CN104231981A - Adhesive, adhesive sheet and displayer - Google Patents

Abstract

The invention aims to provide an adhesive having excellent adhesiveness, transparency, non whitening, foaming resistance and peeling resistance and also having a step difference tracing ability. The adhesive contains an acrylic copolymer (A), a polyisocyanate curing agent (B) and a silane coupling agent (C), wherein the acrylic copolymer (A) is formed through free radical polymerization of 20-90 wt% of an ethylenically unsaturated monomer (A1) having the SP value of 8 or more and less than 9.00 and having alkyl, and 10-80 wt% of an ethylenically unsaturated monomer (A2) having the SP value of 9.00 or more and 15 or less and having polar groups, and is a polymer with the weight average molecular weight of 200000-1000000; the ethylenically unsaturated monomer (A2) has more than one polar group selected from the group consisting of hydroxyl (a1), amide (a2), amino (a3) and nitrile (a4), and the glass transition temperature (Tg) of the homopolymer is -40 DEG C or more and 120 DEG C or less.

Description

Tackiness agent, adhesive sheet and indicating meter

Technical field

The present invention relates to tackiness agent.Further, the adhesive sheet using described tackiness agent to be formed and indicating meter is related to.

Background technology

Along with the leap progress of electronic technology in recent years, the various flat-panel monitors (FPD) such as liquid-crystal display (LCD), plasma display (PDP), rear projection display (RPJ), EL indicating meter, light emitting diode indicator are widely used as display unit.In this display unit, usually employ for preventing the anti-reflective film of the reflection produced by external light source, for preventing the various films such as the protective membrane (protective film) of display unit galled spots.Such as, light polarizing film or phase retardation film is employed in the liquid crystal cell parts used in an lcd.

Further, FPD is also used as the input unit as touch-screen etc.In touch-screen, usually employ protective membrane, anti-reflective film and ELD etc.These films use tackiness agent (being also referred to as " pressure-sensitive adhesives ") to paste usually.

For the tackiness agent used in touch-screen purposes, except requiring binding property, the transparency, when also requiring at high temperature and use in high humidity environment binder layer do not produce bubble (resistance to foaminess), each film of pasting do not float or peel off (peel resistance), binder layer do not bleach (non-whitening resistance) and do not corrode the character (non-aggressive) of transparency electrode.Further, owing to there is the step difference because the circuit on base material causes on the transparent electrodes, the performance of the character (step difference tracing ability) being embedded into this step difference with binder layer etc. when therefore bonding adhesive sheet on the transparent electrodes, is needed to have.

Touch-screen is normally formed based on LCD, and uses tackiness agent on liquid crystal cell, pasted Polarizer.As the tackiness agent of Polarizer, even if need also with Polarizer at high temperature and when using in the severe rugged environment of high humidity can not peel off from liquid crystal cell or produce the performance floated, and do not reveal the performance (non-light leak) of the light that liquid crystal cell is not expected.The reason producing this light leakage phenomenon is, at high temperature and when using in high humidity environment, the stress that the dimensional change because of Polarizer contraction or expansion produces can not get buffering at binder layer, thus retains the cause of the residual stress being derived from Polarizer.

Further, because touch-screen is used in the portable data assistance of smart mobile phone etc., therefore consider that the shock-resistance of problems such as dropping is also very important.Therefore, usually use at the upper layer of touch-screen the plastic film that the transparency of polycarbonate (PC), polymethylmethacrylate (PMMA) or cycloolefin (COP) etc. is high.But transparent high plastics, because material is hard, flexibility is poor, therefore need to obtain desired flexibility, workability and plasticity by mixing a large amount of softening agent.But, between this plastic film and binder layer, when be result in be used touch-screen by this softening agent in hot environment, produce the problem of gas (being also referred to as " venting ").

For above-mentioned problem, in order to improve resistance to foaminess and peel resistance, there will be a known the method etc. that copolymerization contains the method for the monomer of the functional groups such as carboxyl, the high monomer (high Tg monomer) of second-order transition temperature (Tg) of mixing homopolymer and/or the oligomer (low-molecular weight polymer) of high Tg.Further, in order to improve non-whitening resistance and non-aggressive, there will be a known the method that crosslinkable functional acrylate beyond by carboxyl and alkoxyalkyl acrylate carry out copolymerization.Further, in order to prevent venting, there will be a known and add the method for tackifier or the method for hybrid metal couplings.

Specifically, there will be a known a kind of tackiness agent, contain (methyl) alkoxyalkyl acrylate as main component in this tackiness agent, and the carboxylic monomer of copolymerization wherein and binding property polymer 100 weight part obtained, alkyl methacrylate will be selected from, cycloalkyl methacrylate, benzyl methacrylate or one or more monomer cinnamic are as main component, and low-molecular weight polymer 5 ~ 40 weight part that copolymerization wherein obtains containing the monomer of amino or amide group, and linking agent 0.001 ~ 2.0 weight part (with reference to patent documentation 1).

And, there will be a known a kind of metal adhesive sheet for bonding, employ in this metal adhesive sheet for bonding using carboxylic monomer as neccessary composition and by the acrylic copolymer of monomer in fact not containing hydroxyl and benzotriazole or derivatives thereof with specified weight than the tackiness agent carrying out mixing, and by have can carry out the functional group of reacting with the carboxyl in described acrylic copolymer epoxy crosslinking agent with specified weight than carrying out mixing and the tackiness agent being cross-linked and obtaining (reference patent documentation 2).

And, there will be a known a kind of tackiness agent, be mixed with alkoxyalkyl acrylate as main component in this tackiness agent, and the carboxylic monomer of copolymerization wherein 0.1 ~ 10 % by weight and binding property polymer 100 weight part of weight-average molecular weight more than 600,000 obtained, alkyl methacrylate will be selected from, cycloalkyl methacrylate, benzyl methacrylate or cinnamic monomer are as main component, and the second-order transition temperature obtained containing the monomer of amino or the monomer of amide-containing of copolymerization wherein 0.5 ~ 10 % by weight is more than 60 DEG C, and low-molecular weight polymer 5 ~ 40 weight part of weight-average molecular weight below 50,000, and linking agent 0.001 ~ 2.0 weight part (with reference to patent documentation 3).

