homopolymer of monomer b ...；
Wa, Wb ...: monomer a, monomer b the construction unit from each monomer at (methyl) acrylic acid Weight fraction in based copolymer (A)；
* (methyl) acrylic monomer (a-1)～(a-4) and other monomers, can arbitrarily be assigned as monomer a, Monomer b ....
Above-mentioned (methyl) acrylic acid series copolymer (A) can be the random copolymer of above-mentioned each monomer component, It is alternatively block copolymer.
It addition, in the present invention, (methyl) acrylic acid series copolymer (A) can be used alone a kind, it is possible to It is used in combination.
[(B) cross-linking agent]
The adhesive composition used for optical part of the present invention, except (methyl) described above acrylic copolymer Thing (A), contains cross-linking agent (B) the most simultaneously.
Cross-linking agent (B), as long as reaction can be crosslinked with (methyl) acrylic acid series copolymer (A), does not has Particularly limit, can enumerate as an example: isocyanates system cross-linking agent, metal-chelating system cross-linking agent and epoxy It it is cross-linking agent.
As the object lesson of above-mentioned isocyanates system cross-linking agent, can enumerate: toluene di-isocyanate(TDI), chlorobenzene two Isocyanates, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, The isocyanides such as XDI, methyl diphenylene diisocyanate, hydrogenated diphenyl methane diisocyanate Acid ester monomer；The isocyanation esterification that these several isocyanate-monomer additions are formed on trihydroxy methyl propane etc. Compound；Isocyanurate compounds；Biuret form compound；With known polyether polyols or polyester polyalcohols, third Olefin(e) acid polyalcohols (acryl polyol), polybutadiene polyalcohols, polyisoprene polyalcohols etc. carry out additive reaction and obtain The isocyanates of urethanes prepolymer type.
As above-mentioned metal-chelating system cross-linking agent, can be set forth in aluminum, ferrum, copper, zinc, stannum, titanium, nickel, antimony, What on the polyvalent metals such as magnesium, vanadium, chromium or zirconium, coordination isopropanol, acetylacetone,2,4-pentanedione or ethyl acetoacetate etc. obtained joins Position compound.
As specific example, can enumerate: aluminum isopropylate., diisopropanol bis-acetylacetonate titanium and triacetyl acetic acid Ethyl ester aluminum.
The object lesson of above-mentioned epoxy cross-linking agent, can enumerate: hexanediol glycidyl ethers, Polyethylene Glycol bicyclo- Double (N, the N-diepoxy propyl group amine of oxygen propyl ether, glycerol bisglycidyl ethers, glycerol three glycidyl ethers, 1,3- Ylmethyl) hexamethylene, N, N, N ', N '-four glycidyl-hexichol two methylene amine, N, N, N ', N '-four epoxy third Base aminocarbonyl phenyl methane, triglycidyl isocyanurate, a N, N-diepoxy propyl group aminocarbonyl phenyl glycidyl Ether, N, N-diepoxy propyltoluene amine, N, N-diepoxy propyl group aniline.
Cross-linking agent described above (B), can be used alone a kind, it is possible to two or more is applied in combination.
In the adhesive composition used for optical part of the present invention, relative to (methyl) acrylic acid series copolymer (A) 100 weight portions, this cross-linking agent (B) containing 0.01～3 weight portions.
By containing the most a certain amount of cross-linking agent (B), the suitable degree of cross linking can be realized, and can realize excellent Caking property, dimensional stability and the light leakage performance under hygrothermal environment and durability.From these points of view, The content of above-mentioned cross-linking agent, relative to (methyl) acrylic acid series copolymer (A) 100 weight portion, preferably 0.03～ 2.5 weight portion.
[other compositions]
In the adhesive composition used for optical part of the present invention, silane coupler, antistatic can be contained as required Agent, antioxidant, UV absorbent, coloring agent, pigment, dyestuff, tackifying resin, surface lubricant, Levelling agent (leveling agent), softening agent, age resistor, light stabilizer, light trigger, polymerization inhibitor, fill out Fill other compositions such as agent, organic filler, inorganic particulate or plasticiser.Further, the compositions of the present invention is also Can be containing other solvents manufactured beyond the solvent used in the method for (methyl) acrylic acid series copolymer (A). The above-mentioned silane coupler of following description and antistatic additive.
<silane coupler>
As above-mentioned silane coupler, can enumerate: ethylene trimethoxy silane, vinyl triethoxysilane and first The silicon compound containing polymerism unsaturated group such as base acryloxypropyl trimethoxy silane；3-epoxy third Epoxide propyl trimethoxy silicane, 3-glycidoxypropyl dimethoxysilane and 2-(3,4-epoxide ring Hexyl) silicon compound with epoxy construction of ethyl trimethoxy silane；3-aminocarbonyl propyl trimethoxy silane, N-(2-amido ethyl) 3-aminocarbonyl propyl trimethoxy silane and N-(2-amido ethyl)-3-aminocarbonyl propyl methyl The silicon compound containing amido such as dimethoxysilane；With 3-r-chloropropyl trimethoxyl silane；Oligomer type silane Coupling agent etc..
