CN105431500A - Pressure-sensitive adhesive composition for optical member, pressure-sensitive adhesive sheet, and laminate - Google Patents
Pressure-sensitive adhesive composition for optical member, pressure-sensitive adhesive sheet, and laminate Download PDFInfo
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- CN105431500A CN105431500A CN201380077480.5A CN201380077480A CN105431500A CN 105431500 A CN105431500 A CN 105431500A CN 201380077480 A CN201380077480 A CN 201380077480A CN 105431500 A CN105431500 A CN 105431500A
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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
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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Abstract
Provided are: a pressure-sensitive adhesive composition for optical members which is capable of inhibiting the optical member from deforming and has excellent long-term durability; a pressure-sensitive adhesive sheet; and a laminate. The pressure-sensitive adhesive composition for optical members comprises (A) a copolymer, (B) an isocyanate-based crosslinking agent, and (C) an epoxy-based crosslinking agent, wherein the isocyanate-based crosslinking agent (B) is contained in an amount of 8-50 parts by mass per 100 parts by mass of the copolymer (A) and the copolymer (A) is a copolymer of a monomer mixture that contains a carboxylated monomer in an amount which is larger than 0 mass% but less than 0.5 mass%.
Description
Technical field
The present invention relates to optical component adhesive composite, adhesive sheet and multilayer body.
Background technology
Image display device, uses in recent years under various uses, condition, and such as, under being not only room temperature condition, situation about using under the rigor condition that high temperature, even high temperature and humidity are so also becomes many.As the use at high temperature or high temperature and humidity condition, the use of inside of the use of such as tropical area, vehicle interior or outdoor surveying instrument can be enumerated.
And image display device carries out slimming in recent years.Be accompanied by this, the optical component (such as: Polarizer) being such as used in a kind of liquid crystal indicator of image display device also has the trend of slimming.But, due to the slimming of Polarizer, become and more easily produce distortion.
On the other hand, in liquid crystal indicator, there will be a known and mainly result from the generation of " light leakage phenomena " that distortion that Polarizer shrinks causes.In order to suppress light leakage phenomena, having by adding a large amount of linking agent in adhesive composite, making the hardening method (patent documentation 1) suppressing to be out of shape of caking agent.
But, when using the liquid crystal indicator of such caking agent to be placed under high temperature or high humidity environment, caking agent cannot follow the distortion of current slimming Polarizer fully, sometimes can produce to float, peel off between the Polarizer, liquid crystal panel of adherend.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2010-090354 publication
Summary of the invention
Invent problem to be solved
The invention provides the distortion and the optical component adhesive composite of long durability excellence, adhesive sheet and multilayer body that can suppress optical component.
For solving the method for problem
The present inventor etc., in view of above-mentioned problem, found a kind of optical component adhesive composite, it is contained in the amount of the functional group of multipolymer and the ratio of multipolymer and linking agent by adjustment, can suppress the distortion of optical component and can obtain long durability.
1. the optical component adhesive composite that relates to of a mode of the present invention, comprises: (A) multipolymer, (B) isocyanate-based linking agent and (C) epoxy linking agent,
Wherein relative to above-mentioned (A) copolymer 1 00 mass parts, containing above-mentioned (B) isocyanate-based linking agent 8 ~ 50 mass parts,
Above-mentioned multipolymer is containing being less than the multipolymer of the monomer mixture of the above-mentioned carboxyl group-containing monomer of 0.5 quality % more than 0 quality %.
2. the optical component adhesive composite described in above-mentioned 1, wherein, relative to above-mentioned (A) copolymer 1 00 mass parts, containing above-mentioned (C) epoxy linking agent 0.05 ~ 4 mass parts.
3. the optical component adhesive composite described in above-mentioned 1 or 2, wherein, the use level of above-mentioned (C) epoxy linking agent is (B) relative to the pass of the content of above-mentioned (B) isocyanate-based linking agent: (C)=(10 ~ 40 mass parts): (0.1 ~ 2 mass parts).
4. the optical component adhesive composite according to any one of above-mentioned 1 ~ 3, wherein, above-mentioned monomer mixture is the mixture (wherein, above-mentioned monomer (a1) ~ (a4) adds up to 100 quality %) of following monomer (a1) ~ (a4):
(a1) carboxyl group-containing monomer: be less than 0.5 quality % more than 0 quality %;
(a2) (methyl) alkyl acrylate monomer: 90 ~ 99.9 quality %;
(a3) hydroxyl monomer: 0 ~ 0.3 quality %;
(a4) co-polymerized monomer beyond above-mentioned (a1) ~ (a3): 0 ~ 9 quality %.
5. the optical component adhesive composite according to any one of above-mentioned 1 ~ 4, wherein, also comprises (D) silane coupling agent.
6. the optical component adhesive composite described in above-mentioned 5, wherein, relative to above-mentioned (A) copolymer 1 00 mass parts, containing above-mentioned (D) silane coupling agent 0.01 ~ 1 mass parts.
7. the optical component adhesive composite according to any one of above-mentioned 1 ~ 6, wherein, above-mentioned (C) epoxy linking agent has epoxy group(ing) and amino.
8. the optical component adhesive composite according to any one of above-mentioned 1 ~ 7, wherein, also comprises (E) basic cpd.
9. the adhesive sheet that relates to of another mode of the present invention, its be by the optical component adhesive composite according to any one of above-mentioned 1 ~ 8 is configured as membranaceous and carry out heating, drying obtains.
10. the multilayer body that relates to of another mode of the present invention, comprise: glass substrate, light polarizing film and the bond layer be arranged between above-mentioned glass substrate and above-mentioned light polarizing film, this bond layer be by the optical component adhesive composite according to any one of above-mentioned 1 ~ 8 is configured as membranaceous and carry out heating, drying obtains.
Multilayer body described in 11. above-mentioned 10, wherein, above-mentioned glass substrate can be the glass substrate that image display device uses.
The effect of invention
Above-mentioned optical component adhesive composite, comprise: (A) multipolymer, (B) isocyanate-based linking agent and (C) epoxy linking agent, relative to above-mentioned (A) copolymer 1 00 mass parts, containing above-mentioned (B) isocyanate-based linking agent 8 ~ 50 mass parts, be containing being less than the multipolymer of the monomer mixture of the above-mentioned carboxyl group-containing monomer of 0.5 quality % more than 0 quality % by above-mentioned (A) multipolymer, suppress the carboxyl-content being contained in above-mentioned (A) multipolymer, can prevent thus the bond layer caused by the reaction of this carboxyl and other compositions through time deterioration.Therefore, by using the bond layer utilizing above-mentioned optical component adhesive composite to obtain, the optical component of long durability excellence can be obtained.
And, in above-mentioned optical component adhesive composite, because above-mentioned (B) isocyanate-based linking agent is adjusted to above-mentioned scope relative to the ratio of above-mentioned (A) multipolymer, so the hardness of the bond layer using above-mentioned optical component adhesive composite to obtain is suppressed.Therefore, by using this bond layer, the distortion of optical component can be suppressed.In addition, be contained in the carboxyl of above-mentioned (A) multipolymer, by reacting with the functional group's functional group of other compositions (or from) being contained in other compositions, the intermiscibility being somebody's turn to do (A) composition and these other compositions uprises, therefore the bond layer using above-mentioned optical component adhesive composite to obtain not easily produces white casse, and the transparency is excellent.
And, above-mentioned optical component adhesive composite is configured as membranaceous and carry out heating, the dry above-mentioned adhesive sheet obtained, the distortion of optical component can be suppressed, and long durability is excellent.
In addition, above-mentioned multilayer body by comprise be arranged between glass substrate and light polarizing film by above-mentioned optical component adhesive composite is configured as membranaceous and carry out heating, the dry bond layer obtained, the distortion of light polarizing film can be suppressed and the light polarizing film of long durability excellence can be obtained.