And, there will be a known a kind of transparent double-sided adhesive tape formed by the tackiness agent being mixed with acrylic polymers and oligomer, described acrylic polymers is the carbonatoms containing the alkyl of more than 50 % by weight relative to whole monomer component is the acrylate monomer of 4 ~ 12, and the carboxylic monomer as monomer component of 3 ~ 10 weight parts is contained relative to whole monomer components of 100 weight parts, and weight-average molecular weight is 500,000 ~ 900,000, second-order transition temperature when described oligomer is the formation homopolymer containing more than 50 % by weight relative to whole monomer component is 60 ~ 190 DEG C and has the ethylene unsaturated monomer of ring texture, and the carboxylic monomer as monomer component of 3 ~ 10 weight parts is contained relative to whole monomer components of 100 weight parts, and weight-average molecular weight is that 3000 ~ 6000(is with reference to patent documentation 4).

Moreover, there will be a known a kind of tackiness agent, the acrylic polymers of this tackiness agent for containing the weight-average molecular weight of carrying out being polymerized as neccessary composition using alkoxyalkyl acrylate (composition A) and the acrylic monomer (composition B) with crosslinkable functional group being 400,000 ~ 1,600,000, with the tackiness agent of linking agent, wherein, relative to whole monomer components 100 weight part forming acrylic polymers, the content of composition A is 45 ~ 99.5 weight parts, the content of composition B is 0.5 ~ 4.5 weight part, and form in the monomer component of acrylic polymers in fact not containing carboxylic monomer (with reference to patent documentation 5).

And, there will be a known a kind of transparent pressure-sensitive adhesive sheet, this transparent pressure-sensitive adhesive sheet by be the acrylate monomer (composition A) of 4 ~ 18 by the carbonatoms of alkyl, the acrylate monomer (composition B) of amide-containing and alkoxyalkyl acrylate carry out copolymerization and obtain, and acid number is at below 5mg KOH/g (with reference to patent documentation 6).

And, there will be a known a kind of tackiness agent, this tackiness agent is for carrying out copolymerization and the acrylic polymers obtained by alkoxyalkyl acrylate monomer (composition A) 45 ~ 99.5 weight parts, acrylate monomer 0.5 ~ 4.5 weight part with hydroxyl, the percent gel of this acrylic polymers after forming crosslinking structure is 40 ~ 80%, and in fact not containing carboxylic monomer (with reference to patent documentation 7).

And, there will be a known a kind of tackiness agent, this tackiness agent is for the purpose of the venting suppressing adherend, by tackifier 0.5 ~ 15 weight part relative to acrylic polymers 100 weight part benzene mixed vinyl or alpha-methyl styrene class in acrylic polymers, and isocyanates linking agent is utilized to carry out being cross-linked to be formed (with reference to patent documentation 8).

And, there will be a known a kind of tackiness agent, this tackiness agent is for the purpose of the venting suppressing adherend, formed by mixing acrylic copolymer and metal couplings, described acrylic copolymer is contain the butyl acrylate of 40 ~ 99 weight parts or ethyl propenoate or their mixture (composition A) relative to whole monomer, the α of 1 ~ 15 weight part, β-ethylene type unsaturated carboxylic acid (composition B), and the methyl acrylate of 0 ~ 55 % by weight, methyl methacrylate, vinyl cyanide or vinylbenzene or their mixture (composition C), and weight-average molecular weight is the acrylic copolymer of more than 400,000, described metal couplings is 0.5 ~ 2.0 weight part (with reference to patent documentation 9) relative to described acrylic copolymer 100 weight part.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2002-327160 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2006-45315 publication

Patent documentation 3: Japanese Patent No. 4788937 publication

Patent documentation 4: Japanese Patent No. 4515118 publication

Patent documentation 5: Japanese Unexamined Patent Publication 2009-79203 publication

Patent documentation 6: Japanese Unexamined Patent Publication 2011-74308 publication

Patent documentation 7: Japanese Unexamined Patent Publication 2010-215923 publication

Patent documentation 8: Japanese Patent No. 4437631 publication

Patent documentation 9: Japanese Unexamined Patent Publication 6-49425 publication

Summary of the invention

The problem that invention will solve

But due to the existence of carboxyl, there is the problem of corroding metal in the tackiness agent of patent documentation 1 and 2.

Further, due to low with the adaptation of base material film, tackiness agent poor performance in resistance to foaminess and peel resistance of patent documentation 3 and 4.Moreover, due to low with the adhesivity of transparency electrode, so there is the problem of step difference tracing ability difference in this tackiness agent.

Further, although the tackiness agent of patent documentation 5,6 and 7 uses alkoxyalkyl acrylate to seek to improve non-whitening resistance, there is it and improve the low problem of non-whitening resistance level.Further, owing to being easy to remain polymerization starter in the adhesive, the alkoxyalkyl therefore in polymkeric substance is easy to decompose, thus there is the problem of resistance to foaminess and peel resistance difference.Moreover, due to the Tg of used alkoxyalkyl acrylate low (generally below-45 DEG C), so the cohesive force that there is tackiness agent is low and bond hypodynamic problem.

Further, the tackiness agent of patent documentation 8 be in high temperature and the environment of high humidity time, because the tackifier be blended in tackiness agent ooze out, therefore cannot guarantee the performance of resistance to foaminess and peel resistance aspect.Moreover, exist because this oozes out the problem causing polluting.Further, due to the existence of metal couplings, there is the problem that metal is corroded in the tackiness agent of patent documentation 9.

In view of above problem, the object of the present invention is to provide binding property, the transparency, non-whitening resistance, resistance to foaminess and peel resistance excellent, and with the tackiness agent of step difference tracing ability, adhesive sheet and indicating meter.