In these compounds, if used, there is the contained official with (methyl) acrylic acid series copolymer (A) Can roll into a ball the silane coupler of the functional group of reaction, then be not likely to produce peeling phenomenon under hygrothermal environment, this point is Highly desirable.
The use level of the silane coupler in the adhesive composition used for optical part of the present invention, relative to (methyl) Acrylic acid series copolymer (A) 100 weight portion, usually 0.01～0.5 weight portion, preferably 0.05～0.3 weight Amount part.
<antistatic additive>
In order to reduce the sheet resistance value of the adhesive composition used for optical part of the present invention, use antistatic additive. The present invention can use known antistatic additive, this antistatic additive generally can divide into (i) surfactant, (ii) ionic compound and (iii) electric conductive polymer.
I (), as above-mentioned surfactant, can use following compound: quaternary ammonium salt, amide groups quaternary ammonium salt Class, pyridine salt, there is the cationic surfactant of the cationic groups such as primary amine groups～tertiary amine groups.
The anionic surface with anionic property groups such as sulphonate-base, sulfuric ester alkali, phosphate ester alkali lives Property agent.
The both sexes such as alkyl betaines bases, alkyl imidazole betaines, oxidation of alkyl amine, aminoacid sulfuric acid ester Surfactant.
Glycerine fatty acid esters, Span class, polyoxyethylene alkyl amine class, polyoxyethylene alkyl amine The nonionic tables such as fatty acid ester, N-hydroxyethyl-N-2-hydroxyalkylamines, alkyl diethanolamide base class Face activating agent.
Additionally, also can enumerate the reactive emulsifier with polymerizable group as surfactant, can use by Live in the polymer system surface that the monomer component macromolecule of above-mentioned surfactant or reactive emulsifier quantifies to obtain Property agent.
(ii) above-mentioned ionic compound is to be made up of with anionicsite cationic moiety, at room temperature (23 DEG C 50%RH) it can be solid, shaped, it is possible to for liquid.
Above-mentioned cationic moiety can be any one or two kinds in inorganic cation or organic system cation.
As above-mentioned inorganic cation, preferred as alkali ion and alkaline-earth metal ion, more preferably antistatic The Li that property is excellent+、Na+And K+。
As above-mentioned organic system cation, can enumerate: pyridiniujm cation, piperidinium salt cation, pyrrolidine Salt cation, pyrrolin cation, pyrroles's cation, glyoxaline cation, tetrahydropyrimidine cation, dihydro Pyrimidine cation, pyrazoles cation, dihydropyazolo cation, tetraalkylammonium cation, trialkyl sulfonium sun from Son, tetra alkyl phosphonium cation etc. and derivant thereof.
On the other hand, as long as can carry out with above-mentioned cation as the anionicsite constituting ionic compound Ionic bonding and form the material of ionic compound, be not particularly limited.Specifically, can enumerate: F-、 Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、SCN-、ClO4 -、NO3 -、CH3COO-、CF3COO-、 CH3SO3 -、CF3SO3 -、(CF3SO2)2N-、(F2SO2)2N-、(CF3SO2)3C-、AsF6 -、SbF6 -、NbF6 -、 TaF6 -、F(HF)n -、(CN)2N-、C4F9SO3 -、(C2F5SO2)2N-、C3F7COO-and (CF3SO2)(CF3CO)N- Deng.In these ions, containing the anion containing fluorine atom of the ionic compound that preferably can provide low melting point, More preferably (F2SO2)2N-(CF3SO2)2N-。
The ionic compound used as the antistatic additive in the present invention, preferably: double (fluoroform sulphonyl Base) imidization lithium, double (two fluorosulfonyls) imidization lithium, lithium three (trifluoromethane sulfonyl group) methane, double (trifluoromethane sulfonyl group) imidization potassium, double (two fluorosulfonyls) imidization potassium, hexafluorophosphoric acid 1-ethyl pyrrole Pyridine, hexafluorophosphoric acid 1-butyl-pyridinium, hexafluorophosphoric acid 1-hexyl-4-picoline, hexafluorophosphoric acid 1-octyl group -4-picoline, 1-octyl group-4-picoline double (fluorosulfonyl) imines, Tetrafluoroboric acid (N, N-diethyl Base-N-methyl-N-(2-methoxy ethyl) ammonium), N, N-diethyl-N-methyl-N-(2 methoxy ethyl) ammonium Double (trifluoromethane sulfonyl group) imines, fluorine sulfonium imines 1-octylpyridinium, 1-octyl group 3-picoline and three Fluorine sulfonium imines etc..
