CN104250524A - Adhesive Composition, Adhesive And Adhesive Sheet - Google Patents

Adhesive Composition, Adhesive And Adhesive Sheet Download PDF

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Publication number
CN104250524A
CN104250524A CN201410301348.4A CN201410301348A CN104250524A CN 104250524 A CN104250524 A CN 104250524A CN 201410301348 A CN201410301348 A CN 201410301348A CN 104250524 A CN104250524 A CN 104250524A
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methyl
monomer
adhesive composition
mass parts
acrylic ester
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CN201410301348.4A
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CN104250524B (en
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又野仁
荒井隆行
所司悟
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Lintec Corp
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Lintec Corp
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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
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides an adhesive composition, an adhesive and an adhesive sheet, which do not influence the adhered objects, such as the transparent conductive film, etc., at the same time, are excellent in durability. In order to solve the above subject, the adhesive composition which contains a (methyl) acrylate polymer (A), an isocyanate class cross-linking agent (B), a silane coupling agent possessing sulfydryl (C) and an active energy linear curing component (D),is provided, and the weight-average molecular weight of the above (methyl) acrylate polymer (A) is 1.0-2.5 millions. A monomeric unit as the polymer, contains a monomer possessing the hydroxy, a monomer possessing the aromatic nucleus and a monomer possessing the carboxyl. The (methyl) acrylate polymer (A) as the monomeric unit of the polymer, contains 1-5% by mass of the monomer possessing the hydroxy, 5-30% by mass of the monomer possessing the aromatic nucleus and 0.1-0.8 % by mass of the monomer possessing the carboxyl.

Description

Adhesive composition, caking agent and adhesive sheet
Technical field
The present invention about a kind of adhesive composition, caking agent (making the material that adhesive composition solidifies) and adhesive sheet, especially in regard to a kind of adhesive composition, caking agent and the adhesive sheet that are suitable as the optical component of polarized light piece etc.
Background technology
In recent years in electronic equipment of various, many uses are also used as the contact panel of display unit and input unit.The kind of contact panel mainly contains resistance-type, condenser type, optical profile type and ultrasonic type, and electric resistance touch-control panel has analog electrical resistive and resistance matrix formula, and capacitance type touch-control panel has surface type and projection type.
The contact panel of the mobile electronic equipments such as the smart mobile phone attracted attention recently, panel computer terminal, the capacitive contact panel of many use projection types.As the projection type capacitance type touch-control panel of described mobile electronic equipment; such as, the contact panel having researched and proposed from bottom to top the protective layer such as stratified liquid crystal display unit (LCD), bond layer, nesa coating (tin-doped indium oxide: ITO), glass substrate, nesa coating (ITO) and chilled glass is in order had.
As the optical component forming described liquid crystal indicator, generally use liquid crystal cells.Liquid crystal cells is generally that the oriented layer of two panels transparent electrode substrate using being formed with oriented layer is as inner side, by spacing piece (ス ペ ー サ), be configured in the mode forming predetermined distance, by its peripheral sealing, between two panels transparent electrode substrate, clamp the unit of liquid crystal material.Usually, the outside of the two panels transparent electrode substrate in liquid crystal cells, the bonding polarized light piece respectively by caking agent.
At this, as mentioned above, in the formation of being fitted on nesa coating (ITO) by bond layer by the polarized light piece of liquid crystal indicator, caking agent directly contacts with ITO.Therefore, owing to comprising in a large number as the caking agent of the carboxyl of sour composition, the problem that ITO is corroded or the resistance value of ITO changes can be produced.
As the caking agent of optics, such as, there will be a known the caking agent shown in patent documentation 1.It is the alkyl ester monomer of 4 ~ 12 that this caking agent contains by 50 quality % ~ 90 quality % (methyl) acrylic acid carbonatomss, the acrylic acid ester ring type alkyl ester monomer of 3 quality % ~ 10 quality % (methyl), the multipolymer that the alkyl ester monomer (amounting to 100 quality %) that 0.1 quality % ~ 1.0 quality % (methyl) acrylic acid hydroxyalkyl acrylate monomer and 3 quality % ~ 10 quality % (methyl) acrylic acid carbonatomss are 1 ~ 3 is formed is (containing hydroxyl in multipolymer, but not containing carboxyl, weight-average molecular weight is 700,000 ~ 1,200,000), linking agent is (relative to 100 mass parts multipolymers, be 0.02 mass parts ~ 1 mass parts) and crosslinking coagent (relative to 100 mass parts multipolymers, be 0.5 mass parts ~ 5.0 mass parts).Due to not containing the carboxyl as sour composition, therefore not easily there are the problems referred to above in this caking agent.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Publication 2012-001647 publication
Summary of the invention
(1) technical problem that will solve
On the other hand, along with the slimming of mobile electronic equipment in recent years, the polarized light piece as composition component also starts slimming.Specifically, the polarized light piece that both sides keep the thickness as the protective film of the polyvinyl alcohol of polarizer to decrease is used in.Described polarized light piece, owing to being prevented the ability of polarizer thermal contraction by protective film, therefore thermal contraction has the tendency larger than original change.In addition, as the material of described protective film, the optically functional film etc. also using cyclic olefin polymer (COP) etc. that exhaust easily occurs replaces cellulosetri-acetate.Therefore, to for these caking agent, require that there is the reliability (weather resistance) than now higher.
But when using the caking agent of patent documentation 1 in polarized light piece as above, weather resistance is insufficient, under the high temperature conditions or under wet heat condition, can float or peel off.
The present invention completes in view of such present situation, and object is that providing a kind of can not bring detrimentally affect to the bonded object of nesa coating etc., meanwhile, and the adhesive composition of excellent in te pins of durability, caking agent and adhesive sheet.
(2) technical scheme
In order to reach above-mentioned purpose, first, the invention provides a kind of adhesive composition, it contains (methyl) acrylic ester polymer (A), isocyanates linking agent (B), the silane coupling agent (C) with sulfydryl and active energy ray-curable composition (D), the weight-average molecular weight of described (methyl) acrylic ester polymer (A) is 1,000,000 ~ 2,500,000, as form the monomeric unit of polymkeric substance contain there is hydroxyl monomer, there is the monomer of aromatic nucleus and there is the monomer of carboxyl; Described (methyl) acrylic ester polymer (A), as the monomeric unit forming this polymkeric substance, containing the monomer described in 1 quality % ~ 5 quality % with hydroxyl, containing the monomer described in 5 quality % ~ 30 quality % with aromatic nucleus, containing the monomer (invention 1) described in 0.1 quality % ~ 0.8 quality % with carboxyl.
Foregoing invention (invention 1) described adhesive composition is cross-linked obtained caking agent, the monomer containing the monomer with hydroxyl, the monomer with aromatic nucleus using specified amount respectively due to (methyl) acrylic ester polymer (A) and have a carboxyl is as the monomeric unit being formed this polymkeric substance, the silane coupling agent (C) with sulfydryl plays excellent coupling effect, and active energy ray-curable composition (D) solidification, with the crosslinked winding etc. of (methyl) acrylic ester polymer (A), therefore excellent in te pins of durability.In addition, the amount of the carboxyl comprised due to (methyl) acrylic ester polymer (A) suppresses in lower degree, therefore can suppress the unfavorable condition of the bonded object of the nesa coating caused due to acid etc.
In foregoing invention (invention 1), described isocyanates linking agent (B), is preferably TriMethylolPropane(TMP) modification first phenylene vulcabond (invention 2).
Foregoing invention (invention 1, invention 2) in, the content of isocyanates linking agent described in described adhesive composition (B), relative to (methyl) acrylic ester polymer (A) described in 100 mass parts, be preferably 0.01 mass parts ~ 1 mass parts (invention 3).
In foregoing invention (invention 1 ~ invention 3), the content of silane coupling agent described in described adhesive composition (C), relative to (methyl) acrylic ester polymer (A) described in 100 mass parts, be preferably 0.01 mass parts ~ 0.5 mass parts (invention 4).
In foregoing invention (invention 1 ~ invention 4), described in there is the monomer of aromatic nucleus, be preferably (methyl) vinylformic acid 2-phenylethylester (invention 5).
In foregoing invention (invention 1 ~ invention 5), described active energy ray-curable composition (D), is preferably the polyfunctional acrylic ester class monomer (invention 6) that molecular weight is less than 1000.
In foregoing invention (invention 6), described polyfunctional acrylic ester class monomer, preferably has ring texture (invention 7).
In foregoing invention (invention 1 ~ invention 7), the content of active energy ray-curable composition described in described adhesive composition (D), relative to (methyl) acrylic ester polymer (A) described in 100 mass parts, be preferably 1 mass parts ~ 50 mass parts (invention 8).
The second, the invention provides a kind of caking agent, described adhesive composition (invention 1 ~ invention 8) solidification forms (invention 9) by irradiating active energy ray by it.
In foregoing invention (invention 9), gel fraction is preferably 55% ~ 85% (invention 10).