The method of dealing with problems

Tackiness agent of the present invention contains acrylic copolymer (A), polymeric polyisocyanate class solidifying agent (B) and silane coupling agent (C), described acrylic copolymer (A) be more than 8 by radical polymerization SP value and be less than 9.00 the ethylene unsaturated monomer (A1) 20 ~ 90 % by weight with alkyl and SP value be less than more than 9.00 15 the ethylene unsaturated monomer (A2) 10 ~ 80 % by weight with polar group formed.And, the described ethylene unsaturated monomer (A2) with polar group has more than one polar groups in the group selecting free hydroxyl (a1), amide group (a2), amino (a3) and itrile group (a4) to form, and the second-order transition temperature (Tg) of homopolymer is set as more than-40 DEG C less than 120 DEG C.Here, SP value refers to solubility parameter.Further, acrylic copolymer (A) for weight-average molecular weight be more than 200,000,1,000,000 polymkeric substance.

The effect of invention

According to the present invention of above-mentioned formation, the SP value of the ethylene unsaturated monomer (A2) with polar group used in acrylic copolymer (A) synthesis more than 9.00 less than 15 high scope.Further, use the acrylic copolymer of this monomer (A2) (A) affinity to water high.After tackiness agent is processed into adhesive tape, be placed on high temperature such as, on the sheet glass pasting liquid crystal cell after and in the environment of high humidity time, water can be immersed in binder layer.But, because binder layer contains the multipolymer (A) employing the high monomer (A2) of a large amount of SP value, therefore high with the affinity of water.Thus transparent binder layer is not easy to bleach, therefore non-whitening resistance excellence.That is, in the present invention, water is made suitably to be immersed in binder layer.Further, because this binder layer contains polar group, though be therefore placed on high temperature and in the environment of high humidity time bounding force be also not easy to reduce, therefore peel resistance is excellent, and is not easy to produce bubble due to binder layer, and therefore resistance to foaminess is excellent.Moreover step difference tracing ability is also excellent.In addition, high temperature and the environment of high humidity refers to the environment that temperature is high, humidity is also high.

According to the present invention, binding property, the transparency, non-whitening resistance, resistance to foaminess and peel resistance can be provided excellent, and with the tackiness agent of step difference tracing ability, adhesive sheet and indicating meter.

Embodiment

As tackiness agent of the present invention, be at least mixed with acrylic copolymer (A), polymeric polyisocyanate class solidifying agent (B) and silane coupling agent (C).

Acrylic copolymer (A) be more than 8 by radical polymerization SP value and be less than 9.00 the ethylene unsaturated monomer (A1) 20 ~ 90 % by weight with alkyl and SP value be less than more than 9.00 15 the ethylene unsaturated monomer (A2) 10 ~ 80 % by weight with polar group obtain.

As tackiness agent of the present invention, by acrylic copolymer (A) synthesis in use SP value be less than more than 9.00 15 the ethylene unsaturated monomer (A2) 10 ~ 80 % by weight with polar group, binding property and peel resistance are improved, and are non-to be whitening resistancely improved especially.As this reason, can enumerate and use acrylic copolymer (A) affinity to water of this monomer high.And, after tackiness agent of the present invention is processed into adhesive tape, such as, on the sheet glass pasting liquid crystal cell and be placed on high temperature and in the environment of high humidity time, although water can be immersed in binder layer, but it is due to the multipolymer (A) containing the high monomer (A2) of the SP value employing specified quantitative, therefore high with the affinity of water.Thus transparent binder layer is not easy to bleach, therefore non-whitening resistance excellence.That is, in the present invention, water is made suitably to be immersed in binder layer.Further, because this binder layer contains polar group, though be therefore placed on high temperature and in the environment of high humidity time bounding force be also not easy to reduce, therefore peel resistance is excellent.And because binder layer is not easy to produce bubble, therefore resistance to foaminess is excellent.Moreover step difference tracing ability is also excellent.As polar group, preferred hydroxyl (a1), amide group (a2), amino (a3), itrile group (a4) and carboxyl (a5).

In the present invention, SP value is solubility parameter.This SP value with reference to the algorithm of Fedors [" Polymer Engineering and Science ", the 14th volume, No. 2 (1974), 148 ~ 154 pages], can calculate according to following mathematical expression 1 and obtains.

$\mathrm{\δ}={\left(\frac{\underset{i}{\mathrm{\Σ}}\mathrm{\Δei}}{\underset{i}{\mathrm{\Σ}}\mathrm{\Δvi}}\right)}^{\frac{1}{2}}\·\·\·$ (formula 1)

In formula, δ is solubility parameter (SP value), and Δ ei is mole vaporization heat, and Δ vi is molecular volume, and the unit of solubility parameter is here (cal/cm ³) ^0.5.

For above-mentioned formula 1, list in Table 1 and be imparted into the Δ ei of main atom or atomic group and the proper value of Δ vi.

[table 1]

Atom or atomic group	Δei(cal/mol)	Δvi(cm 3/mol)
			C	350	-19.2
-CH 2-	1180	16.1
			-CH 3	1125	33.5
CH 2=	1030	28.5
			-CH=	1030	13.5
Phenyl	7630	71.4
			-O-	800	3.8
-CO-	4150	10.8
			-COO-	4300	18.0
-OH	7120	10.0
			-CONH 2	10000	17.5
-CONH-	8000	9.5
			-NH 2	3000	19.2
-NH-	2000	4.5
			-CN	6100	24.0
-COOH	6600	28.5
			Si	810	0.0
F	1000	18.0
			Cl	2760	24.0

In table 1, Δ ei is mole vaporization heat (cal/mol), Δ vi is molecular volume (cm ³/ mol).

Further, the solubility parameter (SP value) of the principal monomer calculated according to above-mentioned formula and the second-order transition temperature of homopolymer is listed in table 2.