(iii) as above-mentioned electric conductive polymer, polythiophene, polyaniline, polypyrrole and derivant thereof can be enumerated Deng.
In the adhesive composition used for optical part of the present invention, the use level of antistatic additive, relative to (methyl) Acrylic acid series copolymer (A) 100 weight portion, usually 0.01～3 weight portion, preferably 0.05～2.5 weight Part.
[adhesive composition used for optical part]
The adhesive composition used for optical part of the present invention is with above-mentioned (methyl) acrylic acid series copolymer (A) It is neccessary composition with cross-linking agent (B), can be containing any of the above-described other compositions etc..
Then in above-mentioned (methyl) acrylic acid series copolymer (A), by by (methyl) acrylate (a-2) (a-3) with special ratios copolymerization, had both excellent stiffness characteristic and optical compensation function, and due to (first Base) acrylic acid (a-1) copolymerization together, the most merely enhance hardness property, it is possible at (methyl) propylene Acid based copolymer (A) introduces suitable flexibility, thus realizes excellent dimensional stability.
Further, in (methyl) acrylic acid series copolymer (A), copolymerization (methyl) acrylic acid series Monomer (a-4), because it crosslinks reaction with a certain amount of cross-linking agent (B) coordinated, creates the friendship of appropriateness Connection, it is thus achieved that excellent caking property, excellent dimensional stability under hygrothermal environment and durability.
Due to dimensional stability under hygrothermal environment of the compositions of the present invention and excellent durability, even if therefore existing In hygrothermal environment, deform the most considerably less, and be difficult to the phenomenon occurring foaming etc. to reduce value of the product.
Such as, when using the compositions of the present invention to carry out small creep test by following description condition, at 60 DEG C The measured value of lower enforcement is logical with the ratio (60 DEG C of measured value/23 DEG C measured values) of the measured value implemented at 23 DEG C It is often 1.05～2.00, preferably 1.05～1.95.
Small creep test
The adhesive composition used for optical part of the present invention is coated on release-treated mylar and does Dry, make the bonding sheet with the adhesive layer that thickness is 25 μm.
By this bonding sheet and the polarisation being made up of TAC (Triafol T)-PVA (polyvinyl alcohol)-TAC Plate (plano-polarized light plate), fits in the way of above-mentioned adhesive layer contacts with above-mentioned Polarizer, makes evaluation and uses Bonding processing Polarizer.
The evaluation made bonding processing Polarizer is cut into wide 10mm × long 100mm, peels above-mentioned stripped The mylar processed, processes by adhesive layer and above-mentioned glass contact on glass at alkali, and presses 10mm × 10mm The carrying out of fitting area is fitted.
Then, to the evaluation of above-mentioned glass gluing bond processing Polarizer carry out autoclave process (50 DEG C, 5atm), under 23 DEG C/50%RH environment, stand 24 hours, and as small creep test sample.
Above-mentioned examination is carried out at the long 15mm of chuck section fixing in the cavity BOX of small creep test machine Test with the setting of sample, measure temperature (23 DEG C or 60 DEG C) by being heated in cavity BOX.Measuring temperature Lower standing is after 40 minutes, to stretch loading 800g, stretching time 1000 seconds, with this Polarizer and above-mentioned glass The contact surface of glass is parallel and on the length direction of above-mentioned Polarizer, to the above-mentioned evaluation in above-mentioned test sample Stretch with bonding processing Polarizer.
After stretching, measure the distance (mm) of glass and the skew of the fitting part of Polarizer, as micro- The result of the test (measured value) of little creep.
The measured value of 23 DEG C in small creep test is usually 0.05～1.00mm, preferably 0.08～0.50mm, More preferably 0.10～0.30mm；
The measured value of 60 DEG C in small creep test be preferably 0.15～1.00mm, more preferably 0.15～ 0.50mm。
That is, even if the compositions of the present invention is difficult to deformation and excellent size stability under hygrothermal environment, it addition, The degree of the deformation caused because of the change of temperature is almost unchanged.
Measured value in these small creep tests, is mainly advised by the hardness property of the compositions of the present invention Fixed, by being adjusted this characteristic, measured value also can change.Generally, if improving hardness property, The i.e. copolymerization ratios of (methyl) acrylate (a-2) in raising (methyl) acrylic copolymer (A), Improve the copolymerization ratios of (methyl) acrylic monomer (a-4) with polar functional group, increase cross-linking agent (B) Usage amount, then said determination value tend to diminish.If it addition, reducing (methyl) acrylic acid series copolymer (A) In (methyl) acrylate (a-2) copolymerization ratios, reduce there is (methyl) propylene of polar functional group Acid is the copolymerization ratios of monomer (a-4), the usage amount of reduction cross-linking agent (B), and said determination value then tends to become Greatly.