Accompanying drawing explanation
Fig. 1 is the sectional view of the example schematically showing the multilayer body comprising the bond layer using the optical component adhesive composite of an embodiment of the invention to obtain.
Embodiment
Below, with reference to accompanying drawing, while explain the present invention.In addition, in the present invention, unless otherwise stated, " part " expression " quality % ", " % " expression " quality % ".
1. optical component adhesive composite
The optical component adhesive composite (being sometimes also only recited as below " adhesive composite ") of an embodiment of the invention comprises (A) multipolymer (being sometimes also only recited as below " (A) composition "), (B) isocyanate-based linking agent (being sometimes also only recited as below " (B) composition ") and (C) epoxy linking agent (being sometimes also only recited as below " (C) composition ").
1.1. (A) composition
(A) multipolymer of composition is the polymkeric substance containing carboxyl.(A) composition is more specifically for containing being less than the multipolymer of the monomer mixture of the above-mentioned carboxyl group-containing monomer of 0.5 quality % more than 0 quality %.Be containing being less than the multipolymer of the monomer mixture of the above-mentioned carboxyl group-containing monomer of 0.5 quality %, because of containing a small amount of carboxyl, so the rheological parameters' change with time of the bond layer using composition to obtain can be reduced more than 0 quality % by (A) composition.And, by (B) composition and (C) composition and this carboxyl reaction, because the intermiscibility of (A) composition with (B) composition and (C) composition improves, so the bond layer using the adhesive composite of present embodiment to obtain not easily produces white casse, even if drying temperature is high, also not easily albefaction.
And (A) composition can also contain hydroxyl.By (A) composition also containing hydroxyl, (B) result of composition and (C) composition and this hydroxyl reaction, because the intermiscibility of (A) composition with (B) composition and (C) composition improves, so the albefaction of the bond layer using the adhesive composite of present embodiment to obtain can be prevented.
More specifically, above-mentioned monomer mixture is preferably the mixture (wherein, above-mentioned monomer (a1) ~ (a4) adds up to 100 quality %) of following monomer (a1) ~ (a4).
(a1) carboxyl group-containing monomer (being sometimes also only recited as below " (a1) composition "): be less than 0.5 quality % more than 0 quality %
(a2) (methyl) alkyl acrylate monomer (being sometimes also only recited as below " (a2) composition "): 90 ~ 99.9 quality %
(a3) hydroxyl monomer (being sometimes also only recited as below " (a3) composition "): 0 ~ 0.3 quality %
(a4) co-polymerized monomer (being sometimes also only recited as below " (a4) composition ") beyond above-mentioned (a1) ~ (a3): 0 ~ 9 quality %
More specifically, from the viewpoint of more excellent with the intermiscibility of (B) composition and (C) composition, (A) composition preferably has the acrylic copolymer of carboxyl, is more preferably the acrylic copolymer with carboxyl and hydroxyl.
Wherein, in the present invention, so-called " acrylic copolymer " refers to that Component units comprises the polymkeric substance of at least a kind be selected from vinylformic acid, acrylate, acrylate, methacrylic acid, methacrylate and methacrylic ester of more than 50 quality %.
By the multipolymer that (A) composition is above-mentioned monomer mixture, (A) composition can for having the polymkeric substance of carboxyl and hydroxyl, and then the content of carboxyl is suppressed in (A) composition, and the content of hydroxyl is adjusted in the scope of regulation.Thus, as described later, the hardness of the bond layer obtained owing to using the adhesive composite of present embodiment is suppressed, so optical component is not yielding, and can obtain the bond layer that rheological parameters' change with time is few, long durability is excellent.
Usually in the carboxylic situation of (A) composition bag, in the bond layer obtained by the adhesive composite of present embodiment, the functional group's (such as: be contained in the functional group of (B) composition and/or (C) composition, from the functional group being contained in (B) composition and/or (C) composition) being contained in other compositions and this carboxyl through time react, this bond layer have through time hardening tendency.
Relative to this, adhesive composite according to the present embodiment, the carboxyl group-containing monomer comprised for the preparation of the monomer mixture of (A) composition is less than 0.5 quality %, so the amount being contained in the carboxyl of (A) composition is suppressed, therefore in the bond layer obtained at the adhesive composite by present embodiment, can suppress with the functional group being contained in other compositions (such as: be contained in the functional group of (B) composition and/or (C) composition, functional group from (B) composition and/or (C) composition) through time the amount of carboxyl of reacting.Thereby, it is possible to prevent this bond layer through time hardening.That is, the bond layer using the adhesive composite of present embodiment to obtain, the excellent in te pins of durability of its long-term (such as: more than 1 month, being preferably more than 3 months).
And, when (A) composition comprises hydroxyl, because the functional group's (such as: be contained in the functional group of (B) composition and/or (C) composition, functional group from (B) composition and/or (C) composition) being contained in other compositions reacts, so the bond layer obtained by the adhesive composite of present embodiment has hardening tendency with this hydroxyl.
Relative to this, adhesive composite according to the present embodiment, because the amount of the hydroxyl being contained in (A) composition is reduced to below the amount of regulation, or (A) composition not hydroxyl, so the hydroxyl reacted with the functional group's (further from the functional group of (B) composition and/or (C) composition) being contained in (B) composition and/or (C) composition tails off (maybe can eliminate).Therefore, it is possible to prevent the bond layer that obtains from the adhesive composite of present embodiment hardening.
1.1.1. (a1) composition
Carboxyl group-containing monomer as (a1) composition is the monomer in the molecular structure with carboxyl, and (a1) composition can become the source of the carboxyl being contained in (A) composition.
When the content of (a1) composition of above-mentioned monomer mixture is 0 quality %, react because producing with (B) composition and (C) composition, therefore weather resistance has the situation of variation, on the other hand, when the content of (a1) composition in above-mentioned monomer mixture is more than 0.5 quality %, the bond layer obtained by the adhesive composite of present embodiment have through time hardening, weather resistance through time the situation that is deteriorated.Weather resistance and long durability more excellent in, the content of (a1) composition in above-mentioned monomer mixture is preferably 0.01 ~ 0.48 quality %, is more preferably 0.05 ~ 0.45 quality %.
As (a1) composition, can enumerate such as: vinylformic acid, methacrylic acid, maleic acid, methylene-succinic acid, combination one kind or two or more separately wherein can be used.
1.1.2. (a2) composition
Above-mentioned monomer mixture, by comprising (methyl) alkyl acrylate monomer as (a2) composition, can give weather resistance to (A) composition.When the content of (a2) composition in above-mentioned monomer mixture is less than 90 quality %, weather resistance has the situation of variation, on the other hand, when the content of (a2) composition in above-mentioned monomer mixture is more than 99.9 quality %, because of the relative step-down of ratio of (a1) composition, so weather resistance has the situation of variation.Weather resistance more excellent in, the content of (a2) composition in above-mentioned monomer mixture is preferably 95 ~ 99.6 quality %, is more preferably 98 ~ 99.6 quality %.
As (a2) composition, can enumerate such as: methyl acrylate, ethyl propenoate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-propyl, n propyl methacrylate, n-butyl acrylate, n-BMA, vinylformic acid n-pentyl ester, the just own ester of vinylformic acid, the just own ester of methacrylic acid, the positive heptyl ester of vinylformic acid, n-octyl, n octyl methacrylate, vinylformic acid ester in the positive ninth of the ten Heavenly Stems, methacrylic acid n-dodecane ester, vinylformic acid n-dodecane ester, methacrylic acid n-tetradecane ester, vinylformic acid n-hexadecane ester, methacrylic acid n-hexadecane ester, stearyl acrylate ester, stearyl methacrylate etc. have alkyl (methyl) alkyl acrylate monomer of straight-chain alkyl at esteratic site,
Isopropyl acrylate, isobutyl acrylate, tert-butyl acrylate, isopropyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, Isooctyl acrylate monomer, Isooctyl methacrylate, 2-EHA, 2-Ethylhexyl Methacrylate etc. have (methyl) alkyl acrylate monomer of branched-chain alkyl at esteratic site;
Cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, vinylformic acid two ring pentyl ester etc. have (methyl) alkyl acrylate monomer of alicyclic alkyl at esteratic site, can use wherein one or combination of more than two kinds separately.