[table 2]

As the ethylene unsaturated monomer (A2) [following, to be referred to as monomer (A2)] with polar group that SP value is less than more than 9.00 15, such as, can enumerate (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-3-hydroxy propyl ester, (methyl) vinylformic acid-2-hydroxybutyl, (methyl) vinylformic acid-3-hydroxybutyl, the ethylene unsaturated monomer (a1) of the hydroxyl of (methyl) hydroxyalkyl acrylates of (methyl) vinylformic acid-4-hydroxybutyl etc. etc., (methyl) acrylamide, N hydroxymethyl acrylamide, N, N-dimethyl (methyl) acrylamide, diacetone (methyl) acrylamide, N-vinyl acetamide, the ethylene unsaturated monomer (a2) of the amide-containings such as NVP, amino methyl (methyl) acrylate, dimethylaminomethyl (methyl) acrylate, dimethyl aminoethyl (methyl) acrylate, the ethylene unsaturated monomer (a3) containing amino of dimethylaminopropyl (methyl) acrylate etc., vinyl cyanide, the ethylene unsaturated monomer (a4) of the nitrile group-containing of methacrylonitrile etc., (methyl) vinylformic acid, phthalic acid monohydroxy ethyl propylene acid esters, to carboxybenzyl acrylate, the addition mole number of oxyethane is the phthalic acid acrylate of 2 ~ 18, phthalic acid monohydroxy propyl acrylate, mono succinate hydroxyethylmethacry,ate, vinylformic acid-2-carboxyethyl, 2-(4-benzoyl-3-hydroxyphenoxy) ethyl propylene acid esters, toxilic acid, ethyl maleate, methylene-succinic acid, methyl-maleic acid, and the carboxylic ethylene unsaturated monomer (a5) etc. such as FUMARIC ACID TECH GRADE.These monomers both may be used singly or in combination of two or more use.In these monomers, based on the viewpoint of non-whitening resistance, resistance to foaminess and peel resistance, the ethylene unsaturated monomer (a1) of preferred hydroxyl, the ethylene unsaturated monomer (a2) of amide-containing and the ethylene unsaturated monomer (a3) containing amino, particularly, the ethylene unsaturated monomer (a1) of further preferably hydroxyl.In addition, although do not exist in above-mentioned enumerating, the monomer of SP value less than 15 scopes more than 9.00 when calculating according to the calculation formula of mathematical expression 1 can be used.

Further, as monomer (A2), the preferably second-order transition temperature (Tg) of its homopolymer more than-40 DEG C less than 120 DEG C.When the second-order transition temperature (Tg) of homopolymer is in described scope, bounding force and peel resistance can be further improved.The second-order transition temperature (Tg) of homopolymer preferred more than-30 DEG C less than 100 DEG C further.

In the present invention, the second-order transition temperature (Tg) of the homopolymer of monomer (A2) with reference to " polymer handbook " the 4th edition (Polymer Handbook that J.Brandrup, E.H.Immergut and E.A.Grulke write, Fourth Edition, 1999).

In whole monomer 100 % by weight, preferably use monomer (A2) with 10 ~ 80 % by weight.By using monomer (A2) with 10 ~ 80 % by weight, to be non-ly whitening resistancely improved, and binding property and peel resistance are also improved.Further, preferred with 20 ~ 60 % by weight uses monomer (A2) further.

In the synthesis of acrylic copolymer (A), preferably beyond monomer (A2), use SP values more than 8 with 20 ~ 90 % by weight and be less than 9.00 the ethylene unsaturated monomer (A1) with alkyl.When SP value is more than 8 and is less than the scope of 9.00, because the polarity of acrylic copolymer (A) is suitable for, therefore, it is possible to improve the binding property for metal, glass, adherend that plastics isopolarity is high, thus peel resistance is improved, and to be non-ly whitening resistancely also improved.

In the present invention, as monomer (A1), such as, the carbonatoms of preferred alkyl is (methyl) alkyl acrylate monomer of 1 ~ 20.Specifically, include, for example (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) amyl acrylate, (methyl) Ethyl acrylate, (methyl) cyclohexyl acrylate, (methyl) ethyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) vinylformic acid tetradecyl ester, (methyl) aliphatic acrylate, (methyl) octadecyl acrylate, and (methyl) cyclohexyl acrylate, (methyl) acrylate base ester etc. of the different camphyl ester of (methyl) vinylformic acid etc.These monomers both may be used singly or in combination of two or more use.In these monomers, particularly (methyl) butyl acrylate and (methyl) ethyl acrylate, due to can obtain appropriateness binding property and owing to easily regulating weight-average molecular weight, therefore more preferred.

Preferably in whole monomer 100 % by weight, use monomer (A1) with 20 ~ 90 % by weight.By using monomer (A1) with 20 ~ 90 % by weight, the acrylic copolymer (A) being in suitable weight average molecular weight range can be synthesized, and peel resistance and non-ly whitening resistancely can be improved further.As the usage quantity of monomer (A1), more preferably 40 ~ 80 % by weight.

In the present invention, in the scope not damaging invention effect, other ethylene unsaturated monomers can be used.Specifically, the ethylene unsaturated monomer containing alkylene oxygen base of (methyl) methoxyethyl acrylate, (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, oxyethyl group polyoxyethylene glycol (methyl) acrylate, phenoxy group polyoxyethylene glycol (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate etc. can be enumerated, and the vinyl monomer of vinyl acetate, vinyl crotonate, vinylbenzene etc.These monomers both may be used singly or in combination of two or more use.

In addition, the acrylic polymers in the present invention refers to the polymkeric substance of the ethylene unsaturated monomer containing (methyl) acrylate monomer.In addition, in the present invention, (methyl) acrylate monomer refers to both acrylate monomer and methacrylate monomer.Other similar terms are also same.Further, polymkeric substance refers to both " homopolymer " and " multipolymer ".

In the present invention, the synthesizing propylene acid copolymers (A) such as solution polymerization, emulsion polymerization, suspension polymerization can be passed through.In these coincidence method, based on the transparency and fusible viewpoint, preferred solution is polymerized.Further, the weight-average molecular weight of preferred acrylic copolymer (A) is 200,000 ~ 1,000,000.By weight-average molecular weight being controlled in described scope, binding property and peel resistance can be improved further.Further, further preferable weight-average molecular weight is 400,000 ~ 800,000.As acrylic copolymer (A), also the multipolymer that two or more weight-average molecular weight is different can be used.