In foregoing invention (invention 9, invention 10), the storage modulus at 23 DEG C is preferably 0.15MPa ~ 0.3MPa, and the storage modulus at 80 DEG C is preferably 0.05MPa ~ 0.2MPa (invention 11).
3rd, the invention provides a kind of adhesive sheet, it is characterized in that, it possesses base material and bond layer, and described bond layer contains described caking agent (invention 9 ~ invention 11) (invention 12).
In foregoing invention (invention 12), described base material is preferably optical component (invention 13).
In foregoing invention (invention 13), described optical component is preferably polarized light piece (invention 14).
4th, the invention provides a kind of adhesive sheet, it is characterized in that, it bond layer possessing two panels stripping film and clamped by described stripping film in the mode connected with the release surface of described two panels stripping film, described bond layer contains described caking agent (invention 9 ~ invention 11) (invention 15).
In foregoing invention (invention 12 ~ invention 15), to the duplexer of described bond layer and nesa coating, carry out 65 DEG C, expose the damp and hot promotion test of 500 hours to the open air under the atmosphere of 95%RH time, the resistance value increment rate calculated according to following formula of described nesa coating is preferably less than 15% (invention 16).
Resistance value increment rate (%)={ (R-R 0)/R 0} × 100
(in formula, R 0for the damp and hot initial resistivity value promoted before test, R is the resistance value after damp and hot promotion test.)
(3) beneficial effect
According to adhesive composition of the present invention, caking agent and adhesive sheet, detrimentally affect can not be brought to the bonded object of nesa coating etc., meanwhile, excellent in te pins of durability.
Accompanying drawing explanation
The sectional view of the adhesive sheet of Fig. 1 involved by first embodiment of the present invention.
The sectional view of the adhesive sheet of Fig. 2 involved by second embodiment of the present invention.
Fig. 3 is the sectional view of the resistance value working sample made in test example 3.
Fig. 4 is the oblique drawing be described the test method of test example 3.
Embodiment
Below, embodiments of the present invention are described.
(adhesive composition)
Adhesive composition described in present embodiment is (hereinafter referred to as " adhesive composition P ".), containing (methyl) acrylic ester polymer (A), isocyanates linking agent (B), the silane coupling agent (C) with sulfydryl and active energy ray-curable composition (D), the weight-average molecular weight of described (methyl) acrylic ester polymer (A) is 1,000,000 ~ 2,500,000, as the monomer (carboxyl group-containing monomer) that the monomeric unit forming polymkeric substance contains the monomer (hydroxyl monomer) with hydroxyl, the monomer (containing aromatic nucleus monomer) with aromatic nucleus and has carboxyl, preferably also containing Photoepolymerizationinitiater initiater (E).In addition, (methyl) acrylic ester polymer (A) is containing 1 quality % ~ 5 quality % hydroxyl monomer, containing 5 quality % ~ 30 quality % containing aromatic nucleus monomer, containing 0.1 quality % ~ 0.8 quality % carboxyl group-containing monomer as the monomeric unit forming this polymkeric substance.In addition, in this specification sheets, said (methyl) acrylate, refers to two sides of acrylate and methacrylic ester.Other similar term too.In addition, the concept of " multipolymer " in " polymkeric substance ", is also comprised.
In described adhesive composition P, (methyl) acrylic ester polymer (A), as the monomeric unit forming this polymkeric substance, by containing hydroxyl monomer, containing aromatic nucleus monomer and carboxyl group-containing monomer with specified amount respectively, thus this adhesive composition P is solidified the caking agent obtained, have cohesive force and stress retentivity concurrently, excellent in te pins of durability.
In addition, if described adhesive composition P is solidified, then the sulfydryl of silane coupling agent (C) isocyanate group that is easy and isocyanates linking agent (B) forms thiocarbamate key, other isocyanate group of this isocyanates linking agent (B) and the hydroxyl reaction of (methyl) acrylic ester polymer (A), (methyl) acrylic ester polymer (A) is cross-linked, forms the 1st three-dimensional net structure.And by inference, alkoxysilyl and (methyl) acrylic ester polymer (A) of silane coupling agent (C) keep suitable distance, are suspended on (methyl) acrylic ester polymer (A).Thus, excellent coupling effect is played.On the other hand, multiple active energy ray-curable composition (D) be combined with each other, and forms the 2nd three-dimensional net structure.By inference, described 1st three-dimensional net structure and the 2nd three-dimensional net structure are wound around mutually, form overall three-dimensional net structure and (this structure are called " structure X " below.)。By this structure X and described coupling effect, the caking agent obtained, under the high temperature conditions or under wet heat condition, adhesion durability is also excellent.
In addition, in described adhesive composition P, because the content of the carboxyl group-containing monomer contained as monomeric unit of (methyl) acrylic ester polymer (A) suppresses in lower degree, therefore the unfavorable condition that the attaching object of obtained caking agent causes due to acid can be suppressed, such as, when for nesa coating and metallic membrane etc., also can suppress these unfavorable conditions because acid causes.Particularly when to attach object be nesa coating, this nesa coating can be suppressed to be corroded or the resistance value of this nesa coating changes.
(1) (methyl) acrylic ester polymer (A)
(methyl) acrylic ester polymer (A), as the monomeric unit forming this polymkeric substance, except described hydroxyl monomer, containing except aromatic nucleus monomer and carboxyl group-containing monomer, be preferably (methyl) alkyl acrylate of 1 ~ 20 containing the carbonatoms of alkyl, particularly preferably contain as principal constituent.In addition, as required, can also containing other monomer.
(methyl) acrylic ester polymer (A), by the carbonatoms containing alkyl be (methyl) alkyl acrylate of 1 ~ 20 as forming the monomeric unit of this polymkeric substance, excellent cementability can be showed.Carbonatoms as alkyl is (methyl) alkyl acrylate of 1 ~ 20, such as, (methyl) methyl acrylate can be listed, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butylacrylate, (methyl) vinylformic acid n-pentyl ester, (methyl) vinylformic acid n-hexyl ester, (methyl) 2-ethylhexyl acrylate, (methyl) isooctyl acrylate ester, the positive decyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid dodecyl ester, (methyl) myristyl base ester, (methyl) vinylformic acid palmityl ester, (methyl) stearyl acrylate base ester etc.Wherein, from the viewpoint of more improving cementability, the carbonatoms of preferred alkyl is (methyl) acrylate of 1 ~ 8, particularly preferably (methyl) methyl acrylate and (methyl) n-butylacrylate.And these may be used singly or in combination of two or more use.
(methyl) acrylic ester polymer (A), as the monomeric unit forming this polymkeric substance, preferably containing 50 quality % ~ 93.9 quality %, the carbonatoms of alkyl be 1 ~ 20 (methyl) alkyl acrylate, particularly preferably containing 64.2 quality % ~ 93 quality %, further preferably containing 80 quality % ~ 90 quality %.In addition, if (methyl) alkyl acrylate containing more than 50 quality %, then (methyl) acrylic ester polymer (A) can be endowed excellent cementability.In addition, by (methyl) alkyl acrylate containing below 93.9 quality %, in (methyl) acrylic ester polymer (A), other monomer components can be imported preferably to measure.
(methyl) acrylic ester polymer (A), as the monomeric unit forming this polymkeric substance, containing hydroxyl monomer.The isocyanate group reactivity of this hydroxyl and isocyanates linking agent (B) is high, and by their reaction, (methyl) acrylic ester polymer (A) is cross-linked by isocyanates linking agent (B).By this crosslinking structure, the excellent in te pins of durability of the caking agent obtained.
As hydroxyl monomer, such as, can list (methyl) hydroxyalkyl acrylates etc. of (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid 2-hydroxy-propyl ester, (methyl) vinylformic acid 3-hydroxy-propyl ester, (methyl) vinylformic acid 2-hydroxybutyl ester, (methyl) vinylformic acid 3-hydroxybutyl ester, (methyl) vinylformic acid 4-hydroxybutyl ester etc.Wherein, consider from the reactive viewpoint with isocyanates linking agent (B), preferably (methyl) vinylformic acid 2-hydroxyethyl ester or (methyl) vinylformic acid 4-hydroxybutyl ester.These may be used singly or in combination of two or more use.
(methyl) acrylic ester polymer (A), as the monomeric unit forming this polymkeric substance, the hydroxyl monomer containing 1 quality % ~ 5 quality %, preferably containing 2 quality % ~ 4 quality %.The content of hydroxyl monomer is in above-mentioned scope, then the crosslinking structure formed becomes good, and the caking agent obtained has excellent weather resistance.If the content of hydroxyl monomer is less than 1 quality %, then cross-linking set is very few, and cohesive force reduces, and the caking agent obtained cannot play excellent weather resistance.On the other hand, if the content of hydroxyl monomer is more than 5 quality %, then cross-linking set is too much, and the caking agent obtained becomes not soft, and stress retentivity declines, and thus, cannot tackle the contraction of base material, and weather resistance is deteriorated.