Wherein, more excellent weather resistance can be obtained from the viewpoint of the bond layer that uses the adhesive composite of present embodiment to obtain, (a2) composition preferably forms the alkyl chain that the alkyl chain at alkyl ester position is straight-chain or branched, more preferably has the alkyl chain of straight-chain.In this case, can obtain more excellent weather resistance from the viewpoint of the bond layer using the adhesive composite of present embodiment to obtain, the carbonatoms being more preferably contained in the abovementioned alkyl chain of (a2) composition is 1 ~ 20 (preferably 1 ~ 10).
1.1.3. (a3) composition
Hydroxyl monomer as (a3) composition is the monomer in molecular structure with hydroxyl, and (a3) composition can become the source of the hydroxyl being contained in (A) composition.
When the content of (a3) composition in above-mentioned monomer mixture is more than 0.3 quality %, the bond layer obtained by the adhesive composite of present embodiment is hardening, and the optical component possessing this bond layer produces distortion sometimes.And, such as, when optical component is Polarizer, produce sometimes because of the light leak caused by the distortion of this optical component.In being out of shape suppressing optical component generation more reliably, the content of (a3) composition in above-mentioned monomer mixture is preferably below 0.25 quality %, is more preferably below 0.2 quality %.In addition, when above-mentioned monomer mixture comprises (a3) composition, the content of (a3) composition in above-mentioned monomer mixture is preferably 0.01 ~ 0.25 quality %, is more preferably 0.01 ~ 0.2 quality %.
As (a3) composition, can enumerate such as: vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, vinylformic acid 2-hydroxy propyl ester, methacrylic acid 2-hydroxy propyl ester, vinylformic acid 3-hydroxy propyl ester, methacrylic acid 3-hydroxy propyl ester, vinylformic acid 4-hydroxybutyl, methacrylic acid 4-hydroxybutyl, vinylformic acid 2-hydroxyl-3-chlorine propyl ester, methacrylic acid 2-hydroxyl-3-chlorine propyl ester, vinylformic acid 2-hydroxyl-3-phenoxy-propyl, methacrylic acid 2-hydroxyl-3-phenoxy-propyl etc., vinylformic acid glycol ester, polyalkylene glycol acrylate ester, vinylformic acid propylene glycol ester, the alkyl acrylate diol esters such as vinylformic acid polypropylene glycol ester, methacrylic acid glycol ester, methacrylic acid macrogol ester, methacrylic acid propylene glycol ester, the methacrylic acid alkane diol esters such as methacrylic acid polypropylene glycol ester, (methyl) acrylate monomer containing hydroxyl of acrylate etc.
1.1.4. (a4) composition
Above-mentioned monomer mixture can comprise the co-polymerized monomer beyond as above-mentioned (a1) ~ (a3) composition of (a4) composition.
(a4) composition, can enumerate such as: vinylformic acid N, N-dimethylamino ethyl ester, methacrylic acid N, N-dimethylamino ethyl ester, methacrylic acid N, (methyl) acrylate monomer containing amido such as N-diethylamino ethyl ester, N, N-dimethylaminopropylacryl acid amides, N, N '-dimethyl acrylamide, N, N '-acrylamide, N, N '-dimethyl aminoethyl acrylamide, N, N '-dimethyl aminopropyl acrylamide, (methyl) acrylamide monomer containing amido such as NIPA, acryloyl morpholine, acrylamide, tertiary octyl group (methyl) acrylamide, the monomer containing nitrogen-atoms such as diacetone acrylamide, carboxyethyl acrylates, vinyl cyanide, pentamethvl methacrylic ester, benzyl methacrylate, benzyl acrylate, vinylformic acid 2-naphthalene ester etc. have (methyl) acrylate monomer of fragrant cyclic group at esteratic site, vinylformic acid dicyclopentenyl oxygen base ethyl ester, glycidyl methacrylate, Tetrahydrofurfuryl Methacrylate etc. have the styrenic monomers such as (methyl) acrylate, vinylbenzene, alpha-methyl styrene, o-methyl styrene, p-methylstyrene of ether at esteratic site, the vinyl carboxylates such as vinyl-acetic ester, vinyl pyridine, NVP, caprolactam, macromonomer etc. containing vinyl (methyl) acryl, can use wherein one or combination of more than two kinds separately.The content of (a4) composition in monomer composition is preferably 0 ~ 9 quality %, is more preferably 0 ~ 8 quality %.
1.1.5. the total amount of (a1) ~ (a3) composition
In the adhesive composite of present embodiment, from the viewpoint of reaching good weather resistance and the height adaptation with adherend, the total amount as above-mentioned (a1) composition in the above-mentioned monomer mixture of the raw material of the multipolymer of (A) composition, (a2) composition and (a3) composition can be 90 ~ 100 quality %.
1.1.6. weight-average molecular weight
(A) weight-average molecular weight (Mw) of composition is 500,000 ~ 2,000,000.(A) when the weight-average molecular weight of composition is less than 500,000, weather resistance can be deteriorated sometimes, and on the other hand, during more than 2,000,000, the bond layer using the adhesive composite of present embodiment to obtain becomes too hard, sometimes cannot prevent the distortion of optical component.From the viewpoint of can preventing the distortion of optical component and improving weather resistance, the weight-average molecular weight of (A) composition is more preferably 800,000 ~ 1,500,000.Herein, the weight-average molecular weight (Mw) of (A) composition and number-average molecular weight (Mn) use GPC (gel permeation chromatography) and obtain with following condition the weight-average molecular weight (Mw) converted by polystyrene standard to obtain.And the molecular weight distribution (Mw/Mn) of (A) composition is preferably 6.0 ~ 9.5.
< GPC condition determination >
Determinator: HLC-8120GPC (eastern Cao (Tosoh) Inc.)
GPC post is formed: following 5 pedestals (being all Dong Cao Inc.)
(i) TSK-GELHXL-H (guard column)
(ii)TSK-GELG7000HXL
(iii)TSK-GELGMHXL
(iv)TSK-GELGMHXL
(v)TSK-GELG2500HXL
Sample concentration: become 1.0mg/cm with tetrahydrofuran (THF) dilution
3
Mobile phase solvent: tetrahydrofuran (THF)
Flow: 1.0cm
3/ min
Column temperature: 40 DEG C
1.1.7. the content of adhesive composite
The content of (A) composition in the adhesive composite of present embodiment, can be 60 ~ 90 mass parts of this adhesive composite, is preferably 65 ~ 90 mass parts.
1.1.8. the polymerization process of (A) composition
(A) polymerization process of composition, be not particularly limited, the known method polymerization such as solution polymerization, emulsion polymerization, suspension polymerization can be passed through, use the mixture of the multipolymer by being polymerized gained, when manufacturing adhesive composite of the present invention, comparatively simple and can carry out the short period of time from the viewpoint for the treatment of step, be polymerized preferably by solution polymerization.
Solution polymerization generally by adding the organic solvent of regulation, each monomer, polymerization starter and chain-transfer agent etc. used as required in polymerization tank, under the reflux temperature of nitrogen gas stream or organic solvent, stir the reacting by heating of carrying out a few hours and carry out.