Further, the weight-average molecular weight (Mw) of expression acrylic copolymer (A) and the molecular weight distribution (Mw/Mn) of number-average molecular weight (Mn) ratio are preferably below 20.By controlling below 20 by this molecular weight distribution, binding property and peel resistance can be improved further.In addition, weight-average molecular weight and number-average molecular weight are carry out by gel permeation chromatography (GPC) the polystyrene conversion value that measures.

As acrylic copolymer (A), obtain through radical polymerization ethylene unsaturated monomer by using radical polymerization initiator.During radical polymerization employing solution polymerization, such as, be preferably polymerized under the solvent of ethyl acetate, toluene, dimethylbenzene, methyl-phenoxide, methylethylketone, pimelinketone etc. exists.Preferred radical polymerization temperature is the scope of 60 ~ 120 DEG C, and the preferred polymeric time is 5 ~ 12 hours.

Known initiator can be used as radical polymerization initiator, as long as but the compound of free radical can be produced under conditions of polymerization temperature vary, just there is no special restriction.Such as, ditertiary butyl peroxide can be enumerated, diisopropylbenzyl superoxide, tert butyl isopropyl benzene peroxide, α, α '-bis-(a t-butylperoxy-sec.-propyl) benzene, the dialkyl peroxide class of 2,5-bis-(t-butylperoxy) hexin-3 grade, t-butylperoxybenzoate, t-butyl peroxy yl acetate, the peroxy ester class of 2,5-dimethyl-2,5-bis-(benzoylperoxy) hexane etc., Cyclohexanone peroxides, 3,3,5-trimethyl hexanone peroxide, the ketone peroxide class of methyl cyclohexanone peroxide etc., two (4, the 4-di-t-butyl peroxy cyclohexyl) propane of 2,2-, 1,1-bis(t-butylperoxy) 3,3,5-trimethyl-cyclohexane, 1,1-bis(t-butylperoxy) cyclohexane, the peroxy ketal class of normal-butyl-4,4-bis(t-butylperoxy) trimethylacetic acid ester etc., isopropyl benzene hydroperoxide, diisopropylbenzenehydroperoxide, the hydroperoxide type of 2,5-dimethyl cyclohexane-2,5-diperoxy hydrogen etc., benzoyl peroxide, decanol peroxide, lauroyl peroxide, the diacyl peroxide class of 2,4 dichloro benzene formyl radical superoxide etc., the organo-peroxide of the peroxy dicarboxylic ester class of two (tert-butylcyclohexyl) peroxy dicarboxylic ester etc. etc., or their mixture.

Further, also azo-compound can be used as radical polymerization initiator.Exemplarily, as can 2 be used, 2 '-azobis isobutyronitrile (referred to as AIBN), 2,2 of 2 '-azo two (2-methylbutyronitrile) etc., the two butyronitrile class of 2 '-azo, 2, two (the 4-methoxyl group-2 of 2 '-azo, 4-methyl pentane nitrile), 2, the two valeronitrile class of 2,2 '-azo of 2 '-azo two (2,4-methyl pentane nitrile) etc., 2, the two propionitrile class of 2,2 '-azo of 2 '-azo two (2-hydroxymethyl propionitrile) etc., 1, two-1-alkane the nitriles of 1,1 '-azo etc. of 1 '-azo two (hexanaphthene-1-formonitrile HCN) etc.

Relative to ethylene unsaturated monomer 100 weight part, radical polymerization initiator preferably uses 0.01 ~ 10 weight part, preferably uses 0.1 ~ 2 weight part further.

In the present invention, polymeric polyisocyanate class solidifying agent (B) preferably have plural isocyanato, aromatic poly-isocyanate, aliphatic polymeric isocyanate, aromatic-aliphatic polymeric polyisocyanate and alicyclic polymeric isocyanate etc.

As aromatic poly-isocyanate, such as, can 1 be enumerated, 3-phenylene vulcabond, 4,4 '-diphenyl diisocyanate, Isosorbide-5-Nitrae-phenylene vulcabond, 4,4 '-diphenylmethanediisocyanate, 2,4-toluylene diisocya-nate, 2,6-toluylene diisocya-nate, 4,4 '-tolidine diisocyanate, 2,4,6-tri-TI, 1,3,5-tri-phenylcarbimide, dianisidine diisocyanate, 4,4 '-diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate etc.

As aliphatic polymeric isocyanate, such as, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (another name is HMDI), pentamethylene diisocyanate, 1 can be enumerated, 2-trimethylene diisocyanate, 2,3-tetramethylene diisocyanate, 1,3-tetramethylene diisocyanate, ten dimethylene diisocyanates, 2,4,4-trimethyl hexamethylene diisocyanates etc.

As aromatic-aliphatic polymeric polyisocyanate, such as, ω can be enumerated, ω '-vulcabond-1,3-dimethyl benzene, ω, ω '-vulcabond-1,4-dimethyl benzene, ω, ω '-vulcabond-Isosorbide-5-Nitrae-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate etc.

As alicyclic polymeric isocyanate, such as, 3-isocyanic ester methylene-3 can be enumerated, 5,5-trimethylcyclohexylisocyanate (another name is IPDI, isophorone diisocyanate), 1,3-pentamethylene vulcabond, 1,3-cyclohexyl diisocyanate, 1,4-cyclohexyl diisocyanate, methyl-2,4-cyclohexyl diisocyanate, methyl-2,6-cyclohexyl diisocyanate, 4,4 '-methylene-bis (cyclohexyl isocyanate), Isosorbide-5-Nitrae-bis-(isocyanic ester methylene) hexanaphthene etc.

Further, the biuret compound of above-mentioned polymeric polyisocyanate, trimerization compound and adducts etc. can be enumerated.