(methyl) acrylic ester polymer (A), as the monomeric unit forming this polymkeric substance, containing containing aromatic nucleus monomer.Thus, (methyl) acrylic ester polymer (A) has suitable hardness, and the caking agent obtained easily has aggegation force and stress retentivity concurrently, excellent in te pins of durability.
As containing aromatic nucleus monomer, such as can enumerate (methyl) phenyl acrylate, (methyl) vinylformic acid 2-phenylethylester, (methyl) benzyl acrylate, (methyl) vinylformic acid naphthyl ester, (methyl) phenoxy ethyl acrylate, (methyl) vinylformic acid phenoxy group butyl ester, ethoxylation orthoxenol acrylate, phenoxy group glycol ether (methyl) acrylate, ethylene-oxide-modified cresols (methyl) acrylate, oxyethane (EO) modification nonylphenol (methyl) acrylate etc., wherein, from the viewpoint of raising cohesive force, preferably (methyl) vinylformic acid 2-phenylethylester.These may be used singly or in combination of two or more use.
(methyl) acrylic ester polymer (A), as the monomeric unit forming this polymkeric substance, containing 5 quality % ~ 30 quality % containing aromatic nucleus monomer, be preferably containing 7 quality % ~ 25 quality %, be particularly preferably containing 10 quality % ~ 20 quality %.Containing the content of aromatic nucleus monomer in above-mentioned scope, then obtained caking agent has excellent stress retentivity and the weather resistance of excellence.If the content containing aromatic nucleus monomer is less than 5 quality %, then the weather resistance of obtained caking agent is deteriorated.On the other hand, if containing the content of aromatic nucleus monomer more than 30 quality %, then the use level of other compositions reduces, and the weather resistance of the caking agent obtained is deteriorated.
(methyl) acrylic ester polymer (A), as the monomeric unit forming this polymkeric substance, containing carboxyl group-containing monomer.This carboxyl can promote the crosslinking reaction of hydroxyl in (methyl) acrylic ester polymer (A) and isocyanates linking agent (B), meanwhile, also there is crosslinking reaction with isocyanates linking agent (B) in carboxyl itself.Thus, the crosslinked degree of the caking agent obtained is suitable, and the crosslinking degree between (methyl) acrylic ester polymer (A) is impartial, thus excellent in te pins of durability.
(methyl) acrylic ester polymer (A), as the monomeric unit forming this polymkeric substance, carboxyl group-containing monomer containing 0.1 quality % ~ 0.8 quality %, is preferably containing 0.1 quality % ~ 0.5 quality %, is particularly preferably containing 0.1 quality % ~ 0.3 quality %.Carboxyl group-containing monomer is in above-mentioned scope, then obtained caking agent has excellent weather resistance.If the content of carboxyl group-containing monomer is less than 0.1 quality %, then the weather resistance of obtained caking agent is deteriorated.On the other hand, if the content of carboxyl group-containing monomer is more than 0.8 quality %, then, when the attaching object of obtained caking agent is nesa coating etc., nesa coating etc. can be corroded, or large change occurs the resistance value of nesa coating.
As other monomers described, even in order to not hinder the reaction of the described hydroxyl of hydroxyl monomer and the carboxyl of carboxyl group-containing monomer and isocyanates linking agent (B), preferably do not comprise the monomer with isocyanates linking agent (B) with reactive functional group yet.As other such monomers, such as, can enumerate (methyl) alkoxyalkyl acrylate of (methyl) methoxyethyl ethyl ester, (methyl) ethioxy ethyl ester etc.; The acrylamide of the non-crosslinked of acrylamide, Methacrylamide etc.; (methyl) vinylformic acid N, N-dimethyl aminoethyl ester, (methyl) vinylformic acid N, (methyl) acrylate with tertiary amino of the non-crosslinked of N-dimethylaminopropyl ester etc.; Vinyl-acetic ester etc.These may be used singly or in combination of two or more use.
The polymerization methods of (methyl) acrylic ester polymer (A) can be random copolymers, also can be segmented copolymer.
The weight-average molecular weight of (methyl) acrylic ester polymer (A) is 1,000,000 ~ 2,500,000, is preferably 1,400,000 ~ 2,200,000, is particularly preferably 1,800,000 ~ 2,000,000.In addition, the weight-average molecular weight in this specification sheets is the value of polystyrene conversion measured according to gel permeation chromatography (GPC) method.
(methyl) acrylic ester polymer (A) if weight-average molecular weight be less than 1,000,000, then obtained caking agent weather resistance is deteriorated.(methyl) acrylic ester polymer (A) if weight-average molecular weight more than 2,500,000, then obtained caking agent processibility is deteriorated.
In addition, in adhesive composition P, (methyl) acrylic ester polymer (A) can be used alone one, also can be used in combination of two or more.In addition, adhesive composition P also can contain hydroxyl monomer further, containing aromatic nucleus monomer or carboxyl group-containing monomer as (methyl) acrylic ester polymer forming monomeric unit.
(2) isocyanates linking agent (B)
The reactivity that isocyanates linking agent (B) has the hydroxyl had with (methyl) acrylic ester polymer (A) and the advantage of the reactivity excellence of sulfydryl had with silane coupling agent (C).
Isocyanates linking agent (B) is the linking agent at least containing polyisocyanate compound.As polyisocyanate compound, such as, can enumerate the aromatic polyisocyanate of first phenylene vulcabond, '-diphenylmethane diisocyanate, xylylene diisocyanate etc.; The aliphatic polyisocyante of hexamethylene diisocyanate etc.; The ester ring type polyisocyanates etc. of isophorone diisocyanate, hydrogenated diphenyl methane diisocyanate etc.; And these biuret body, isocyanuric acid ester body, can enumerate further and contain the adduction object etc. of the reactant of low molecule active dydrogen compounds as with ethylene glycol, propylene glycol, neopentyl glycol, TriMethylolPropane(TMP), castor-oil plant wet goods, wherein when for polarized light piece, from the viewpoint of weather resistance and processibility, be preferably TriMethylolPropane(TMP) modified aromatic race polyisocyanates, be particularly preferably TriMethylolPropane(TMP) modification first phenylene vulcabond.Described isocyanates linking agent (B) can be used alone one, or also can be used in combination of two or more.
In adhesive composition P, the content of isocyanates linking agent (B), relative to 100 mass parts (methyl) acrylic ester polymer (A), be preferably 0.01 mass parts ~ 1 mass parts, be particularly preferably 0.05 mass parts ~ 0.5 mass parts, more preferably 0.1 mass parts ~ 0.3 mass parts.By making the content of isocyanates linking agent (B) in above-mentioned scope, then, in obtained caking agent, the crosslinking structure of stress retentivity and excellent in te pins of durability can be formed.
(3) silane coupling agent (C)
Silane coupling agent (C) in present embodiment has sulfydryl.This sulfydryl easily and the isocyanic ester radical reaction of isocyanates linking agent (B).As previously mentioned, by inference in the caking agent that adhesive composition P is solidified, alkoxysilyl and (methyl) acrylic ester polymer (A) of silane coupling agent (C) keep suitable distance, namely, in isocyanates linking agent (B), multiple isocyanate group is kept at a distance each other, hangs on (methyl) acrylic ester polymer (A).Like this, alkoxysilyl is by keeping suitable distance with (being cross-linked) (methyl) acrylic ester polymer (A) and exist, excellent coupling effect can be played, caking agent obtained thus, excellent in adhesion, even if under the high temperature conditions and under wet heat condition, adhesion durability is also excellent.This effect, when the attaching object of caking agent is the inorganic materials such as glass or metal, plays especially remarkable.
As silane coupling agent (C), for at least there is in molecule a sulfydryl, at least there are the silicoorganic compound of an alkoxysilyl, good with the consistency of caking agent composition, and the person that has photopermeability, to be such as essentially transparent person be preferred.
As the concrete example of described silane coupling agent (C), such as, what can list 3-mercaptopropyi Trimethoxy silane, 3-Mercaptopropyltriethoxysilane, 3-mercaptopropyi dimethoxymethylsilane etc. contains sulfydryl low molecule type silane coupling agent; The cocondensation compound etc. containing alkyl silane cpd containing mercaptosilane compound and Union carbide A-162, ethyl triethoxysilane, methyltrimethoxy silane, ethyl trimethoxy silane etc. of 3-mercaptopropyi Trimethoxy silane, 3-Mercaptopropyltriethoxysilane, 3-mercaptopropyi dimethoxymethylsilane etc. contain sulfydryl oligomeric silane coupling agent etc.Wherein, from the viewpoint of raising weather resistance, be preferably containing sulfydryl oligomeric silane coupling agent, particularly preferably containing mercaptosilane compound and the cocondensation compound containing alkyl silane cpd, the more preferably cocondensation compound of 3-mercaptopropyi Trimethoxy silane and Union carbide A-162.These can be used alone one, also can be used in combination of two or more.