In addition, in this case, organic solvent, monomer and/or polymerization starter can successively be added at least partially.As organic solvent, can enumerate such as: benzene, toluene, ethylbenzene, n-propylbenzene, tert.-butylbenzene, o-Xylol, m-xylene, p-Xylol, naphthane, perhydronaphthalene, aromatic naphthas etc. are aromatic hydrocarbon based; Such as: normal hexane, normal heptane, octane, octane-iso, n-decane, limonene, petroleum spirit, petroleum naphtha, turpentine wet goods fatty series or alicyclic ring family hydro carbons; Such as: the ester classes such as ethyl acetate, n-butyl acetate, n-amyl acetate, acetic acid 2-butoxyethyl, acetic acid 3-methoxybutyl, methyl benzoate; Such as: the ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), isophorone, pimelinketone, methylcyclohexanone; Such as: the glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, glycol ether list ether, diethylene glycol monobutyl ether; Deng.These organic solvents can individually use, or mix two or more use.
In these polymerization organic solvents, during the polymerization of (A) composition, such as, preferably use ester class, ketone, particularly from the viewpoint of the easness etc. of the solvability of (A) composition, polyreaction, preferably use methyl ethyl ketone, acetone etc.
As above-mentioned polymerization starter, the organo-peroxide, azo-compound etc. that can use in common solution polymerization can be used.As such organo-peroxide, can enumerate such as: tertbutyl peroxide, isopropyl benzene hydroperoxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, peroxidation hexanoyl, di-isopropyl peroxydicarbonate, peroxy dicarbonate two-2-ethylhexyl, the peroxidation trimethylacetic acid tert-butyl ester, 2, 2-two (4, 4-bis--tert-butyl hydroperoxide cyclohexyl) propane, 2, 2-two (4, 4-bis--t-amyl peroxy cyclohexyl) propane, 2, 2-two (4, 4-bis--tertiary octyl group peroxidation cyclohexyl) propane, 2, 2-two (4, 4-bis--α-cumyl peroxy cyclohexyl) propane, 2, 2-two (4, 4-bis--tert-butyl hydroperoxide cyclohexyl) butane, 2, 2-two (4, 4-bis--tertiary octyl group peroxidation cyclohexyl) butane etc., as azo-compound, can enumerate such as: 2, 2 '-azobis isobutyronitrile, 2, 2 '-azo two-2, 4-methyl pentane nitrile, 2, two-4-the methoxyl group-2 of 2 '-azo, 4-methyl pentane nitrile etc.
In these polymerization starters, in the polyreaction of (A) composition, preferably do not cause the polymerization starter of graft reaction, particularly preferably azo system.Relative to total 100 weight part of monomer mixture, its usage quantity is generally 0.01 ~ 2 weight part, is preferably 0.1 ~ 1.0 weight part.
And, when manufacturing (A) composition that the adhesive composite of present embodiment comprises, not usage chain transfer agent usually, but in the scope of harmless object of the present invention and effect, can use as required.
As such chain-transfer agent, can enumerate such as: cyanoacetic acid; The alkyl esters of the carbonatoms 1 ~ 8 of cyanoacetic acid; Bromoacetic acid; The alkyl esters of the carbonatoms 1 ~ 8 of bromoacetic acid; The aromatics classes such as anthracene, phenanthrene, fluorenes, 9-phenyl fluorenes; The aromatic nitro compound classes such as p-Nitroaniline, oil of mirbane, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol, para-nitrotoluene; The quinone derivatives classes such as benzoquinones, 2,3,5,6-duroquinones; The borane derivative classes such as tri-n-butylbo-rane; The halogenated hydrocarbon such as carbon tetrabromide, tetracol phenixin, 1,1,2,2-tetrabromoethane, tribromo-ethylene, trieline, bromo-trichloromethane, methenyl bromide, 3-chloro-1-propene; The aldehydes such as trichoro-aldehyde, furfural; The alkyl sulfide alcohols of carbonatoms 1 ~ 18; The aromatic mercaptans such as thiophenol, toluenethiol class; The alkyl esters of the carbonatoms 1 ~ 10 of Thiovanic acid, Thiovanic acid; The hydroxyalkylthiol class of carbonatoms 1 ~ 12; The terpene such as firpene, terpinolene; Deng.
As the polymerization temperature of (A) composition, be generally about 30 ~ 180 DEG C, be preferably 40 ~ 150 DEG C, be more preferably the scope of 50 ~ 90 DEG C.In addition, when comprising unreacted monomer in the polymkeric substance obtained by solution polymerization process etc., in order to remove this monomer, refine by utilizing the reprecipitation method of methyl alcohol etc.
1.2. (B) composition
(B) the isocyanate-based linking agent of composition, preferably there is isocyanate group (-N=C=O) and normal temperature or the lower linking agent that can be cross-linked with (A) composition of heating, can illustrate such as: xylylene diisocyanate, tolylene diisocyanate, chlorine phenylene vulcabond, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, the isocyanate-monomers such as hydrogenated diphenyl methane diisocyanate, the isocyanate compound that the addition reactions such as the alkylol cpd of these and TriMethylolPropane(TMP) etc. more than 2 yuan obtain, isocyanurate compound etc.
The polyurethane prepolymer type isocyanic ester etc. that known polyether glycol, polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyol etc. obtain with isocyanate compound addition reaction can also be enumerated.Among these, preferably use xylylene diisocyanate and derivative etc. thereof.
The content of (B) composition in the adhesive composite of present embodiment, relative to (A) composition 100 mass parts, is preferably 8 ~ 50 mass parts, is more preferably 9 ~ 48 mass parts.The content of (B) composition of the adhesive composite of present embodiment, relative to (A) composition 100 mass parts, when being less than 8 mass parts, the bonding force of the bond layer using the adhesive composite of present embodiment to obtain is not enough, on the other hand, during more than 50 mass parts, the bond layer using the adhesive composite of present embodiment to obtain becomes too hard, and the optical component comprising this bond layer produces intentional deformation sometimes.
In addition, in the adhesive composite of present embodiment, relative to (A) composition, the more amount of (B) components matching 8 ~ 50 mass parts, therefore isocyanate group condensation each other in system, can generate so-called isocyanate polymer.When water in the isocyanate group of the activity in this isocyanate polymer and system reacts, via decarboxylation, generate amino in polymer chain.This amino can with the epoxy reaction of (C) described later composition, therefore, it is possible to the new polymer network that construction is different from the polymer network that the reaction by linking agent is formed with the cross-linking set (such as: (A) composition is acrylic acid polymer, be contained in the cross-linking set of this acrylate copolymer) being contained in (A) composition in system.Thus, the excellent in te pins of durability of the bond layer using the adhesive composite of present embodiment to obtain.
1.3. (C) composition
As the epoxy linking agent of (C) composition, as long as there is epoxy group(ing) (with reference to following formula (1)) and normal temperature or the lower linking agent that can be cross-linked with (A) composition of heating.
The content of (C) composition in the adhesive composite of present embodiment, relative to (A) composition 100 mass parts, is preferably 0.05 ~ 4 mass parts, is more preferably 0.08 ~ 3 mass parts.The content of (C) composition in the adhesive composite of present embodiment, relative to (A) composition 100 mass parts, when being less than 0.05 mass parts, bonding force is not enough, on the other hand, during more than 4 mass parts, bond layer becomes too hard, and the optical component comprising this bond layer produces intentional deformation sometimes.
And, the distortion of the weather resistance taking into account the bond layer using the adhesive composite of present embodiment to obtain from the viewpoint of realization and the optical component preventing from comprising this bond layer, the relation of the content of above-mentioned (B) isocyanate-based linking agent and the use level of above-mentioned (C) epoxy linking agent is preferably (B): (C)=(10 ~ 40 mass parts): (0.1 ~ 2 mass parts).
And (C) composition can for having epoxy group(ing) and amino epoxy linking agent (amine type epoxy linking agent).Be amine type by the epoxy group(ing) of (C) composition, the nucleophilicity of this epoxy group(ing) to other compositions (such as: (A) composition and/or (B) composition) can be improved, can promote to be cross-linked.
In addition, (C) composition has epoxy group(ing) and amino situation (situation for amine type epoxy linking agent), even and if then under (C) composition do not comprise amino situation (situation for non-amine type epoxy linking agent), the adhesive composite of present embodiment still can comprise (E) basic cpd (being sometimes also only recited as below " (E) composition ").