The self-condensation thing of what biuret compound was formed after referring to above-mentioned isocyanate-monomer self-condensation have biuret key, such as, the biuret compound (Sumidur N-75, firmly change Baeyer Polyurethane Inc., Duranate24A-90CX, Asahi Kasei Corporation's system) etc. of hexamethylene diisocyanate can be enumerated.

Trimerization compound refers to the tripolymer of above-mentioned isocyanate-monomer, such as, tripolymer (the Sumidur N-3300 of hexamethylene diisocyanate can be enumerated, live to change Baeyer Polyurethane Inc., Coronate HX, Japanese polyurethane industrial system, Aquanate100, Japanese polyurethane industrial system, Aquanate110, Japanese polyurethane industrial system, Duranate TPA100, Asahi Kasei Corporation's system), tripolymer (the VESTANAT T-1890 of isophorone diisocyanate, Evonik Degussa Japanese firm system, Desmodur Z-4370, live to change Baeyer Polyurethane Inc.), tripolymer (the Coronate2030 of toluylene diisocya-nate, Japanese polyurethane industrial system) etc.

Adducts is that the compound reaction of instigating above-mentioned isocyanate-monomer and low molecule to contain active hydrogen is formed, isocyanate compound more than difunctionality, such as, as the isocyanate compound of three-functionality-degree, can enumerate and make TriMethylolPropane(TMP) and hexamethylene diisocyanate react compound (the Coronate HL formed, Japanese polyurethane industrial system, Sumidur HT, live to change Baeyer Polyurethane Inc., Takenate D-160N, Mitsui Chemicals urethane Inc.), TriMethylolPropane(TMP) and toluylene diisocya-nate is made to react compound (the Coronate L formed, Japanese polyurethane industrial system, Sumidur L-75, live to change Baeyer Polyurethane Inc., Takenate D-102, Mitsui Chemicals urethane Inc.), TriMethylolPropane(TMP) and xylylene diisocyanate is made to react compound (the Takenate D-110N formed, Mitsui Chemicals urethane Inc.), TriMethylolPropane(TMP) and isophorone diisocyanate is made to react compound (the Takenate D-140N formed, Mitsui Chemicals urethane Inc., Mitec NY215A, Mitsubishi Chemical Ind's system), as the isocyanate compound of difunctionality, allophanate compound (the Duranate D-201 obtained by 1,6-hexamethylene diisocyanate and monohydroxy-alcohol can be enumerated, Asahi Kasei Corporation's system, Coronate2770, Japanese polyurethane industrial system) etc.

In addition, as the compound of low molecule containing active hydrogen, ethylene glycol can be enumerated, propylene glycol, Diethylene Glycol, butyleneglycol, 1,6-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 3,3 '-dihydroxymethyl heptane, 2-methyl isophthalic acid, 8-ethohexadiol, 3,3 '-dihydroxymethyl heptane, 2-butyl-2-ethyl-1,3-PD, polyoxyethylene glycol (addition mole number is below 10), polypropylene glycol (addition mole number is below 10), BDO, 1,5-PD, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,9-nonanediol, neopentyl glycol, butyl ethyl pentanediol, 2-ethyl-1,3-hexylene glycol, cyclohexanediol, cyclohexanedimethanol, Tricyclodecane Dimethanol, cyclopentadiene dimethanol, the aliphatics of two polyalcohols etc. or cycloaliphatic diols class, 1,3-two (2-hydroxyl-oxethyl) benzene, two (2-hydroxyl-oxethyl) benzene of 1,2-, Isosorbide-5-Nitrae-bis-(2-hydroxyl-oxethyl) benzene, 4,4 '-methylene-di-phenol, 4,4 '-(the sub-norcamphyl of 2-) xenol, 4,4 '-dihydroxybiphenyl diphenol, adjacent, between and hydroquinol, 4,4 '-different methylene radical propyl benzene phenol, or on the bisphenols of dihydroxyphenyl propane or Bisphenol F etc. addition of ethylene oxide, the epoxy alkane of propylene oxide etc. and the aromatic diol class of bisphenols formed etc., 1,1,1-TriMethylolPropane(TMP), 1,1,1-tri hydroxy methyl butane, 1,1,1-trishydroxymethyl pentane, 1,1,1-Trimethylolhexane, 1,1,1-trimethylolheptane, 1,1,1-trishydroxymethyl octane, 1,1,1-trishydroxymethyl nonane, 1,1,1-trishydroxymethyl decane, 1,1,1-trimethylolundecane, 1,1,1-trishydroxymethyl dodecane, 1,1,1-trishydroxymethyl tridecane, 1,1, the 1-trishydroxymethyl tetradecane, 1,1,1-trishydroxymethyl pentadecane, 1,1,1-trishydroxymethyl n-Hexadecane, 1,1,1-trishydroxymethyl heptadecane, 1,1,1-trishydroxymethyl octadecane, 1,1,1-trishydroxymethyl nonadecane, the secondary butane of 1,1,1-trishydroxymethyl, the tertiary pentane of 1,1,1-trishydroxymethyl, the tertiary nonane of 1,1,1-trishydroxymethyl, the tertiary tridecane of 1,1,1-trishydroxymethyl, the tertiary heptadecane of 1,1,1-trishydroxymethyl, 1,1,1-trishydroxymethyl-2-methyl-hexane, 1,1,1-trishydroxymethyl-3-methyl-hexane, 1,1,1-trishydroxymethyl-2-ethyl-hexan, 1,1,1-trishydroxymethyl-3-ethyl-hexan, the trishydroxymethyl branch alkanes of the different heptadecane of 1,1,1-trishydroxymethyl etc., trishydroxymethyl butylene, trishydroxymethyl heptene, trishydroxymethyl amylene, trishydroxymethyl hexene, trishydroxymethyl heptene, trishydroxymethyl octene, trishydroxymethyl decene, trishydroxymethyl laurylene, trishydroxymethyl tridecylene, trishydroxymethyl ten pentaene, trishydroxymethyl hexadecylene, trishydroxymethyl 17 alkene, trishydroxymethyl octadecylene, 1,2,6-butane triol, 1,2,4-butane triol, the three-functionality-degree polyalcohols of glycerine etc., tetramethylolmethane, Dipentaerythritol, sorbyl alcohol, polyalcohols more than four functionality of Xylitol etc., quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, diamino-dicyclohexyl methane, 3-amino methyl-3,5,5-trimethyl cyclohexylamine, two (amino methyl) hexanaphthene of 1,3-, Triethylenetetramine (TETA), diethylenetriamine, the aliphatic polyamine class of triaminopropane etc., phenylenediamine, tolylene diamines, diaminodiphenyl-methane, the aromatic polyamine class of diamino-diphenyl ether etc., dithioglycol, dimercaptopropane, succinimide mercaptans, pentane disulfide thioalcohol, ethanthiol, heptan two mercaptan, pungent two mercaptan, the ninth of the ten Heavenly Stems two mercaptan, dimercapto dicyclohexyl methyl hydride, 3-mercapto methyl-3,5,5-3-methyl cyclohexanol mercaptan, two (mercapto methyl) hexanaphthene of 1,3-, Isosorbide-5-Nitrae-bis-(3-sulfydryl butyryl acyloxy) butane, the multi-thiol class of tetramethylolmethane four (3-mercaptobutylate) etc.