The content of silane coupling agent (C) in adhesive composition P, relative to 100 mass parts (methyl) acrylic ester polymer (A), be preferably 0.01 mass parts ~ 0.5 mass parts, be particularly preferably 0.1 mass parts ~ 0.4 mass parts.Silane coupling agent (C) if content be less than 0.01 mass parts, then have the situation being difficult to obtain the effect produced by this silane coupling agent (C).On the other hand, silane coupling agent (C) if content more than 0.5 mass parts, then the reaction of isocyanates linking agent (B) and (methyl) acrylic ester polymer (A) has situation about being hindered.
(4) active energy ray-curable composition (D)
Active energy ray-curable composition (D), as long as not hinder effect of the present invention, the composition solidified by the irradiation of active energy ray, is just had no particular limits, can be any one in monomer, oligopolymer or polymkeric substance, also can be these mixture.Wherein, can preferably enumerate with the excellent compatibility of (methyl) acrylic ester polymer (A) etc., polyfunctional acrylic ester class monomer that molecular weight is less than 1000.
The polyfunctional acrylic ester class monomer of 1000 is less than as molecular weight, such as can list 1, 4-butyleneglycol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, neopentyl glycol hexanodioic acid two (methyl) acrylate, hydroxypivalic acid neopentyl glycol two (methyl) acrylate, bicyclopentyl two (methyl) acrylate, caprolactone modification dicyclopentenyl two (methyl) acrylate, ethylene-oxide-modified di(2-ethylhexyl)phosphate (methyl) acrylate, two (acryloyl-oxyethyl) isocyanuric acid ester, 2 functional-type of allylation cyclohexyl two (methyl) acrylate etc., 3 functional-type of trimethylolpropane tris (methyl) acrylate, Dipentaerythritol three (methyl) acrylate, propionic acid modification Dipentaerythritol three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, three (acryloyl-oxyethyl) isocyanuric acid ester etc., 4 functional-type of two glycerine four (methyl) acrylate, tetramethylolmethane four (methyl) acrylate etc., 5 functional-type of propionic acid modification Dipentaerythritol five (methyl) acrylate etc., 6 functional-type etc. of Dipentaerythritol six (methyl) acrylate, caprolactone modification Dipentaerythritol six (methyl) acrylate etc.These can be used alone one, also can be used in combination of two or more.
In described polyfunctional acrylic ester class monomer, more excellent owing to having ring texture person's endurance quality in skeleton, so preferably.Ring texture can be carbon-ring type structure, also can be hetero ring type structure, and in addition, can be monocyclic structure, also can be polycycle structure.As described polyfunctional acrylic ester class monomer, such as can list two (acryloyl-oxyethyl) isocyanuric acid ester, three (acryloyl-oxyethyl) isocyanuric acid ester etc. has isocyanurate structure person, or dihydroxymethyl bicyclopentane diacrylate, ethylene-oxide-modified hexahydrophthalic acid diacrylate, Tricyclodecane Dimethanol acrylate, diamantane diacrylate etc.
As active energy ray-curable composition (D), the acrylate quasi-oligomer of active energy ray-curable also can be utilized.It is 50, less than 000 that this acrylate quasi-oligomer is preferably weight-average molecular weight.As described acrylate quasi-oligomer, such as, can enumerate polyester acrylate class, Epoxy Acrylates, urethane acrylate class, polyether acrylate class, PBAA ester class, silicon acrylate etc.
At this, polyester acrylate oligomer, such as can by using (methyl) vinylformic acid, and what the polycondensation by polycarboxylic acid and polyvalent alcohol obtained has the hydroxy esterification of the polyester oligomer of hydroxyl at two ends and obtain; Or, by with (methyl) vinylformic acid, the hydroxy esterification of the oligomer end of addition epoxy alkane gained on polycarboxylic acid can be obtained.Epoxy Acrylates oligopolymer, such as can by the oxyethane ring of the lower bisphenol-type epoxy resin of molecular weight or phenolic resin varnish type epoxy resin, (methyl) vinylformic acid is reacted and esterification and obtaining.In addition, the carboxy-modified type epoxy acrylate oligomer of this Epoxy Acrylates oligopolymer dicarboxylic acid anhydride being carried out partly modification gained can also be used.Urethane acrylate quasi-oligomer, such as, can by with (methyl) vinylformic acid, will the urethane oligomer esterification obtained be reacted by polyether glycol or polyester polyol and polyisocyanates and obtain.Polyalcohol acrylate quasi-oligomer, by with (methyl) vinylformic acid, can make the hydroxy esterification of polyether glycol and obtains.
The weight-average molecular weight of described acrylate quasi-oligomer is preferably 50, less than 000, is particularly preferably 500 ~ 50,000, and more preferably 3,000 ~ 40,000.These acrylate quasi-oligomers can be used alone one, also can be used in combination of two or more.
In addition, as active energy ray-curable composition (D), the adduction acrylic polymer that side chain has imported the group gained with (methyl) acryl also can be used in.Such adduction acrylic polymer; can by using the multipolymer in (methyl) acrylate and molecule with the monomer of cross-linking functional group; the compound of the group making to have (methyl) acryl and react with cross-linking functional group, carries out reacting with the cross-linking functional group's of this multipolymer part and obtains.
As described (methyl) acrylate, carbonatoms preferably containing alkyl is (methyl) alkyl acrylate of 1 ~ 20, such as can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate cores, (methyl) vinylformic acid amyl group ester, (methyl) vinylformic acid polyhexamethylene, (methyl) cyclohexyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) isooctyl acrylate ester, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) myristyl base ester, (methyl) vinylformic acid palmityl ester, (methyl) stearyl acrylate base ester etc.These may be used singly or in combination of two or more use.
There is the monomer of cross-linking functional group, as functional group, preferably containing at least one being selected from hydroxyl, carboxyl, amino and amide group in described molecule.As described monomer, such as, can enumerate (methyl) hydroxyalkyl acrylates of (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid 2-hydroxy-propyl ester, (methyl) vinylformic acid 3-hydroxy-propyl ester, (methyl) vinylformic acid 2-hydroxybutyl ester, (methyl) vinylformic acid 3-hydroxybutyl ester, (methyl) vinylformic acid 4-hydroxybutyl ester etc.; The acrylic amide of acrylamide, Methacrylamide, N methacrylamide, N-methyl methacrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide etc.; (methyl) vinylformic acid Mono-alkylaminoalkyl ester of (methyl) vinylformic acid mono-methyl amino ethyl ester, (methyl) vinylformic acid list ethylaminoethyl ester, (methyl) vinylformic acid mono-methyl amino propyl diester, (methyl) vinylformic acid list diethylaminobutyyl ester etc.; The alkene class unsaturated carboxylic acid etc. of vinylformic acid, methacrylic acid, β-crotonic acid, toxilic acid, methylene-succinic acid, citraconic acid etc.These monomers may be used singly or in combination of two or more use.
As having the compound carrying out the group reacted with (methyl) acryl and cross-linking functional group, such as, preferably can enumerate 2-methylacryoyloxyethyl isocyanic ester, methacrylic acid 2-(0-[1 '-methyl propylene is amino] carboxyamino) ethyl ester, 2-[(3, 5-dimethyl pyrazole) carbonylamino] ethylmethyl acrylate, 1, 1-(two acryloyloxymethyl) ethyl isocyanate, 2-acryloyloxyethyl isocyanate, 2-acryloyloxyethyl succinate, 2-acrylyl oxy-ethyl hexahydrophthalic phthalimide, ω-carboxyl-polycaprolactone single-acrylate, phthalic acid list hydroxy ethyl methacrylate, 2-hydroxyl-3-phenoxypropylacrylate etc.These compounds may be used singly or in combination of two or more use.
The weight-average molecular weight of described adduction acrylic polymer, is preferably 300,000 ~ about 2,000,000, is particularly preferably 500,000 ~ 850,000.
Active energy ray-curable composition (D), both a kind of use can have been selected from described polyfunctional acrylic ester class monomer, acrylate quasi-oligomer and adduction acrylic polymer, also can by the two or more use that combines, can also with these beyond active energy ray-curable composition combine and use.
The content of the active energy ray-curable composition (D) in adhesive composition P, relative to 100 mass parts (methyl) acrylic ester polymer (A), be preferably 1 mass parts ~ 50 mass parts, be particularly preferably 2 mass parts ~ 20 mass parts, more preferably 3 mass parts ~ 10 mass parts.By inference, the caking agent obtained by the adhesive composition P containing active energy ray-curable composition (D) within the scope of this, can form described structure X well.Particularly, by inference, by making the content of active energy ray-curable composition (D) be 3 mass parts ~ 10 mass parts, described structure X can have flexibility and cohesive force concurrently in higher level, becomes the caking agent that weather resistance is excellent especially.
(5) Photoepolymerizationinitiater initiater (E)
As the active energy ray irradiated to adhesive composition P, in the ultraviolet situation of use, adhesive composition P is preferably also containing Photoepolymerizationinitiater initiater (E).Like this, by containing Photoepolymerizationinitiater initiater (E), active energy ray-curable composition (D) effectively can be made to solidify, in addition, the irradiation dose of polymerizing curable time and active energy ray can be reduced.