As (C) composition, commercially available epoxy linking agent can be used.As amine type epoxy linking agent, can enumerate such as: two (N, the N-diglycidyl amino methyl) hexanaphthene (trade(brand)name: TETRADC of 1,3-; Mitsubishi Gas Chemical Co., Ltd), 1,3-two (N, N-diglycidyl amino methyl) benzene (trade(brand)name: TETRADX; Mitsubishi Gas Chemical Co., Ltd), as non-amine type epoxy linking agent, can enumerate such as: 2,2 '-[[2, two (oxyethane-2-ylmethoxymethyl)-1, the 3-glyceryl of 2-] two (Oxymethylene)] bisoxirane (trade(brand)name: DENACOLEX-411; NagaseChemteX Inc.).
And, when using (C) composition with epoxy group(ing) and amino, when using the adhesive composite of present embodiment to form bond layer, infer the electron donating property of the nitrogen-atoms by being contained in this amino, can promote to be contained in (B) composition from the hydroxyl of isocyanate group and the reaction of this epoxy group(ing), and be contained in the carboxyl of (A) composition and the reaction of this epoxy group(ing).Thereby, it is possible to improve the cementability of the bond layer using the adhesive composite of present embodiment to obtain.
Also comprise (E) composition by the adhesive composite of present embodiment, (E) composition can improve the nucleophilicity of the hydroxyl being contained in other compositions (and/or from other compositions).The content of (E) composition in the adhesive composite of present embodiment, relative to (A) composition 100 mass parts, is preferably 0 ~ 0.1 mass parts, is more preferably 0 ~ 0.08 mass parts.
As (E) composition, have good electron donating property in, be preferably the compound of alkaline nitrogen atom, such as: KAOLIZERNo.1 (trade(brand)name, Kao Corp).
1.4. (D) composition
The adhesive composite of present embodiment also can comprise (D) silane coupling agent (being sometimes only recited as below " (D) composition ").Also comprise (D) composition by the adhesive composite of present embodiment, when using the adhesive composite of present embodiment to form bond layer on the surface of optical component, optical component and adherend can keep good bonding.
More specifically, in the adhesive composite of present embodiment, reacted with (D) composition by the isocyanate group group of this isocyanate group (or from) being contained in (A) composition and/or (B) composition, the adhesive composite of present embodiment and the cementability of adherend (such as: glass) can be improved.
(C) composition can be such as: the silicon compound containing polymerizability unsaturated group such as vinyltrimethoxy silane, vinyltriethoxysilane and methacryloxypropyl trimethoxy silane; 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl dimethoxysilane and 2-(3,4-expoxycyclohexyl) ethyl trimethoxy silane etc. have the silicon compound of epoxy group(ing) structure; 3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330 and N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane etc. are containing amino silicon compound; And 3-r-chloropropyl trimethoxyl silane; Oligomer type silane coupling agents etc., wherein in excellent in adhesion, preferably have (D) composition with the functional group of the functional group reactions be contained in (A) composition, (B) composition or (C) composition.
In the adhesive composite of present embodiment, from the viewpoint of the cementability improving said composition further, relative to (A) composition 100 mass parts, (D) composition of 0.01 ~ 1 mass parts can be contained.
1.5. other compositions
The adhesive composite of present embodiment, also can comprise the composition beyond (A) composition, (B) composition, (C) composition, (D) composition, (E) composition as required.Such as, in the adhesive composite of present embodiment, in the scope of harmless effect of the present invention, can matching surface promoting agent, antioxidant, UV light absorber, tackifier, softening agent etc.
1.6. other embodiments
The optical component adhesive composite of other embodiments of the present invention, comprises: (A) has the multipolymer of carboxyl, (B) isocyanate-based linking agent and (C) epoxy linking agent; Relative to above-mentioned (A) copolymer 1 00 mass parts, containing above-mentioned (B) isocyanate-based linking agent 8 ~ 50 mass parts; Relative to above-mentioned (A) copolymer 1 00 mass parts, containing above-mentioned (C) epoxy linking agent 0.05 ~ 4 mass parts.In this case, above-mentioned (A) multipolymer can for containing being less than the multipolymer of the monomer mixture of the above-mentioned carboxyl group-containing monomer of 0.5 quality % more than 0 quality %.According to the optical component adhesive composite of other embodiments above-mentioned, there is the action effect identical with the optical component adhesive composite of above-mentioned present embodiment.
1.7. the manufacture of adhesive composite
The adhesive composite of present embodiment, prepares above-mentioned (A) ~ (E) composition and any composition as required usually simultaneously or with random order mixing.And, (A) composition and (B) composition and (C) composition are when mixing, when being prepared (A) composition by solution polymerization, containing in the solution of (A) composition after polymerization terminates can add (B) composition and (C) composition, when by mass polymerization preparation (A) composition, because of polymerization terminate after be difficult to Homogeneous phase mixing, therefore preferably in the midway of this polymerization, add (B) composition and mix with (C) composition.
1.8. purposes
The adhesive composite of present embodiment can be used in the laminating of optical component and adherend, wherein can be applicable to being used in the laminating of the optical component of the weather resistance requiring long-term (such as: more than 1 month, being preferably more than 3 months).
As the optical component of laminating object becoming the adhesive composite using present embodiment, can enumerate such as: be selected from the blooming in light polarizing film (Polarizer), phase retardation film, elliptical polarized light film, anti-reflective film, brightness enhancement film, optical diffusion film and hard coat film.And, as adherend, can enumerate such as: the base material that the metal level of ITO layer etc., glass or plastics are formed, wherein cementability more excellent in, the laminating of optical component and glass can be suitable for.
And, such as when optical component is Polarizer, across the bond layer using the adhesive composite of present embodiment to obtain, when making Polarizer bonding with other adherend (such as: glass substrate), because this bond layer has suitable hardness, the distortion of Polarizer can be prevented, and the rheological parameters' change with time of this bond layer can be suppressed.Thus, the long durability of this bond layer is excellent.
1.9. adhesive sheet
The adhesive sheet of other embodiments of the present invention be the adhesive composite of present embodiment is configured as membranaceous and suitably heat, dry gained.The adhesive sheet of present embodiment such as can by the adhesive composite of present embodiment is coated barrier film (stripping film) upper formed membranaceous after, carry out heating, dry and obtain.By being arranged between optical component and other adherend by the adhesive sheet (bond layer) of present embodiment, the laminating of this adherend and this optical component can be carried out.
The thickness of the adhesive sheet (bond layer) of present embodiment, is generally 1 ~ 50 μm, is preferably about 5 ~ 30 μm.
1.10. action effect
In the adhesive composite of present embodiment, comprise (A) composition, (B) composition and (C) composition, relative to above-mentioned (A) 100 weight part, containing above-mentioned (B) composition 8 ~ 50 weight part, be containing being less than the multipolymer of the monomer mixture of the above-mentioned carboxyl group-containing monomer of 0.5 quality % more than 0 quality % by above-mentioned (A) composition, the content of the carboxyl being contained in above-mentioned (A) composition can be suppressed, and be adjusted to above-mentioned scope relative to the ratio of above-mentioned (A) composition because of above-mentioned (B) composition, so the distortion of optical component can be suppressed, and long durability is excellent.
More specifically, because the content of the carboxyl being contained in above-mentioned (A) composition can be suppressed, so this carboxyl and the functional group reactions in the bond layer using the adhesive composite of present embodiment to be formed can be suppressed, and the hardness of this bond layer through time change.
And, generally speaking, if (A) composition is poor with the intermiscibility of (B) composition, then bond layer produces white casse after the drying sometimes, and then the situation of the high or dry length of the drying temperature of bond layer, this bond layer has the tendency of easy albefaction.