Polymeric polyisocyanate class solidifying agent (B) of the present invention obtains containing the compound reaction of active hydrogen by making above-mentioned isocyanate-monomer and low molecule.At this moment, the compound that isocyanate-monomer and these low molecule contain active hydrogen both can individually use, and also can be used in combination of two or more.

Based on forming the reason of sufficient crosslinking structure, the isocyanate compound in polymeric polyisocyanate class solidifying agent (B) also preferably more than two functionality.Moreover, consider adaptation and adhere to persistence etc., preferred adducts, and the three-functionality-degree isocyanate compound of the preferred trimethylolpropane adduct of hexamethylene diisocyanate, the trimethylolpropane adduct, the trimethylolpropane adduct of isophorone diisocyanate, the trimethylolpropane adduct of xylylene diisocyanate etc. of toluylene diisocya-nate, and by the obtained allophanate compound of 1,6-hexamethylene diisocyanate and monohydroxy-alcohol.Particularly, based on the viewpoint of adaptation, humidity resistance, preferred difunctionality isocyanate compound further.These polymeric polyisocyanate class solidifying agent (B) both can be used alone one, also can be used in combination of two or more.

In the present invention, relative to acrylic copolymer (A) 100 weight part, polymeric polyisocyanate solidifying agent (B) preferably uses 0.01 ~ 10 weight part, preferably uses 0.05 ~ 8 weight part further, more preferably uses 0.1 ~ 5 weight part.

In the present invention, in the scope not damaging effect of the present invention, also can be used together multi-functional epoxy compound as solidifying agent.By also using multi-functional epoxy compound, the thermotolerance of binder layer can be improved further.As multi-functional epoxy compound, such as, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, 1 can be enumerated, 6-hexanediol diglycidyl ether, dihydroxyphenyl propane/Epicholorohydrin type epoxy resin, N, N, N ' N '-four glycidyl group-m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N-diglycidylaniline, N, N-diglycidyl Tolylamine etc.

In the present invention, relative to multipolymer (A) 100 weight part, multi-functional epoxy compound preferably uses 0.1 ~ 5 weight part.

On the indicating meter of touch-screen etc., the situation at the edge part of nesa coating with the conducting wire of about 10 ~ 30 μm step differences formed by silver paste etc. is more.Thus, when pasting adopting the adhesive tape of tackiness agent of the present invention on this conducting wire, can be implemented in that the corner of step difference etc. does not remain bubble, excellent step difference tracing ability by the combined effect of acrylic copolymer (A) and polymeric polyisocyanate class solidifying agent (B).Here, as nesa coating, such as, ITO(indium/tin can be enumerated) electroconductive polymer thin film etc. of metallic film, Polythiophene or the polyaniline etc. of film etc.In addition, in the present invention, being embedded into property of step difference refers to the being embedded into property of step difference when the low-temperature heat lamination of 40 DEG C ~ about 50 DEG C, should with implement in printed-wiring board (PWB) technical field, by by the adhesive sheet of dry film shape 80 DEG C ~ about 200 DEG C be laminated to wired circuit is embedded into step difference, heat lamination distinguished.

In the present invention, by using silane coupling agent (C), the bounding force of binder layer and adherend can be improved, and also can improve resistance to foaminess and peel resistance.

As silane coupling agent (C), specifically, γ-(methyl) acryloyloxymethyl Trimethoxy silane can such as be enumerated, γ-(methyl) acryloxypropyl Trimethoxy silane, γ-(methyl) acryloxypropyl triethoxyl silane, γ-(methyl) acryloxypropyl three butoxy silane, γ-(methyl) acryloxypropyl dimethoxysilane, the alkoxysilane compound containing trialkylsilyl group in molecular structure with (methyl) acryloxy of γ-(methyl) acryloxypropyl diethoxy silane etc., vinyltrimethoxy silane, vinyltriethoxysilane, vinyltributoxysilane, the alkoxysilane compound containing trialkylsilyl group in molecular structure with vinyl of vinyl methyl dimethoxysilane etc., gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, gamma-amino hydroxypropyl methyl dimethoxysilane, the alkoxysilane compound containing trialkylsilyl group in molecular structure with aminoalkyl group of gamma-amino hydroxypropyl methyl diethoxy silane etc., γ mercaptopropyitrimethoxy silane, γ-Mercaptopropyltriethoxysilane, γ-mercaptopropyi methyl dimethoxysilane, γ-mercaptopropyi methyldiethoxysilane, β-mercaptomethylphenyl ethyl trimethoxy silane, mercapto methyl Trimethoxy silane, 6-sulfydryl hexyl Trimethoxy silane, the alkoxysilane compound containing trialkylsilyl group in molecular structure with sulfydryl of 10-sulfydryl decyl Trimethoxy silane etc., methyltrimethoxy silane, Union carbide A-162, dimethyldimethoxysil,ne, dimethyldiethoxysilane, ethyl trimethoxy silane, ethyl triethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, hexyl Trimethoxy silane, the alkoxysilane compound containing trialkylsilyl group in molecular structure with alkyl of decyl Trimethoxy silane etc., phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl tripropoxy silane, the alkoxysilane compound containing trialkylsilyl group in molecular structure with phenyl of phenyl three butoxy silane etc., tetramethoxy-silicane, tetraethoxysilane, four butoxy silanes, tetrapropoxysilane etc. there is no substituent alkoxysilane compound containing trialkylsilyl group in molecular structure, 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxyl silane, the alkoxysilane compound containing trialkylsilyl group in molecular structure with glycidyl of 3-glycidoxypropyl dimethoxysilane etc., in addition, as alkoxysilane compound containing trialkylsilyl group in molecular structure, can enumerate 2-(3,4-expoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-expoxycyclohexyl) ethyl triethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, hexa methyl silazane, dimethoxydiphenylsilane, 1,3,5-tri-(3-trimethoxy-silylpropyl) isocyanuric acid ester, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, 3-isocyanate group propyl-triethoxysilicane etc.