Owing to this kind deformation in hygrothermal environment is the least, therefore when the optics of compositions of the present invention that fitted Parts present under hygrothermal environment contraction, floating stick up, the deformation such as distortion time, the compositions of the present invention presents it Resistance to stress, can prevent above-mentioned deformation well.
Its result is to prevent the light leak caused due to above-mentioned deformation well.And, even if can not be the most anti- Leak-stopping light, it is possible to by the optical compensation function from above-mentioned (methyl) acrylic acid series copolymer (A), press down Make these small light leaks.
[bonding sheet]
Using the adhesive composition used for optical part of the present invention as binding agent use time, if on base film Formation adhesive layer is as bonding sheet, the most simple to operate and convenient.
If it is considered that operability when using above-mentioned bonding sheet in the manufacturing process of flat faced display etc., above-mentioned The preferred stripping film of base film；As its material, can enumerate: such as polyester, polyolefin, polyethers.
Such as can be by the painting of the coating adhesive composition used for optical part containing the present invention on base film Liquid, and it is dried gasifications such as making the solvent that contains in masking liquid, the adhesive layer forming desired thickness makes this The bonding sheet of invention.The thickness of above-mentioned adhesive layer is not particularly limited, the scope of preferably 5～100 μm, The scope of more preferably 10～50 μm.If the thickness of this adhesive layer is less than 5 μm, then there will be and can not play The situation of fixed performance (wet heat durability etc.), if it exceeds 100 μm, then easy when severing bonding sheet The situation occurring binding agent to overflow thus to cause processability to reduce.
It addition, in the bonding sheet of the present invention, with stripping film cover above-mentioned bonding basic unit not with above-mentioned base material The face of film contacts, can peel above-mentioned stripping film during use.
[optics of attachment adhesive layer]
By the adhesive layer of the adhesive composition used for optical part containing the present invention is formed at optics At least one side on, available above-mentioned under hygrothermal environment, realize excellent light leakage performance and the attachment of durability The optics of adhesive layer.
As the optics in the present invention, it is not particularly limited, the light being applicable to flat faced display can be enumerated Learn thin film, such as Polarizer, polarizer, elliptical polarization plate, optical compensating film, briliancy promote thin film, Infrared resistant/electromagnetic wave thin film, above with antireflective film, surface protective film, and the stacking of these thin film Film etc..
And the most particularly Polarizer, due to the deformation extent of the structure sheaf under at hygrothermal environment Difference, therefore produces warp or physical distortion and multiple bending occurs.This multiple bending is that light leak occurs Reason, in turn results in serious problem.The present invention compositions, because its hardness property can suppress Polarizer Deformation, thus the distortion of optics can be suppressed thus suppress light leak, and the durability of its suppression peeling etc. is the most excellent. Even if additionally, from producing warp slightly, also can be suppressed this point of light leak by optical compensation function from the point of view of, It is especially suitable for being applied to Polarizer and glass plate laminating.
It addition, from the point of view of can suppressing, because of its hardness property, this point that Polarizer deforms, the compositions of the present invention can be fitted Liquid crystal panel for relatively large-sized TV purposes.It is particularly suitable for being applied to VA pattern liquid crystal surface Polarizer in plate and glass substrate laminating.
<manufacture method of the optics of attachment adhesive layer>
The optics of attachment adhesive layer, such as, can be made by the method for following (1)～(3).
(1) by known method (die coating methods, blade rubbing method etc.) by the optic containing the present invention The masking liquid of part adhesive composition is coated on the peel ply of stripping film, makes to contain in masking liquid by heated drying Solvent gasification, formed and there is the adhesive layer of desired thickness, and by itself and optical member adhering.
(2) by known method (die coating methods, blade rubbing method etc.) by the optic containing the present invention The masking liquid of part adhesive composition is coated on optics, is made the solvent gas contained in masking liquid by heated drying Change, form the adhesive layer with desired thickness, and it is fitted with the peel ply of stripping film.
(3) by known method (die coating methods, blade rubbing method etc.) by the optic containing the present invention The masking liquid of part adhesive composition is coated on the peel ply of the 1st stripping film, is made in masking liquid by heated drying The solvent gasification contained, is formed and has the adhesive layer of desired thickness, and by its with the 2nd in stripping thin The peel ply of film (generally low than the peeling force of the stripping film in the 1st) is fitted, and makes non-carrier adhesive film. Then, the 2nd stripping film and optical member adhering are peeled.