As described Photoepolymerizationinitiater initiater (E), such as, bitter almond oil camphor can be enumerated, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, bitter almond oil camphor n-butyl ether, benzoin isobutyl ether, methyl phenyl ketone, dimethylamino methyl phenyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methyl thio) phenyl]-2-morpholine-propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-2-(hydroxyl-2-propyl group) ketone, benzophenone, to phenyl benzophenone, 4,4 '-diethylamino benzophenone, dichloro benzophenone, 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 2-aminoanthraquinone, 2-methyl thioxanthone, 2-ethyl thioxanthone, CTX, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, benzyl dimethyl ketal, methyl phenyl ketone dimethyl ketal, ESCAROL 507 ester, oligomeric (2-hydroxy-2-methyl-1 [4-(1-methyl ethylene) benzene] acetone], 2,4,6-trimethylbenzoy-dipheny-phosphine oxide etc.These may be used singly or in combination of two or more use.
Photoepolymerizationinitiater initiater (E), relative to 100 mass parts active energy ray-curable compositions (D), is preferably 2 mass parts ~ 15 mass parts, particularly preferably uses with the amount of the scope of 5 mass parts ~ 12 mass parts.
(6) various additive
Adhesive composition P, as required, can be added on normally used various additive in acrylic-based adhesives, such as, and antistatic agent, tackifier, antioxidant, UV light absorber, photostabilizer, softening agent, weighting agent, refractive index adjusters etc.
As the object lesson of antistatic agent, N-butyl-4-picoline hexafluorophosphate, N-hexyl-4-picoline hexafluorophosphate, N-butyl-2-hexyl pyridine perchlorate, two (fluorine sulfimide) potassium (KFSI), two (fluoroform sulfimide) potassium (KTFSI), two (fluorine sulfimide) lithium (LiFSI), two (trifluoromethanesulfonimide) lithium (LiTFSI), two (trifyl) imines of N-butyl-2-hexyl pyridine etc. can be enumerated.These antistatic agents, can be used alone one, also can be used in combination of two or more.
(manufacture method of adhesive composition)
Adhesive composition P can by manufacturing (methyl) acrylic ester polymer (A), obtained (methyl) acrylic ester polymer (A) is mixed with isocyanates linking agent (B), silane coupling agent (C), active energy ray-curable composition (D), simultaneously, as required, add Photoepolymerizationinitiater initiater (E), additive etc. in any stage to manufacture.
(methyl) acrylic ester polymer (A), by using common radical polymerization, can manufacture the polymerization of mixtures of the monomeric unit forming polymkeric substance.The polymerization of (methyl) acrylic ester polymer (A), can use polymerization starter as required, be undertaken by solution polymerization process etc.As polymer solvent, such as, can enumerate ethyl acetate, ro-butyl acetate, Sucrose Acetate base ester, toluene, acetone, hexane, methyl ethyl ketone etc., can use two or more simultaneously.
As polymerization starter, can azo compound, organo-peroxide etc. be enumerated, can use two or more simultaneously.As azo compound, such as can enumerate 2,2 '-azobis isobutyronitrile, 2,2 '-azo two (2-methylbutyronitrile), 1,1 '-azo two (hexanaphthene 1-formonitrile HCN), 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (2,4-dimethyl-4-methoxyl-valeronitrile), dimethyl 2,2 '-azo two (2 Methylpropionic acid ester), 4,4 '-azo two (4-cyano group valeric acid), 2,2 '-azo two (2-hydroxymethyl propionitrile), 2,2 '-azo two (2-(2-tetrahydroglyoxaline-2-base) propane) etc.
As organo-peroxide; such as; benzoyl peroxide, peroxybenzoate, hydrogen phosphide cumene, diisopropyl peroxydicarbonate, diη-propyl peroxy dicarbonate, two (2-ethoxyethyl group) peroxy dicarbonate, peroxidation neodecanoic acid tertiary butyl ester, peroxidation trimethylacetic acid tertiary butyl ester, (3 can be listed; 5,5-trimethyl acetyl base) superoxide, two propionyl superoxide, diacetyl superoxide etc.
In addition, in above-mentioned polymerization process, by coordinating the chain-transfer agent of 2 mercapto ethanol etc., can regulate the weight-average molecular weight of the polymkeric substance obtained.
After obtaining (methyl) acrylic ester polymer (A), in the solution of (methyl) acrylic ester polymer (A), add isocyanates linking agent (B), silane coupling agent (C), active energy ray-curable composition (D) and add Photoepolymerizationinitiater initiater (E), diluting solvent, additive etc. as required, fully mix, the adhesive composition P (coating solution) obtained with solvent cut.
As for diluting adhesive composition P, obtain the diluting solvent of coating solution, such as, can use the aliphatic hydrocarbon of hexane, heptane, hexanaphthene etc.; The aromatic hydrocarbons of toluene, dimethylbenzene etc.; The halohydrocarbon of methylene dichloride, ethylene dichloride etc.; The alcohol of methyl alcohol, ethanol, propyl alcohol, butanols, 1-methoxy-2-propanol etc.; The ketone of acetone, methyl ethyl ketone, 2 pentanone, isophorone, pimelinketone etc.; The ester of ethyl acetate, acetic acid butyl ester etc.; The cellosolve type solvents etc. of ethyl cellosolve etc.
As concentration, the viscosity of the coating solution of so modulation, as long as being coated with possible scope, have no particular limits, can according to circumstances carry out suitable selected.Such as, the concentration of adhesive composition P can be diluted to 10 quality % ~ 40 quality %.In addition, when obtaining coating solution, the interpolation of diluting solvent etc. is not prerequisite, as long as adhesive composition P is coated with possible viscosity etc., can not add diluting solvent yet.In this situation, adhesive composition P becomes the polymer solvent of (methyl) acrylic ester polymer (A) directly as the coating solution of diluting solvent.
(caking agent)
Caking agent described in present embodiment, preferably by being carried out by adhesive composition P being coated with on desired object, after drying, by the irradiation of active energy ray, makes adhesive composition P solidify and obtain.After carrying out these process, as required, during the maturation of about 1 ~ 2 week can being set under normal temperature (such as, 23 DEG C, 50%RH).When during needing this maturation, after during maturation, forming caking agent (layer); When during not needing maturation, after active energy ray irradiates, form caking agent (layer).
The drying of adhesive composition P, by air-dry and carry out, but can be undertaken by heat treated (being preferably warm air drying) usually.When carrying out heat treated, Heating temperature is preferably 50 DEG C ~ 150 DEG C, is particularly preferably 70 DEG C ~ 120 DEG C.In addition, be preferably 10 seconds ~ 10 minutes heat-up time, particularly preferably 50 seconds ~ 2 minutes.
As active energy ray, usually use ultraviolet, electron beam etc.The irradiation dose of active energy ray is different according to the kind of energy line, and such as, under using ultraviolet situation, light quantity is preferably 50mJ/cm 2~ 1000mJ/cm 2, be particularly preferably 100mJ/cm 2~ 500mJ/cm 2.In addition, when using electron beam, be preferably about 10krad ~ 1000krad.
By above-mentioned heat treated (and maturation), by isocyanates linking agent (B), (methyl) acrylic ester polymer (A) is cross-linked, and forms the 1st three-dimensional net structure.In addition, the sulfydryl of silane coupling agent (C) easily and the isocyanic ester radical reaction of isocyanates linking agent (B), the alkoxysilyl of this silane coupling agent (C) by inference, by this isocyanates linking agent (B), with (methyl) acrylic ester polymer (A), keep suitable distance with above-mentioned three-dimensional net structure further and exist, playing excellent coupling effect.On the other hand, by the irradiation of active energy ray, multiple active energy ray-curable composition (D) be combined with each other, and forms the 2nd three-dimensional net structure.2nd three-dimensional net structure and described 1st three-dimensional net structure are wound around mutually by inference, form said structure X.Owing to having the caking agent of described structure X, there is suitable bonding force and stress retentivity and there is high cohesive force, therefore there is excellent weather resistance.
In addition, adhesive composition P is solidified the caking agent obtained, even if when described 1st three-dimensional net structure presents comparatively loose state, due to containing aromatic nucleus, also there is suitable cohesive force.Thus, cohesive force can not be made to reduce, can improve stress retentivity, therefore, the weather resistance of caking agent is high.In addition, rely on the coupling effect of the excellence obtained by silane coupling agent (C), excellent in adhesion to glass surface etc., under the high temperature conditions or under wet heat condition, also can play excellent adhesion durability.Described caking agent, such as, under the hot conditions of 85 DEG C or 60 DEG C, when placing 250 hours under the wet heat condition of 90%RH, also can prevent from/suppress floating, peel off, the generation of bubble etc.
The gel fraction of caking agent described in present embodiment, is preferably 55% ~ 85%, is particularly preferably 60% ~ 80%.If gel fraction is less than 55%, then the cohesive force of caking agent is not enough, has the situation that weather resistance and re-workability reduce.Particularly when for COP polarized light piece, there is the situation that at high temperature can not get sufficient adhesion durability.On the other hand, if gel fraction is more than 85%, then stress retentivity becomes too low, has the situation that weather resistance reduces.