Relative to this, when using the adhesive composite of present embodiment to form bond layer, because above-mentioned (A) composition comprises carboxyl, the carboxyl reaction that the group (and then from the group of (B) composition and/or the group from (C) composition) that the group comprised by (B) composition and/or (C) composition are comprised and (A) composition comprise, (A) composition improves with the intermiscibility of (B) composition and (C) composition, therefore not easily produce white casse, even if the drying temperature of bond layer is high or long when, bond layer also not easily produces albefaction.
And, in the adhesive composite of present embodiment, because above-mentioned (B) composition is adjusted to above-mentioned scope relative to the ratio of above-mentioned (A) composition, therefore when using the adhesive composite of present embodiment to form bond layer, bond layer can be suppressed to become too hard.
Such as, when optical component is Polarizer, by utilizing the bond layer using the adhesive composite of present embodiment to obtain, this bond layer has suitable hardness, and have excellent bonding force, therefore the distortion of optical component is suppressed, therefore, it is possible to prevent light leak.Particularly this bond layer, easily adapts to the surface of glass, can improve the adaptation of glass substrate and optical component.And this bond layer can play excellent weather resistance under high temperature and many wet conditions, and can reduce light leak.
2. multilayer body
The multilayer body of an embodiment of the invention comprises glass substrate, Polarizer and bond layer (adhesive sheet), this bond layer is arranged between above-mentioned glass substrate and above-mentioned Polarizer, is by being configured as by the optical component adhesive composite of above-mentioned embodiment membranaceous and carrying out heating obtained.
2.1. rhythmo structure
Fig. 1 is the sectional view of an example (multilayer body 100) of the multilayer body schematically showing an embodiment of the invention.Multilayer body 100, as shown in Figure 1, the bond layer 20 comprising glass substrate 10, light polarizing film 30 and be arranged between glass substrate 10 and light polarizing film 30.
More specifically, multilayer body 100 comprises glass substrate 10, is arranged at the bond layer 20 on glass substrate 10 and is arranged at the light polarizing film 30 on glass substrate 10 across bond layer 20.Glass substrate 10 is bonding across bond layer 20 with light polarizing film 30.
In Fig. 1, bond layer 20 is formed at the surface of adherend (glass substrate 10).As the method for the adhesive composite in the surface of adherend formation present embodiment, the surface coated adhesive composite of the good stripping film of smoothness (barrier film) can be set forth in, film after drying, by this adhering molding transfer to the transfer printing on surface of specific resin molding.
The multilayer body of present embodiment is such as contained in image display device (particularly liquid crystal indicator).In this case, the glass substrate included by multilayer body of present embodiment is the glass substrate of liquid crystal indicator.
2.2. glass substrate
The glass substrate forming the multilayer body of present embodiment can be for device used for image display glass substrate on the way.As image display device, can enumerate such as: TFT (thin film transistor) liquid crystal indicator that the watch-dog, portable phone, flat board etc. of LCD TV, computer use.
2.3. action effect
The multilayer body of present embodiment by comprise glass substrate, light polarizing film and be arranged between above-mentioned glass substrate and above-mentioned light polarizing film the optical component adhesive composite of above-mentioned embodiment is configured as membranaceous and carry out heating, the dry bond layer obtained, in the optical component adhesive composite of above-mentioned embodiment, (A) content of the carboxyl of composition is suppressed, therefore, it is possible to suppress this carboxyl and the reaction of functional group being contained in this adhesive composite.Thus, long durability is excellent.
And, in the optical component adhesive composite of above-mentioned embodiment, carboxyl in content repressed (A) composition, with the functional group reactions being contained in (B) composition and (C) composition, therefore this bond layer can play suitable hardness and excellent bonding force.Thereby, it is possible to suppress the distortion of light polarizing film.
3. embodiment
Below, according to following embodiment, the present invention is described, but the present invention not limited by embodiment.
3.1. the preparation of (A) composition
3.1.1. embodiment 1 (manufacture of multipolymer)
In the reaction vessel possessing cooling tube, nitrogen ingress pipe, thermometer, addition funnel and whipping appts, put into 2 as polymerization starter, 2 '-azobis isobutyronitrile 0.1 weight part, ethyl acetate 130 weight part as solvent, butyl acrylate 99.6 weight part as monomer component, vinylformic acid 0.4 weight part, after room temperature carries out 1 hour nitrogen reflux, by the temperature to 67 DEG C of the monomer composition solution in reaction vessel, in stream of nitrogen gas, carry out polymerization in 5 hours, obtain the solution of multipolymer ((A) composition of embodiment 1).
For the multipolymer of gained, the weight-average molecular weight recorded by gel permeation chromatography (GPC) is 1,000,000, and molecular weight distribution (Mw/Mn) is 8.0.
3.1.2 embodiment 2 ~ 14 and comparative example 1 ~ 10 (manufacture of multipolymer)
Except using the monomer mixture of the composition shown in table 1 and table 2 respectively, the method recorded by above-described embodiment 1, obtains the solution of the multipolymer of embodiment 2 to 14 and comparative example 1 to 10 respectively.The weight-average molecular weight of the multipolymer of gained, the result that the method recorded with above-described embodiment 1 measures, summary sheet is shown in table 1 and table 2.
3.2. with the making of the Polarizer of caking agent
To (solids component) 100 parts of adhesive solution, add the CORONATEL20 part as the tolylene diisocyanate of (B) isocyanate-based linking agent, as TETRADX0.1 part of (C) epoxy linking agent, the KBM-4030.2 part as (D) silane coupling agent, they are fully mixed, obtains the adhesive composite of embodiment 1.
After deaeration, use scraper, coat the PET barrier film through lift-off processing, immediately in 90 DEG C of dryings 3 minutes.After drying, fit in Polarizer, under the condition of room temperature 23 DEG C, humidity 65%, leave standstill 1 ~ 7 day, obtain the Polarizer with caking agent of embodiment 1.
Except using the composition shown in table 3 and table 4 respectively, the method recorded by above-described embodiment 1, obtains the Polarizer with caking agent of embodiment 2 to 14 and comparative example 1 to 10.
3.3. test method
3.3.1. wet heat durability
By the Polarizer respectively having caking agent that above-mentioned " 3.2. is with the making of the Polarizer of caking agent " obtains, be cut into 250mm × 350mm respectively, after peeling off PET film, be attached on glass substrate and make coupons, it is placed 500 hours at 60 DEG C/95%RH, carries out wet heat durability test.After this test, the foaming occurred with visual inspection coupons, the state of floating, peeling off, with following benchmark evaluation weather resistance.
[benchmark]
◎: do not peel off
Zero: on 4 limits, the position apart from more than peripheral end 0.5mm is not peeled off
△: on 4 limits, the position apart from more than peripheral end 0.5mm is peeled off, and the position of more than 1.5mm is not peeled off
×: on 4 limits, the position apart from more than peripheral end 1.5mm is peeled off
3.3.2. dry rear albefaction patience
By the Polarizer respectively having caking agent that above-mentioned " 3.2. is with the making of the Polarizer of caking agent " obtains, 120 DEG C of dryings after 10 minutes, haze meter HM-150 (in village color Ji Yan institute) is used to measure mist degree, to the mist degree measured value obtained, evaluated by following benchmark.
[benchmark]
◎: be less than 0.5%
More than zero: 0.5% ~ be less than 1%
More than △: 1% ~ be less than 5%
×: more than 5%
3.3.3. sheet material aging
The thermostatted 10 days respectively putting into 50 DEG C with the Polarizer of caking agent above-mentioned " 3.2. is with the making of Polarizer of caking agent " obtained, leaves standstill 1 day after taking-up under the environment of 23 DEG C.Then, this is cut into the size of 310mm × 385mm with Polarizer of caking agent, use laminating roll, adhere to a face of sheet glass, then, keep 20 minutes being adjusted to 50 DEG C, 5 atmospheric autoclaves, make test board.Make 2 identical test boards, under condition respectively at temperature 60 C, humidity 95%RH (moisture-proof) and temperature 80 DEG C condition under (heat-resisting) place 500 hours, with the generation etc. of peeling off of visual inspection test board, evaluated by following benchmark.