The adhesive composition used for optical part of the present invention is after above-mentioned adhesive layer is formed, at room temperature (23 DEG C 50%RH) under cross-link 3～7 days, or (40 DEG C of 90%RH) cross-links 2～5 days under the conditions of heating promotes, Can be attached on the structure sheaf of flat faced display described later.
It addition, the thickness of adhesive layer in the optics of the attachment adhesive layer obtained there is no particular limitation, The scope of preferably 5～100 μm, the scope of more preferably 10～50 μm.If the thickness of this adhesive layer is not enough 5 μm, then there will be the situation that can not play fixed performance (wet heat durability etc.), if it exceeds 100 μm, The situation being then susceptible to binding agent spilling when severing bonding sheet thus cause processability to reduce.
Further, when using the compositions of the present invention in the manufacture of FPD, formation is made up of said composition Adhesive layer is used as the structure sheaf of FPD.Containing (methyl) third with optical compensation function in adhesive layer The crosslinked of olefin(e) acid based copolymer (A), the photoelastic coefficient of the most above-mentioned adhesive layer is preferably-320～0 (×10-12m2/N).About the assay method of photoelastic coefficient, explanation in embodiment part.
[flat faced display]
Can at least use a piece of present invention attachment adhesive layer optics to manufacture flat faced display, so The FPD manufactured is also contained in the scope of the present invention.
As FPD, liquid crystal display (LCD), plasma display (PDP) and electric field can be enumerated and launch Escope (FED) etc..
LCD is typically constituted by having laminate structure arranged below: by having the glass base of transparency electrode Plate clamps liquid crystal layer, is provided with alignment film or colored filter, further between this glass substrate and liquid crystal layer Ground arranges Polarizer on the face and the back side of the close liquid crystal layer of glass substrate.
PDP is typically constituted by having laminate structure arranged below: there are between relative glass substrate Luminescent coating, is provided with various conductor layer or electricity on the face of the close above-mentioned luminescent coating of above-mentioned glass substrate Pole, other functional layers.
FED is typically constituted by having glass substrate laminate structure arranged below: glass substrate, at this base The anode electrode (anode) that formed on plate, formed luminescent coating on this electrode, vacuum space and across The cathode electrode (cathode) that this space is relative with luminescent coating.
The optics of the attachment adhesive layer of the present invention constitutes a part for the structure sheaf of these FPD.It addition, The bonding sheet of the present invention can be used, by stacking gradually at least partially of FPD structure sheaf.
Embodiment
The present invention is described in detail by the following examples.
<the manufacture example of the acrylic acid series copolymer used in embodiment 1～13 and comparative example 1～8>
In the reaction unit equipped with blender, reflux cooler, thermometer and nitrogen ingress pipe, according to table Proportioning (weight portion) shown in 1～3 adds the acrylate (a-1) shown in table 1～3～(a-3) and propylene Acid is monomer (a-4), and the use level then pressing monomer concentration 50 weight % adds ethyl acetate.
Then, total 100 weight of relative acrylate (a-1)～(a-3) and acrylic monomer (a-4) Amount part, adds the 2 of 0.1 weight portion, and 2 '-azodiisobutyronitrile, with the sky in nitrogen displacement reaction device Gas, is stirred and is warming up to 60 DEG C, then reacts 4 hours under pressure 1atm.After reaction terminating, The acrylic acid series copolymer diluted ethyl acetate that will obtain, obtains acrylic acid series copolymer solution.
<evaluating the making with bonding processing Polarizer>
Using by manufacturing the acrylic acid series copolymer solution that example obtains, the use level of according to the form below 1～3 is added each Composition, obtains the solution of adhesive composition.This adhesive composition solution is coated on release-treated gathering On the surface of ester film, and it is made to be dried to obtain the bonding sheet with the adhesive layer that thickness is 25 μm.Should Bonding sheet is attached at the one side of the polarizing film of the Rotating fields of TAC-PVA-TAC, then at 23 DEG C/50%RH Dark room conditions under ripening 7 days, obtain evaluation bonding processing Polarizer.
For each evaluation bonding processing Polarizer, carry out shown in table 1～3 about small creep, light leak, Floating stick up, evaluation that bubble, crack are peeled off.
Table 1
Table 2
Table 3
The contents such as the abbreviation in table 1～3 are as follows:
BA-n-butyl acrylate
T-BA: tert-butyl acrylate
POA: acrylate
HEA: acrylic acid 2-hydroxy methacrylate
MA: acrylic acid methyl ester.