The storage modulus of caking agent described in present embodiment at 23 DEG C (G '), consider from weather resistance viewpoint, be preferably 0.15MPa ~ 0.3MPa, be particularly preferably 0.18MPa ~ 0.28MPa, from the viewpoint of making haze value more excellent, more preferably 0.20MPa ~ 0.26MPa.In addition, and storage modulus at 80 DEG C (G '), consider from weather resistance viewpoint, be preferably 0.05MPa ~ 0.2MPa, be particularly preferably 0.08MPa ~ 0.18MPa, from the viewpoint of making haze value more excellent, more preferably 0.1MPa ~ 0.14MPa.In addition, described storage modulus (G ') is for according to the value turned round the method for cutting and measure described later.
(adhesive sheet)
As shown in Figure 1, adhesive sheet 1A described in the 1st embodiment, according to order from the bottom up, by stripping film 12, is laminated in the bond layer 11 in the release surface of stripping film 12 and the base material 13 be laminated on bond layer 11 formed.
In addition, as shown in Figure 2, adhesive sheet 1B described in the 2nd embodiment, by two panels stripping film 12a, 12b, and in the mode connected with the release surface of this two panels stripping film 12a, 12b, the bond layer 11 clamped by this two panels stripping film 12a, 12b form.In addition, the release surface of so-called stripping film in this specification sheets, refers in stripping film the face with separability, also demonstrates any one of the face of separability even if comprise the face that implements lift-off processing and do not implement lift-off processing.
Adhesive sheet 1A, 1B any one in, bond layer 11 all contains the caking agent above-mentioned adhesive composition P solidified.
The thickness of bond layer 11, suitablely according to the application target of adhesive sheet 1A, 1B to determine, but be generally 5 μm ~ 100 μm, be preferably the scope of 10 μm ~ 60 μm, such as, when as optical component, particularly as polarized light piece bond layer use, be preferably 10 μm ~ 50 μm, be particularly preferably 15 μm ~ 30 μm.
As base material 13, have no particular limits, the base material that the substrate sheets as common adhesive sheet uses can use.Such as, except desired optical component, weaving cotton cloth or non-woven fabrics of the fiber employing artificial silk, vinylformic acid (ester), polyester etc. can also be listed; Synthetic paper; The stationery of good quality paper, glassine, impregnation paper, enamelled paper etc.; The tinsel of aluminium, copper etc.; The foam of polyurethane foaming body, foam polyethylene etc.; The polyester film of polyethylene terephthalate, polybutylene terephthalate, PEN etc.; The cellulosefilm of polyurethane film, polyethylene film, polypropylene film, cellulosetri-acetate etc.; The plastics film of polyvinyl chloride film, polyvinylidene chloride film, PVA (PVOH) FILM, vinyl-vinyl acetate copolymer film, polystyrene film, polycarbonate film, acrylic resin films, norbornene resin film, cyclic olefin resins film etc.; These two or more duplexer etc.Plastics film can be the film of uniaxial extension or biaxial stretch-formed film.
As optical component, such as, can list polarized light piece (polarized light film), polarizer, polarizer (phase-contrast film), field angle compensation film, improve brightness film, improve contrast gradient film, liquid crystal polymer film, diffusion film, semi-transparent semi-reflecting film etc.Wherein, polarized light piece (polarized light film) easily shrinks, and dimensional change is large, therefore from the viewpoint of requiring weather resistance, and the base material of the suitable caking agent (described bond layer 11) as formation present embodiment.In addition, particularly polycyclic olefin-based film or possess the polarized light piece (COP polarized light piece) of this film, not only easily shrink, dimensional change is large, and contact angle is large, adaptation is low, therefore from the viewpoint of requiring cementability, adhesion durability, and the base material of the suitable caking agent (described bond layer 11) as formation present embodiment.
The thickness of base material 13, different according to its kind, such as, when optical component, be generally 10 μm ~ 500 μm, be preferably 50 μm ~ 300 μm, be particularly preferably 80 μm ~ 150 μm.
As stripping film 12, 12a, 12b, such as polyethylene film can be used, polypropylene film, polybutene film, polybutadiene membrane, poly-methyl pentene film, polyvinyl chloride film, vinyl chloride copolymer film, pet film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethene-(methyl) acrylic copolymer film, ethene-(methyl) acrylate copolymer film, polystyrene film, polycarbonate film, Kapton, fluorine resin film etc.In addition, these crosslinked film can also be used.Further, also can be these laminate film.
The release surface (face particularly connected with bond layer 11) of described stripping film, preferably implements lift-off processing.As the stripper that lift-off processing uses, such as, can list the stripper of alcohol acids, silicone, fluorine class, unsaturated polyester class, polyolefins, wax class.
About the thickness of stripping film 12,12a, 12b, have no particular limits, be generally 20 μm ~ about 150 μm.
For manufacturing described adhesive sheet 1A, the solution (coating solution) containing adhesive composition P is coated in the release surface of stripping film 12, and dry, after forming the film of adhesive composite P, base material 13 carry out stacked by this film.Then, through stripping film 12, active energy ray is irradiated to described film.Described film, during not needing maturation, directly becomes bond layer 11, during needs maturation, becomes bond layer 11 after during maturation.About dry and maturation condition is described above.
In addition, for manufacturing described adhesive sheet 1B, coating solution containing described adhesive composition is coated in the release surface of a stripping film 12a (or 12b), and it is dry, after forming the film of adhesive composite P, on this film, the release surface of another stripping film 12b (or 12a) is overlapping.Then, through stripping film 12a (or 12b), active energy ray is irradiated to described film.Described film, during not needing maturation, directly becomes bond layer 11, during needs maturation, becomes bond layer 11 after during maturation.
As the method for the above-mentioned coating solution of coating, such as, can utilize excellent coating method, scraper for coating method, roller coating method, plate coating method, die coating methods, gravure coating method etc.
Bond layer 11 in adhesive sheet 1A, 1B, haze value (value based on JIS K7136:2000 measures) is preferably less than 1.0%, is particularly preferably less than 0.9%, more preferably less than 0.8%.If haze value is less than 1.0%, then transparent high, be suitable for being used as optical applications.
Such as, at this, for manufacturing the liquid crystal indicator be made up of liquid crystal cells and polarized light piece, as the base material 13 of adhesive sheet 1A, use polarized light piece, the stripping film 12 of this adhesive sheet 1A is peeled off, the bond layer 11 and the liquid crystal cells that expose are carried out fitting.
Such as, in addition, for being manufactured on the liquid crystal indicator being configured with polarizer between liquid crystal cells and polarized light piece, as an example, first, adhesive sheet 1B stripping film 12a (or 12b) peeled off, the bond layer 11 and the polarizer that are exposed by adhesive sheet 1B are fitted.Then, peeled off by the stripping film 12 employing the adhesive sheet 1A of polarized light piece as base material 13, the bond layer 11 and the above-mentioned polarizer that are exposed by adhesive sheet 1A are fitted.In addition, from the bond layer 11 of above-mentioned adhesive sheet B, peeled off by another stripping film 12b (or 12a), the bond layer 11 and the liquid crystal cells that are exposed by adhesive sheet B are fitted.
According to above adhesive sheet 1A, 1B, the excellent in te pins of durability of bond layer 11, even if therefore under the high temperature conditions or under wet heat condition, also can prevent/suppress and produce between base material 13 or bonded object float, peel off, bubble etc.Particularly using base material 13 as COP polarized light piece when, also can issuable stress be absorbed by bond layer 11, is relaxed by the distortion due to COP polarized light piece, play excellent weather resistance thus.
Adhesive sheet 1A, 1B described in present embodiment, also preferred using nesa coating as bonded object.In (methyl) acrylic ester polymer (A) in adhesive composition P, the amount of the carboxyl group-containing monomer comprised as monomeric unit is a small amount of as mentioned above, therefore can suppress the detrimentally affect because sour composition brings nesa coating.Specifically, nesa coating can be suppressed to be corroded, or the resistance value of nesa coating change.
As above-mentioned nesa coating, such as, can list by the metal of platinum, gold and silver, copper etc.; The oxide compound of stannic oxide, Indium sesquioxide, Cadmium oxide, zinc oxide, zinc oxide etc.; The composite oxides of tin-doped indium oxide (ITO), Zinc oxide doped Indium sesquioxide, Fluorin doped Indium sesquioxide, antimony-doped tin oxide, fluorine-doped tin oxide, aluminium-doped zinc oxide etc.; The nesa coating that the non-oxidized compound etc. of chalkogenide, lanthanum hexaborane, titanium nitride, titanium carbide etc. is formed.