[benchmark]
◎: do not observe bad orders such as peeling off completely.
Zero: only observe bad orders such as seldom peeling off, but it is in no problem scope.
△: only observe bad orders such as peeling off a little.
×: obviously observe bad orders such as peeling off.
3.3.4. damp and hot rear peeling force
By the Polarizer respectively having caking agent that above-mentioned " 3.2. is with the making of the Polarizer of caking agent " obtains, cut into width 25mm, length 100mm, use laminating roll, adhere to a face of sheet glass, be held in and be adjusted to 50 DEG C, 5 atmospheric autoclaves 20 minutes.Take out, leave standstill after 1 hour under the condition of 23 DEG C/50%, measure power when peeling off with the angle of 180 ° from sheet glass, it can be used as initial stage peeling force (P
0).Adhere to sheet glass, be held in and be adjusted to 50 DEG C, 5 atmospheric autoclaves after 20 minutes, put into the controlled thermohygrostat 24 hours of 60 DEG C/90%, after taking-up, leave standstill after 1 hour under the condition of 23 DEG C/50%, measure power when peeling off with the angle of 180 ° from sheet glass, it can be used as damp and hot rear peeling force (P
p).Peeling force (P after wet heat treatment
p) and initial stage peeling force (P
0) ratio (P
p/ P
0), as damp and hot rear peeling force evaluation.After damp and hot, peeling force rises, i.e. (P
p/ P
0) value higher, more not easily cause peeling off in damp and hot long duration test, weather resistance is good.
3.3.5. light leak
At the liquid crystal panel of 19 inches of sizes, to fit the adhesion type Polarizer that above-mentioned " 3.2. is with the making of Polarizer of caking agent " obtain in the mode becoming crossed Nicol (CrossNicole), place under the environment of 60 DEG C/95%RH after 240 hours, place 2 hours under the environment of 23 DEG C/50%RH.Then, with visual inspection light leak, with following benchmark evaluation.
[benchmark]
◎: light leak does not occur.
Zero: in the scope of level no problem on using, produce light leak.
△: use on in-problem level scope in, produce light leak.
×: whole on a large scale in, produce light leak.
[table 1]
[table 2]
[table 3]
[table 4]
Wherein, following meaning is abbreviated as in table 3 and table 4.
CORONATEL: tolylene diisocyanate system linking agent (Nippon Polyurethane Industry Co., Ltd.'s system)
CORONATE342: tolylene diisocyanate system linking agent (Japanese polyurethane industrial system)
TETRADX: amine type epoxy linking agent (Mitsubishi Gas Chemical Co., Ltd)
TETRADC: amine type epoxy linking agent (Mitsubishi Gas Chemical Co., Ltd)
DENACOLEX-411: non-amine type epoxy linking agent (NagaseChemteX Inc.)
KBM-403: silane coupling agent (3-glycidoxypropyltrime,hoxysilane, KCC of SHIN-ETSU HANTOTAI)
KAOLIZERNo.1: amine system crosslinking accelerator (Kao Corp).
As shown in Table 3, the bond layer of above-described embodiment 1 to 14, its wet heat durability, dry rear albefaction patience, sheet material aging, damp and hot rear peeling force and light leak preventive excellence.
More specifically, the adhesive composite of above-described embodiment 1 to 14 comprises (A) multipolymer, (B) isocyanate-based linking agent and (C) epoxy linking agent, relative to above-mentioned (A) copolymer 1 00 mass parts, containing above-mentioned (B) isocyanate-based linking agent 8 ~ 50 mass parts, above-mentioned (A) multipolymer is that after the drying of the bond layer therefore using the adhesive composite of above-described embodiment 1 to 14 to obtain, albefaction patience is excellent containing being less than the multipolymer of the monomer mixture of the above-mentioned carboxyl group-containing monomer of 0.5 quality % more than 0 quality %.
The index of the transparency of the bond layer that albefaction patience obtains for use adhesive composite after dry, after so-called drying, albefaction patience is excellent, refers to that the transparency of the bond layer that use adhesive composite obtains is excellent.
The reason of the transparency excellence of the bond layer using the adhesive composite of above-described embodiment 1 to 14 to obtain, supposition is because above-mentioned (A) multipolymer is containing being less than the monomer mixture of the above-mentioned carboxyl group-containing monomer of 0.5 quality % more than 0 quality %, be contained in the carboxyl of this (A) multipolymer, by reacting with the functional group's functional group of above-mentioned (B) isocyanate-based linking agent and/or above-mentioned (C) epoxy linking agent (or from) being contained in above-mentioned (B) isocyanate-based linking agent and/or above-mentioned (C) epoxy linking agent, and improve should (A) multipolymer with should (B) isocyanate-based linking agent and should the intermiscibility of (C) epoxy linking agent.
And, the adhesive composite of above-described embodiment 1 to 14, owing to containing above-mentioned (B) isocyanate-based linking agent 8 ~ 50 mass parts relative to above-mentioned (A) copolymer 1 00 mass parts, therefore the wet heat durability of the bond layer using the adhesive composite of above-described embodiment 1 to 14 to obtain, sheet material aging and damp and hot rear stripping are evaluated excellent.
The wet heat durability of the bond layer using the adhesive composite of above-described embodiment 1 to 14 to obtain, sheet material aging and damp and hot rear stripping evaluate excellent reason, supposition is because above-mentioned (B) isocyanate-based linking agent is 8 ~ 50 weight parts relative to the content of above-mentioned (A) copolymer 1 00 mass parts, suitable hardness can be had by the bond layer that obtains of this adhesive composite of use, therefore the distortion (Polarizer) of optical component is few, and it is as described above, because should (A) multipolymer be containing being less than the multipolymer of the monomer mixture of the above-mentioned carboxyl group-containing monomer of 0.5 quality % more than 0 quality %, and the content of the carboxyl being contained in this (A) multipolymer can be suppressed, therefore long-term excellent in reliability.
Relative to this, can be interpreted as by the result of table 4, the bond layer of above-mentioned comparative example 1 to 5, uses the multipolymer of the monomer mixture of (a1) carboxyl group-containing monomer containing more than 0.5 quality %, so its damp and hot rear peeling force is poor because of above-mentioned (A) multipolymer.Its reason infer be because the carboxyl being contained in above-mentioned (A) multipolymer be contained in above-mentioned (B) isocyanate-based linking agent and/or above-mentioned (C) epoxy linking agent functional group's (or from above-mentioned (B) isocyanate-based linking agent and/or group from above-mentioned (C) epoxy linking agent) reaction through time occur, the cause that result weather resistance reduces.
More specifically, can be interpreted as that the bond layer of comparative example 2 does not also comprise (D) composition because adhesive composite that the making of this bond layer uses neither comprises (C) composition, so poor durability, peel off with crackle produces, result creates light leak.
And, can be interpreted as that the bond layer of comparative example 3 does not comprise (C) composition due to the adhesive composite used in the making of this bond layer, so (the bond layer albefaction of albefaction under wet heat condition, the transmitance of light reduces, and therefore result is that light leak evaluation is good).
And can be interpreted as by the result of table 4, after the drying of the bond layer of above-mentioned comparative example 6, albefaction patience is poor.Its reason infers it is because in the adhesive composite of above-mentioned comparative example 6, because above-mentioned (A) multipolymer uses not containing the multipolymer of the monomer mixture of above-mentioned carboxyl group-containing monomer, make this (A) multipolymer not containing carboxyl, therefore this carboxyl can not occur with the reaction of the functional group's group of above-mentioned (B) isocyanate-based linking agent and/or above-mentioned (C) epoxy linking agent (or from) being contained in above-mentioned (B) isocyanate-based linking agent and/or above-mentioned (C) epoxy linking agent, this (A) multipolymer is low with the intermiscibility being somebody's turn to do (B) isocyanate-based linking agent and this (C) epoxy linking agent.