CHA: cyclohexyl acrylate
IBOA: isobornyl acrylate
AA: acrylic acid
TD:XDI system isocyanate compound (TD-75: Soken Chemical Company manufacture)
L:TDI addition product type isocyanate compound (manufacture of CORONATE L: Japanese polyurethane company)
KBM-403:3-glycidylpropyl trimethoxy silane (manufacture of chemical industrial company of SHIN-ETSU HANTOTAI)
Antistatic additive: 1-octyl group-4-picoline-bis-(fluorosulfonyl) acid imide
[Tg mensuration]
Carry out the various acrylic monomerss (a-1) shown in table 1～3～the homopolymerization of (a-3) in such a way The mensuration of the Tg of thing.
By polymerisation in solution, prepare the various homopolymer shown in table 4 as test film.
At N2In the environment of, test film ratio with 10 DEG C/min in the range of-60 DEG C to 180 DEG C is carried out Heat up, with DSC (the differential scanning calorimetry DSC8230 that Rigaku company manufactures), according to JIS (Japan Industrial standard) K7121 (the transition temperature assay methods of plastics) carries out calorimetry.
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 acid series copolymer prepared according to embodiment and comparative example, survey according to following GPC condition determination Determine weight average molecular weight (Mw), number-average molecular weight (Mn), try to achieve polydispersity index (PDI=Mw/Mn).
<GPC condition determination>
Determinator: HLC-8120GPC (manufacture of Dong Cao company)
GPC tubular column structure: following 5 series connection tubing string (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 oxolane3。
Mobile phase solvent: oxolane
Flow: 1ml/min
Tubing string temperature: 40 DEG C
[each evaluation methodology]
The various evaluations shown in table 1～3 are carried out by method shown below.
<small creep>
It is cut into wide 10mm × long 100mm, and on the glass that alkali processes, release-treated to having peeled The evaluation bonding processing Polarizer of the mylar crossed, by adhesive layer and above-mentioned glass contact, and with The fitting area of 10mm × 10mm is fitted, after carrying out autoclave process (50 DEG C, 5atm), 24 hours are stood in the environment of 23 DEG C/50%RH.As small creep test sample.In small creep In the cavity BOX of testing machine (great smart machine (strain) company of English manufactures, machine name: TA.TX.PLUS) The setting of test sample is carried out at length 15mm of fixing chuck section.
Temperature is measured, after standing 40 minutes at a temperature of measuring, to stretch loading by being heated in cavity BOX 800g, stretching time 1000 seconds, parallel with the contact surface of above-mentioned glass and along above-mentioned polarisation according to Polarizer The length direction of plate, stretches the evaluation bonding processing Polarizer of above-mentioned test film.After confirming (mensuration) stretching Above-mentioned glass and the distance (mm) of skew of fitting part of Polarizer as the result of the test of small creep.
[light leak]
19 inches of sizes VA type liquid crystal panel (I O DATA company manufactures, model: from The panel that LCD-A191EW takes out) in, the evaluation to the mylar having peeled release-treated mistake is used Bonding processing plate, contacts adhesive layer with above-mentioned liquid crystal panel, and makes above-mentioned evaluation bonding processing partially Tabula rasa is fitted according to the mode of cross-polarized light (crossed-Nicol) with above-mentioned liquid crystal panel, at the environment of 80 DEG C After lower placement 240 hours, place 2 hours in the environment of 23 DEG C/50%RH.
Then, the VA type liquid crystal panel of above-mentioned Polarizer of having fitted is connected in darkroom on computer and makes it Full frame blank screen shows.The display monitor showing this full frame blank screen, with brightness photometer, (Hi-Land company manufactures RISA-COLOR/CD8) measure briliancy in the region of the diameter 1cm of each near corners (La, Lb, Lc, Ld) and the briliancy (Lcenter) in diameter 1cm region of monitor middle body, and by following formula Calculate light leak (Δ L).Δ L is the least means that (from backlight) light leak is the fewest, if the most not enough 2.0, then can use as liquid crystal display panel.
Δ L=(La+Lb+Lc+Ld)/4-Lcenter
Light leak size is when above-mentioned full frame blank screen shows, is visually confirmed to be the part that light leak occurs, such as figure Shown in 1, measure distance d from the angle that light leak part occurs.If distance is at below 30mm, then can conduct Liquid crystal display panel uses.
And, for comparative example 1 and 3～6, after placing 240 hours in the environment of 80 DEG C, confirm display prison Visual organ, there occurs the bad order that foaming, peeling etc. cause because of adhesive layer, it is impossible to carry out light leak test Mensuration.
<wet heat durability>
It is cut into 15 inches at the processing Polarizer that the evaluation having peeled off release-treated mylar bondd Size (233mm × 309mm), in the one side of the alkali-free glass that thickness is 0.5mm, by adhesive layer with Above-mentioned contact glass sheet, and make it attach with stacking-up machine rolling.After attaching, at autoclave, (the former making of chestnut is made Make) in 0.5MPa, 50 DEG C, pressurized treatments under conditions of 20 minutes, obtain test plate.