The resistance change of described nesa coating is specifically described, to adhesive sheet 1A or adhesive sheet 1B described in use present embodiment, bond layer 11 and nesa coating are fitted and the duplexer that obtains, carry out 65 DEG C, expose the damp and hot promotion test of 500 hours to the open air under the atmosphere of 95%RH time, the resistance value increment rate calculated according to following formula of nesa coating is preferably less than 15%, is particularly preferably less than 10%.
Resistance value increment rate (%)={ (R-R 0)/R 0} × 100
(in formula, R 0for the damp and hot initial resistivity value (Ω) promoted before test, R is the resistance value (Ω) after damp and hot promotion test.)
In addition, about the measuring method of the resistance value increment rate of nesa coating details as described later.
The adhesive sheet 1A employing polarized light piece as base material 13 (has the situation being called " polarized light piece with bond layer " below.), relative to the bonding force of non-alkali glass, be preferably 0.1N/25mm ~ 20N/25mm, be particularly preferably 0.5N/25mm ~ 10N/25mm, more preferably 1N/25mm ~ 5N/25mm.Bonding force by above-mentioned scope, can prevent floating or stripping etc. between the bonded object of sheet glass etc.In addition, bonding force mentioned here, substantially the bonding force by measuring based on 180 ° of stripping methods of JIS Z0237:2009 is referred to, but working sample is cut into wide 25mm, long 100mm, after making this working sample pressurization attaching for 20 minutes at 0.5MPa, at 50 DEG C relative to bonded object, normal pressure, 23 DEG C, place 24 hours under the condition of 50%RH after, carry out measuring obtained bonding force with peeling rate 300mm/min.
Embodiment described above, describes for ease of understanding the present invention, is not the description limiting the present invention and carry out.Therefore, each key element disclosed in above-mentioned embodiment, also comprises all design alterations and equipollent that belong to technical scope of the present invention.
Such as, the stripping film 12 of adhesive sheet 1A can omit, and any one in stripping film 12a, 12b in adhesive sheet 1B also can be omitted.
Embodiment
Below, further the present invention is specifically described by embodiment etc., but scope of the present invention is not by the restriction of these embodiments etc.
(embodiment 1)
1. the modulation of (methyl) acrylic ester polymer
76.9 mass parts n-butylacrylate, 10 mass parts methyl acrylate, 10 mass parts vinylformic acid 2-phenylethylesters, 3 mass parts vinylformic acid 2-hydroxyethyl esters and 0.1 mass parts acrylic acid copolymer are closed, modulation (methyl) acrylic ester polymer (A).Measured by aftermentioned method by the molecular weight being somebody's turn to do (methyl) acrylic ester polymer (A), result weight-average molecular weight is 1,500,000.
2. the modulation of adhesive composition
By 100 mass parts (solids component scaled value, as follows) at middle (methyl) acrylic ester polymer (A) obtained of above-mentioned operation (1), 0.1 mass parts is as TriMethylolPropane(TMP) modification first phenylene vulcabond (the Japanese polyurethane industrial system of isocyanates linking agent (B), trade(brand)name " CORONATE L "), 0.3 mass parts is as the 3-mercaptopropyi Trimethoxy silane of silane coupling agent (C) and cocondensation compound (chemical industrial company of the SHIN-ETSU HANTOTAI system of Union carbide A-162 with sulfydryl, trade(brand)name " X-411-1810 ", mercapto equivalents: 450g/ mole), 5 mass parts are as three (acryloyl-oxyethyl) isocyanuric acid ester (East Asia Synesis Company system of active energy ray-curable composition (D), trade(brand)name " ARONIX M-315 ", molecular weight: 423, trifunctional type), 0.5 mass parts is as mixture (Chiba speciality chemical Inc. benzophenone and 1-hydroxycyclohexylphenylketone mixed with the mass ratio of 1:1 of Photoepolymerizationinitiater initiater (E), IRGACURE500) mix, stir fully, by diluting by ethyl acetate, obtain the coating solution of adhesive composition.
At this, the cooperation of this adhesive composition is shown in table 1.In addition, the details of the dummy suffix notation described in table 1 etc. is as described below.
[(methyl) acrylic ester polymer]
BA: n-butylacrylate
MA: methyl acrylate
PhEA: vinylformic acid 2-phenylethylester
HEA: vinylformic acid 2-hydroxyethyl ester
AA: vinylformic acid
[silane coupling agent]
The cocondensation compound (chemical industrial company of SHIN-ETSU HANTOTAI system, trade(brand)name " X-411-1810 ") of C1:3-mercaptopropyi Trimethoxy silane and Union carbide A-162
C2:3-(2,3-epoxy third oxygen) propyl trimethoxy silicane (organosilicon Inc. of SHIN-ETSU HANTOTAI, trade(brand)name " KBM-403 ")
3. with the manufacture of bond layer polarized light piece
By the coating solution of obtained adhesive composition, pet film face silicone stripper is being carried out stripping film (the Lin get Ke Inc. of lift-off processing, SP-PET3811, thickness: 38 μm) lift-off processing face on, be coated with Scraper applicator, make dried thickness be 20 μm, at 90 DEG C, carry out 1 minute heat treated afterwards and form the film of adhesive composition.
Then; by a face with the polarizer that forms of cellulose triacetate film protection PVA (PVOH) FILM, to protect with cyclic olefin polymer film another face gained, thickness is that the COP polarized light piece of 100 μm and above-mentioned film are fitted, and the exposed surface of above-mentioned film is contacted with the surface of cyclic olefin polymer film.Afterwards, through stripping film according to following condition to described film irradiation ultraviolet radiation, and 23 DEG C, carry out maturation in 7 days under 50%RH, obtain the polarized light piece with bond layer thus.
< uviolizing condition >
Use FUSION Inc., Non-polarized lamp H BULB
Illumination 600mW/cm 2, light quantity 150mJ/cm 2
UV illumination quantorecorder uses EYE GRAPHICS Inc., " UVPF-36 "
(embodiment 2 ~ 13, comparative example 1 ~ 4)
Except forming the kind of each monomer of (methyl) acrylic ester polymer (A) and ratio, the weight-average molecular weight of (methyl) acrylic ester polymer (A), the use level of isocyanates linking agent (B), the kind of silane coupling agent (C) and use level, the use level of active energy ray-curable composition (D) and the use level of Photoepolymerizationinitiater initiater (E), outside changing shown in table 1, operate similarly to Example 1, manufacture the polarized light piece with bond layer.In addition, in embodiment 7, when the modulation of adhesive composition, as antistatic agent, coordinated two (trifluoromethanesulfonimide) lithium of 1.8 mass parts and tetraethyleneglycol dimethyl ether etc. mole melange (three Optical Chemical Company's systems, trade(brand)name " SANKONOL TGR ").
At this, above-mentioned weight-average molecular weight (Mw) is the weight-average molecular weight using gel permeation chromatography (GPC) to measure the polystyrene conversion of (GPC mensuration) under the following conditions.
< condition determination >
GPC determinator: TOSOH Inc., HLC-8020
GPC post (sequentially passing through by following): TOSOH Inc.
TSK?guard?column?HXL-H
TSK?gel?GMHXL(×2)
TSK?gel?G2000HXL
Measure solvent: tetrahydrofuran (THF)
Measure temperature: 40 DEG C
(test example 1) (mensuration of gel fraction)
Replace the polarized light piece that the polarized light piece that in embodiment or comparative example, making has bond layer uses, use stripping film (Lin get Ke Inc. pet film face silicone stripper having been carried out lift-off processing, SP-PET3801, thickness: 38 μm), carry out the making of adhesive sheet.Specifically, on the film exposed of the constituting body that the film of the stripping film/adhesive composition obtained in the manufacturing processed by embodiment or comparative example is formed, in the mode making side, lift-off processing face connect, above-mentioned stripping film is carried out stacked, 23 DEG C, carry out maturation in 7 days under the condition of 50%RH.Thus, the adhesive sheet formed with the structure of stripping film (SP-PET3801)/bond layer (thickness: 20 μm)/stripping film (SP-PET3811) is made.
The adhesive sheet obtained is made the sample of 80mm × 80mm size, by its bond layer polyester net (size of mesh 200) parcel, weigh the independent quality of caking agent with accurate Libra.Using quality now as M1.
Then, by the caking agent of above-mentioned polyester net parcel, under room temperature (23 DEG C), in ethyl acetate, 24 h immersion are carried out.Afterwards caking agent is taken out, under the environment of temperature 23 DEG C, relative humidity 50%, carry out 24 hours air-dry, carry out in the baking oven of 80 DEG C further 12 hours dry.The independent quality of dried caking agent is weighed with accurate Libra.Using quality now as M2.Gel fraction (%) represents with (M2/M1) × 100.Show the result in table 2.
(test example 2) (mensuration of haze value)
As working sample, prepare the adhesive sheet that the adhesive sheet used with measuring gel fraction is same.About the bond layer (thickness: 20 μm) of this adhesive sheet, use haze measurement meter (Japanese electricity Se industrial system, NDH2000), based on JIS K7136:2000, haze value (%) is measured.Show the result in table 2.