In addition, can be interpreted as by the result of table 4, wet heat durability and the sheet material aging of the bond layer of above-mentioned comparative example 7 are poor.Its reason infers it is because in the adhesive composite of above-mentioned comparative example 7, because above-mentioned (A) multipolymer uses the multipolymer of the monomer mixture containing (a3) hydroxyl monomer more than 0.3 quality %, (a3) hydroxyl in hydroxyl monomer and the functional group reactions being contained in other compositions, the bond layer that result uses this adhesive composite to obtain becomes too hard.
In addition, can be interpreted as by the result of table 4, after the drying of the bond layer of above-mentioned comparative example 8, albefaction patience is poor.Its reason infers it is because in the adhesive composite of above-mentioned comparative example 8, because not using above-mentioned (B) isocyanate-based linking agent, the carboxyl making to be contained in above-mentioned (A) multipolymer and the functional group being contained in this (B) isocyanate-based linking agent group of this (B) isocyanate-based linking agent (or from) are difficult to produce and react, be somebody's turn to do (A) multipolymer low with the intermiscibility being somebody's turn to do (B) isocyanate-based linking agent, the transparency of the bond layer therefore using this adhesive composite to obtain is low.
In addition, can be interpreted as by the result of table 4, wet heat durability and the damp and hot rear peeling force of the bond layer of above-mentioned comparative example 9 and 10 are poor.Its reason infers it is because in the adhesive composite of above-mentioned comparative example 9 and 10, because not using above-mentioned (C) epoxy linking agent, the carboxyl making to be contained in above-mentioned (A) multipolymer and the functional group being contained in this (C) epoxy linking agent group of this (C) epoxy linking agent (or from) are difficult to produce and react, old friend joins deficiency, and weather resistance is low.
Claims (11)
1. an optical component adhesive composite, is characterized in that:
Comprise: (A) multipolymer,
(B) isocyanate-based linking agent and
(C) epoxy linking agent,
Wherein relative to described (A) copolymer 1 00 mass parts, containing described (B) isocyanate-based linking agent 8 ~ 50 mass parts;
Described (A) multipolymer is containing being less than the multipolymer of the monomer mixture of the described carboxyl group-containing monomer of 0.5 quality % more than 0 quality %.
2. optical component adhesive composite as claimed in claim 1, is characterized in that:
Relative to described (A) copolymer 1 00 mass parts, containing described (C) epoxy linking agent 0.05 ~ 4 mass parts.
3. optical component adhesive composite as claimed in claim 1 or 2, is characterized in that:
The pass of the content of described (B) isocyanate-based linking agent and the use level of described (C) epoxy linking agent is (B): (C)=(10 ~ 40 mass parts): (0.1 ~ 2 mass parts).
4. the optical component adhesive composite according to any one of claims 1 to 3, is characterized in that:
Described monomer mixture is the mixture of following monomer (a1) ~ (a4), and wherein, described monomer (a1) ~ (a4) adds up to 100 quality %,
(a1) carboxyl group-containing monomer: be less than 0.5 quality % more than 0 quality %;
(a2) (methyl) alkyl acrylate monomer: 90 ~ 99.9 quality %;
(a3) hydroxyl monomer: 0 ~ 0.3 quality %;
(a4) co-polymerized monomer beyond described (a1) ~ (a3): 0 ~ 9 quality %.
5. the optical component adhesive composite according to any one of Claims 1 to 4, is characterized in that:
Also comprise (D) silane coupling agent.
6. optical component adhesive composite as claimed in claim 5, is characterized in that:
Relative to described (A) copolymer 1 00 mass parts, containing described (D) silane coupling agent 0.01 ~ 1 mass parts.
7. the optical component adhesive composite according to any one of claim 1 ~ 6, is characterized in that:
Described (C) epoxy linking agent has epoxy group(ing) and amino.
8. the optical component adhesive composite according to any one of claim 1 ~ 7, is characterized in that:
Also comprise (E) basic cpd.
9. an adhesive sheet, is characterized in that:
It is by the optical component adhesive composite according to any one of claim 1 ~ 8 is configured as membranaceous and carry out heating, drying obtains.
10. a multilayer body, is characterized in that, comprising:
Glass substrate;
Light polarizing film; With
Bond layer, it is arranged between described glass substrate and described light polarizing film, this bond layer be by the optical component adhesive composite according to any one of claim 1 ~ 8 is configured as membranaceous and carry out heating, drying obtains.
11. multilayer body as claimed in claim 10, is characterized in that:
The glass substrate that described glass substrate uses for image display device.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2013/069655 WO2015008384A1 (en) | 2013-07-19 | 2013-07-19 | Pressure-sensitive adhesive composition for optical member, pressure-sensitive adhesive sheet, and laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105431500A true CN105431500A (en) | 2016-03-23 |
| CN105431500B CN105431500B (en) | 2018-01-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201380077480.5A Active CN105431500B (en) | 2013-07-19 | 2013-07-19 | Optical component adhesive composite, adhesive sheet and laminated body |
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| Country | Link |
|---|---|
| JP (1) | JP6125636B2 (en) |
| KR (1) | KR101947864B1 (en) |
| CN (1) | CN105431500B (en) |
| WO (1) | WO2015008384A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017160382A (en) * | 2016-03-11 | 2017-09-14 | 日本カーバイド工業株式会社 | Adhesive composition and adhesive sheet |
| JP6534765B1 (en) * | 2018-07-24 | 2019-06-26 | グンゼ株式会社 | Adhesive sheet for image display |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4880315B2 (en) | 2006-02-08 | 2012-02-22 | 日東電工株式会社 | Adhesive composition, adhesive layer, and optical member with adhesive |
| WO2008004650A1 (en) * | 2006-07-06 | 2008-01-10 | Lintec Corporation | Adhesive sheet |
| JP2009058859A (en) * | 2007-09-03 | 2009-03-19 | Sumitomo Chemical Co Ltd | Optical film with pressure-sensitive adhesive and optical laminate |
| JP4963485B2 (en) * | 2008-04-07 | 2012-06-27 | 綜研化学株式会社 | Adhesive composition for polarizing plate and method for producing the same |
| JP4820443B2 (en) * | 2009-11-20 | 2011-11-24 | 日東電工株式会社 | Optical film adhesive composition, optical film adhesive layer, adhesive optical film, and image display device |
| KR101840072B1 (en) * | 2010-08-24 | 2018-03-19 | 닛뽕 카바이도 고교 가부시키가이샤 | Adhesive agent composition |
| JP5554735B2 (en) * | 2010-08-24 | 2014-07-23 | 綜研化学株式会社 | Adhesive for polarizing plate and polarizing plate with adhesive using the same |
| JP2013056963A (en) * | 2011-09-07 | 2013-03-28 | Lintec Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive and pressure-sensitive adhesive sheet |
| JP2013224431A (en) * | 2013-05-20 | 2013-10-31 | Toyo Ink Sc Holdings Co Ltd | Optical pressure-sensitive adhesive agent, and optical pressure-sensitive adhesive sheet |
-
2013
- 2013-07-19 KR KR1020157035820A patent/KR101947864B1/en active IP Right Grant
- 2013-07-19 JP JP2015527130A patent/JP6125636B2/en active Active
- 2013-07-19 CN CN201380077480.5A patent/CN105431500B/en active Active
- 2013-07-19 WO PCT/JP2013/069655 patent/WO2015008384A1/en active Application Filing
Also Published As
| Publication number | Publication date |
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| JP6125636B2 (en) | 2017-05-10 |
| WO2015008384A1 (en) | 2015-01-22 |
| JPWO2015008384A1 (en) | 2017-03-02 |
| KR101947864B1 (en) | 2019-02-13 |
| CN105431500B (en) | 2018-01-02 |
| KR20160034253A (en) | 2016-03-29 |
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