So obtained test plate is placed 500 hours under conditions of 60 DEG C/90%RH.After off-test, Test plate is taken out from experimental enviroment, in the environment of 23 DEG C/50%RH, stands 2 hours, visualization The foaming of adhesive layer, peeling and crack are also evaluated by following standard.
Foaming-size)
Zero: complete invisible foaming
△: foaming diameter is at below 1mm
×: foaming diameter is bigger than 1mm
Foaming-generating capacity)
Zero: complete invisible foaming
△: foaming number is below 10
×: foaming number ratio is more than 10
Crack, peeling-size)
Zero: complete invisible floating stick up, peel off
△: fitting part entirety (100%) of the area relative test plate floating stick up, peeled off is less than 5%
×: fitting part entirety (100%) of the area relative test plate floating stick up, peeled off is more than 5%
Crack, peeling-position)
Zero: complete invisible defect (floating stick up, peel off)
△: only defective in the position less than 0.5mm from end
×: defective from the position of end more than 0.5mm
It addition, crack, peeling-position evaluation in " end " refer to by produce crack, the position of peeling Move down vertical line to each limit of test plate, the intersection point on the shortest vertical line and the limit of test plate.
It addition, about comparative example 5 and 6, observe examination after placing 500 hours under conditions of 60 DEG C/90%RH Test with plate, floating stick up due to produce that a large amount of adhesive layers cause, foam, it is impossible to the situation of fracture and peeling is entered Row is evaluated.
<photoelastic coefficient mensuration>
As described below, prepare binding agent test film thick for 15mm × 50mm × 1mm as measuring sample.
To manufacture in example in the acrylic acid series copolymer solution obtained according to the ratio shown in table 1-3 add cross-linking agent, Silane coupler and antistatic additive, as adhesive composition solution.It is dried according to this adhesive composition solution After the mode that thickness is 1mm, be coated in release-treated PET film, and be dried.After drying, It is obtained binding agent test film 12, as test sample according to 15mm × 50mm cutting.
Test sample is arranged on mensuration device, and (Japan Spectroscopy Corporation manufactures light splitting Ellipsometer M-220), it is measured in the environment of 23 DEG C.
In fig. 2, when in X direction sample being stretched, by the Stress Control of generation 0～0.15N In the range of, measure the wavelength of each stress-through the relation (* 1) of phase contrast of light.By (* 1), for The phase contrast through light of wavelength 600nm, draws point diagram with the relation of phase contrast-stress, and calculates its slope. And then, with slope=(-1) × photoelastic coefficient (10-12m2/ N) relation calculate photoelastic coefficient.
Reference
12 binding agent test films
The 14 fixing fixtures of sample
16 light sources
18 slits
20 detectors

Claims (14)

1. an adhesive composition used for optical part, it is characterised in that described adhesive composition contains:
(A): according to following ratio, following (a-1)～(a-4) are carried out (methyl) third that copolymerization obtains Olefin(e) acid system co-polymer:
(a-1) glass transition temperature of homopolymer be less than-40 DEG C, (methyl) third that do not have aromatic rings Olefin(e) acid ester 40～94.9 weight %；
(a-2) glass transition temperature of homopolymer is more than 0 DEG C, does not has (methyl) acrylic acid of aromatic rings Ester 0.1～50 weight %；
(a-3) there is (methyl) acrylate 0.1～25 weight % of aromatic rings；
(a-4) have (methyl) acrylic monomer of polar functional group of more than two kinds and/or two or more (methyl) acrylic monomer 0.1～6 weight % different, a kind of polar functional group having；
Wherein, (a-2) and (a-3) adds up to 5～59.9 weight %；
Described polar functional group is selected from carboxyl, hydroxyl, amino, amide groups and epoxy radicals；
(a-1)～(a-4) add up to 100 weight %；
(B): relatively described (methyl) acrylic acid series copolymer (A) 100 weight portion, 0.01～3 weight The cross-linking agent of part；Wherein,
Described (methyl) acrylate (a-2) selects free isobutyl methacrylate, (methyl) acrylic acid uncle In the group that butyl ester, (methyl) cyclohexyl acrylate and (methyl) isobornyl acrylate are constituted at least one Kind.
Adhesive composition used for optical part the most according to claim 1, it is characterised in that described (first Base) copolymerization ratios of acrylate (a-2) is 10～40 weight %.
Adhesive composition used for optical part the most according to claim 1 and 2, it is characterised in that described (methyl) acrylate (a-2) choosing freely (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate At least one in the group that (methyl) isobornyl acrylate is constituted.