(test example 3) (mensuration of resistance value increment rate)
By the polarized light piece with bond layer obtained in embodiment or comparative example, according to following test method, measure the resistance value of ito film, calculate resistance value increment rate.
As shown in Figure 3, be the sectional view of resistance value working sample S.Prepare by sputtering at polyethylene terephthalate (PET) film 21 face 21a being provided with ito film 22, with jointing tape 24 (Lin get Ke Inc., trade(brand)name " TACKLINER TL-70 "), a face 23a of the face 21b with sheet glass 23 that PET film 21 are not arranged ito film 22 is engaged.
Then, the reverse side in the face connected with PET film 21 with ito film 22 is (hereinafter referred to as " face ".) on 22a, by the electroconductive resin material containing silver, (Teng Cang changes into Inc., trade(brand)name " FA-301CA ", DOTITE contact panel circuit type) be coated into the rectangular electrodes shape of 20mm × 5mm after, at temperature 80 DEG C, heating makes it dry for 20 minutes, forms the electrode 25 that two become resistance value measuring point.Now, adjust the position of two electrodes 25,25, make distance between it slightly larger than 20mm.
On the other hand, by the polarized light piece 1A ' with bond layer obtained in embodiment or comparative example, be cut into 20mm × 250mm size, stripping film is peeled off (now, with the polarized light piece 1A ' of bond layer, the duplexer for being made up of polarized light piece 13 ' and bond layer 11).Afterwards, with the bond layer 11 of the polarized light piece 1A ' of bond layer along the limit (just not touching with it) of two electrodes 25,25, on a face 22a of ito film 22, attach the polarized light piece 1A ' with bond layer, make resistance value test sample S as shown in Figure 3.
Afterwards, as shown in Figure 4, utilize digital multimeter (Zhi Motor Corporation system, trade(brand)name " 3802-50 ") 30, measure the initial resistivity value R between electrode 25,25 0(Ω).And by resistance value test sample S 60 DEG C, place 500 hours under the environment of 90%RH after, measure the resistance value R (Ω) after damp and hot promotion.According to obtained initial resistivity value R 0and the resistance value R after damp and hot promotion, calculate the resistance value increment rate of resistance value test sample S as follows.Show the result in table 2.
Resistance value increment rate (%)={ (R-R 0)/R 0} × 100
(test example 4) (durability evaluation)
By the polarized light piece severing with bond layer obtained in embodiment or comparative example, make the sample of 200mm × 150mm size.From this sample, stripping film is peeled off, by the bond layer exposed, after non-alkali glass (corning Inc., Eagle XG) attaches, with the autoclave that the former making of chestnut is made, in 0.5MPa, pressurization 20 minutes at 50 DEG C.
Afterwards, put in the environment of following durable condition, after 250 hours, utilize 10 times of magnifying glasses, confirm with or without floating or peeling off.Metewand is as follows.Show the result in table 2.
◎: do not confirm and float or peel off.
Zero: confirm and be less than or equal to floating or peeling off of 0.5mm size.
△: confirm and be greater than 0.5mm and be less than or equal to floating of 1.0mm size or peel off.
×: confirm and be greater than floating or peeling off of 1.0mm size.
The durable condition > of <
85 DEG C of dryings
60 DEG C, relative humidity 90%RH
(test example 5) (mensuration of the sheet resistance value of bond layer)
The polarized light piece with bond layer obtained in embodiment 7 is cut into 50mm × 50mm size, obtained sample is placed 24 hours under temperature 23 DEG C, humidity 50%RH.Afterwards, stripping film is peeled off, to the bond layer surface of exposing, with resistivity meter (analytical technology Inc. of Mitsubishi Chemical, HIRESTA UP MCP-HT450 type), based on JISK6911, measure sheet resistance value (Ω/sq).Show the result in table 2.
In addition, sheet resistance value is preferably 3.0 × 10 11Ω/below sq, is particularly preferably 1.0 × 10 11Ω/below sq, more preferably 8.0 × 10 10Ω/below sq.By making sheet resistance value below above-mentioned value, good static electricity resistance can be played.
(test example 6) (mensuration of storage modulus)
As working sample, the adhesive sheet that the adhesive sheet preparing to use in measuring with gel fraction is same.To the bond layer (thickness: 20 μm) of this adhesive sheet, this bond layer stacked, makes the cylindric test film of diameter 8mm × thickness 3mm, measures storage modulus (G ') under the following conditions according to turning round the method for cutting.Show the result in table 2.
Determinator: Rheometric Inc., Measurement of Dynamic Viscoelasticity device " DYNAMICANALYZER RDAII "
Frequency: 1Hz
Temperature: 23 DEG C and 80 DEG C
Table 1
Table 2
As shown in Table 2, the caking agent of the bond layer obtained in embodiment is while excellent in te pins of durability, and the resistance value as the nesa coating of bonded object is not easily changed.
Industrial utilizability
Caking agent of the present invention and adhesive sheet, be suitable for nesa coating, the nesa coating that is particularly made up of tin-doped indium oxide (ITO) be bonding with optical component, particularly polarized light piece.
Description of reference numerals
1A, 1B ... adhesive sheet
1A ' ... with the polarized light piece of bond layer
11 ... bond layer
12,12a, 12b ... stripping film
13 ... base material
13 ' ... polarized light piece
21 ... PET film
21a, 21b ... face
22 ... ito film
22a ... face
23 ... sheet glass
23a ... face
24 ... jointing tape
25 ... electrode
30 ... digital multimeter
S ... resistance value test sample

Claims (16)

1. an adhesive composition, it contains:
(methyl) acrylic ester polymer (A), weight-average molecular weight is 1,000,000 ~ 2,500,000, as forming the monomeric unit of polymkeric substance, containing have hydroxyl monomer, have aromatic nucleus monomer and have carboxyl monomer,
Isocyanates linking agent (B),
Have sulfydryl silane coupling agent (C) and
Active energy ray-curable composition (D);
Described (methyl) acrylic ester polymer (A), as the monomeric unit forming this polymkeric substance, containing the monomer described in 1 quality % ~ 5 quality % with hydroxyl, containing the monomer described in 5 quality % ~ 30 quality % with aromatic nucleus, containing the monomer described in 0.1 quality % ~ 0.8 quality % with carboxyl.
2. adhesive composition according to claim 1, is characterized in that, described isocyanates linking agent (B) is TriMethylolPropane(TMP) modification first phenylene vulcabond.
3. adhesive composition according to claim 1, it is characterized in that, in described adhesive composition, the content of described isocyanates linking agent (B), relative to (methyl) acrylic ester polymer (A) described in 100 mass parts, it is 0.01 mass parts ~ 1 mass parts.
4. adhesive composition according to claim 1, it is characterized in that, in described adhesive composition, the content of described silane coupling agent (C), relative to (methyl) acrylic ester polymer (A) described in 100 mass parts, it is 0.01 mass parts ~ 0.5 mass parts.
5. adhesive composition according to claim 1, is characterized in that, described in there is aromatic nucleus monomer be (methyl) vinylformic acid 2-phenylethylester.
6. adhesive composition according to claim 1, is characterized in that, described active energy ray-curable composition (D) is less than the polyfunctional acrylic ester class monomer of 1000 for molecular weight.
7. adhesive composition according to claim 6, is characterized in that, described polyfunctional acrylic ester class monomer has ring texture.
8. adhesive composition according to claim 1, it is characterized in that, in described adhesive composition, the content of described active energy ray-curable composition (D), relative to (methyl) acrylic ester polymer (A) described in 100 mass parts, it is 1 mass parts ~ 50 mass parts.
9. a caking agent, the adhesive composition solidification in claim 1 ~ claim 8 described in any one forms by irradiating active energy ray by it.
10. caking agent according to claim 9, is characterized in that, gel fraction is 55% ~ 85%.
11. caking agents according to claim 9, is characterized in that, the storage modulus at 23 DEG C is 0.15MPa ~ 0.3MPa, and the storage modulus at 80 DEG C is 0.05MPa ~ 0.2MPa.
12. 1 kinds of adhesive sheets, is characterized in that,
Possess base material and bond layer,
Described bond layer contains caking agent described in claim 9.
13. adhesive sheets according to claim 12, is characterized in that, described base material is optical component.
14. adhesive sheets according to claim 13, is characterized in that, described optical component is polarized light piece.
15. 1 kinds of adhesive sheets, it is characterized in that, it possesses:
Two panels stripping film, and
With the bond layer that the mode connected with the release surface of described two panels stripping film is clamped by described stripping film;
Described bond layer contains caking agent described in claim 9.
16. adhesive sheets according to claim 12, it is characterized in that, to the duplexer of described bond layer and nesa coating, carry out 65 DEG C, expose the damp and hot promotion test of 500 hours to the open air under the atmosphere of 95%RH time, the resistance value increment rate calculated according to following formula of described nesa coating is less than 15%
Resistance value increment rate (%)={ (R-R 0)/R 0} × 100
In formula, R 0for the damp and hot initial resistivity value promoted before test, R is the resistance value after damp and hot promotion test.
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