Adhesive composition used for optical part the most according to claim 1 and 2, it is characterised in that described (methyl) acrylate (a-2) is (methyl) tert-butyl acrylate.
Adhesive composition used for optical part the most according to claim 1 and 2, it is characterised in that described The copolymerization ratios of (methyl) acrylate (a-1) is 50～90 weight %.
Adhesive composition used for optical part the most according to claim 1 and 2, it is characterised in that described At least one in the group that following compound is constituted of (methyl) acrylate (a-1): the positive fourth of acrylic acid Ester, acrylic acid n-pentyl ester, isoamyl acrylate, Hexyl 2-propenoate, heptylacrylate, acrylic acid isopentenyl ester, 2-ethylhexyl acrylate, n-octyl, Isooctyl acrylate monomer, acrylic acid positive nonyl ester, acrylic acid are different Nonyl ester, (methyl) acrylic acid ester in the positive last of the ten Heavenly stems, (methyl) isodecyl acrylate, methacrylic acid dodecyl Ester, (methyl) acrylic acid n-tridecane base ester, methoxyethyl acrylate, methoxyethyl glycol ester With ethioxy ethoxyethyl group ester.
Adhesive composition used for optical part the most according to claim 1 and 2, it is characterised in that described At least one in (methyl) acrylate (a-3) choosing group that freely following compound is constituted: (methyl) (methyl) acrylate class that benzyl acrylate, logical formula (I) represent and derivant thereof,
In formula (1), R0For hydrogen or methyl；R1For (CH2CH2O)nThe group represented, n is 1～20 Integer, m is the integer of 1～5；R2It is 6～10 for alkyl, carbon number that hydrogen, carbon number are 1～9 Aryl or aralkyl that carbon number is 7～11；When m is more than 2, the multiple R existed2Can identical also may be used Different.
Adhesive composition used for optical part the most according to claim 1 and 2, it is characterised in that described The copolymerization ratios of (methyl) acrylic monomer (a-4) is 1～6 weight %.
Adhesive composition used for optical part the most according to claim 1 and 2, it is characterised in that to institute State adhesive composition used for optical part when carrying out following small creep test, 60 DEG C of measured value/23 DEG C measured values Ratio be 1.05～2.00；
Described adhesive composition used for optical part is coated with on the mylar carrying out lift-off processing and makes It is dried, and preparation has the bonding sheet of the adhesive layer of thickness 25 μm；
With this bonding sheet and the Polarizer being made up of TAC-PVA-TAC, with described adhesive layer and described polarisation Plate contact makes it fit and makes evaluation bonding processing Polarizer；
This evaluation bonding processing Polarizer is cut into wide 10mm × long 100mm, peels at described stripping On the mylar of reason, and alkali process glass, by described adhesive layer and described glass contact, and according to The bond area of 10mm × 10mm makes it bond, as evaluating with bonding processing polarisation test film；
This evaluation bonding processing Polarizer test film is carried out autoclave process, environment at 23 DEG C/50%RH Lower standing 24 hours, autoclave treatment conditions are 50 DEG C, 50atm；
Then come at length 15mm of the fixing chuck section in the cavity BOX of small creep tester Described test film is set；
Temperature is measured, after standing 40 minutes at a temperature of measuring, with stretching by being heated in described cavity BOX Loading 800g, stretching time 1000 seconds, parallel with the contact surface of described glass and along polarisation according to Polarizer The length direction of plate, stretches the described evaluation bonding processing Polarizer of described test film；
Measure the distance of the skew of the fitting part of the described glass in described test film and Polarizer, in terms of mm.
Adhesive composition used for optical part the most according to claim 1 and 2, it is characterised in that phase Above-mentioned for 100 weight portions (methyl) acrylic acid series copolymer (A), contains 0.01～0.5 weight further Part silane coupler.
11. adhesive composition used for optical part according to claim 1 and 2, it is characterised in that phase Above-mentioned for 100 weight portions (methyl) acrylic acid series copolymer (A), contains 0.01～3 weight further Part antistatic additive.
Define containing according to any one of with good grounds claim 1～11 on 12. 1 kinds of base materials is used for optical part The bonding sheet of the adhesive layer of adhesive composition.
13. 1 kinds of opticses adhering to adhesive layer, it is characterised in that it is at least the one of optics Defining the optics of the attachment adhesive layer of adhesive layer on face, described adhesive layer contains claim Adhesive composition used for optical part according to any one of 1～11.
14. 1 kinds of flat faced displays, it is characterised in that it has attachment according to claim 13 and glues The optics of knot oxidant layer.
CN201280065245.1A 2011-12-28 2012-12-18 Adhesive composition used for optical part, bonding sheet, optics and display Active CN104024363B (en)

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