As silane coupling agent (C), within the adhesive layer, the form of the silicon bonding of the silane coupling agent be preferably hydrolyzed with alkoxyl group exists.By taking this form, can be easy to and the water affinity invaded in binder layer, thus can improve non-whitening resistance further.Further, further preferably silane coupling agent (C) more freely move within the adhesive layer and with water affinity.Thus non-whitening resistance in order to improve further, further preferably silane coupling agent (C) does not have the reactive functional groups beyond alkoxyl group or has the functional group that the functional group had with acrylic copolymer (A) is difficult to react.Such as, preferably except alkoxyl group, there is alicyclic epoxy group further.In addition, need be illustrated, described description is not to stop silane coupling agent (C) to have reactive functional groups beyond alicyclic epoxy group.

As the silane coupling agent with alicyclic epoxy group, can 2-(3 be enumerated, 4-expoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-expoxycyclohexyl) ethyl triethoxysilane etc.Further, " there is no the silane coupling agent of the reactive group beyond alkoxyl group " and refer to above-mentioned there is alkyl alkoxysilane compound containing trialkylsilyl group in molecular structure, the alkoxysilane compound containing trialkylsilyl group in molecular structure with phenyl and there is no substituent alkoxysilane compound containing trialkylsilyl group in molecular structure.Further preferably 2-(3,4-expoxycyclohexyl) ethyl trimethoxy silane, Union carbide A-162, tetraethoxysilane, phenyl triethoxysilane.In addition, silane coupling agent (C) both can be used alone one, also can be used in combination of two or more.

Relative to acrylic copolymer (A) 100 weight part, silane coupling agent (C) preferably uses 0.001 ~ 1 weight part.By using silane coupling agent (C) in described scope, bounding force can be improved further.Silane coupling agent (C) preferably uses 0.005 ~ 0.8 weight part further.

As tackiness agent of the present invention, on the basis of acrylic copolymer (A), polymeric polyisocyanate class solidifying agent (B) and silane coupling agent (C), also can be used together other resins as required, such as also with acrylic resin, vibrin, aminoresin, epoxy resin, urethane resin.Further, the additive of the weighting agent, tinting material, tenderizer, UV light absorber, antioxidant, defoamer, photostabilizer, weathering stabilizers, curing catalyst, cure retarder, phosphoric acid ester etc. of coupling drug, tackifier, talcum, calcium carbonate, titanium oxide etc. also can be mixed according to purposes.

As adhesive sheet of the present invention, preferably at least comprise the binder layer formed by above-mentioned binder composition.Adhesive sheet can be obtained by coating adhesive in separate-type paper.Or, also obtain adhesive sheet by coating adhesive direct on base material.With regard to adhesive sheet, after forming binder layer by coating adhesive in separate-type paper, paste the mode of separate-type paper again, can as there is no the adhesive sheet of base material, namely being used as casting adhesive sheet.In addition, base material is can be fully closely sealed and be not easy to the material peeled off with binder layer.On the other hand, separate-type paper be implemented lift-off processing etc., be easy to the material peeled off with binder layer.In the present invention, adhesive tape, adhesive sheet and bonding film are synonym.

Suitable liquid medium can be added carry out adjusting viscosity in the coating of tackiness agent.Specifically, such as can enumerate the varsol of toluene, dimethylbenzene, hexane, heptane etc., the esters solvent of ethyl acetate, N-BUTYL ACETATE etc., the ketones solvent of acetone, methylethylketone etc., the halogenated hydrocarbon solvent of methylene dichloride, chloroform etc., the ether solvent of ether, methoxy toluene, dioxane etc., or other varsols etc.Wherein, water or alcohol, owing to likely causing the response inhabitation of acrylic copolymer (A) and polymeric polyisocyanate class solidifying agent (B), therefore need prudent use.

Special restriction is not had for coating process, the various coating processes such as the coating of silk rod, coating machine coating, hairbrush coating, spraying coating, running roller coating, gravure roll coating, die slot coating, roller coat cloth, comma coating, scraper for coating, reverse roll coating, the rotary coating of coincideing can be enumerated.Special restriction is not had for drying means, warm air drying can be enumerated, utilize infrared rays or decompression method drying means.As drying conditions, hot blast or the steam heating of about 60 ~ 180 DEG C usually can be adopted.

In the present invention, special restriction be there is no for base material, such as, can enumerate the various bloomings of plastic film, antireflection (AR) film, Polarizer, polarizer etc.As described plastic film, polychloroethylene film, polyethylene film, polyethylene terephthalate (PET) film, polyurethane film, nylon membrane, polyolefin film, tri acetyl cellulose film, cycloolefin film etc. can be enumerated.Thickness for base material does not have special restriction, but is preferably 10 ~ 2000 μm.

The thickness of binder layer is preferably 2 ~ 1000 μm, more preferably 5 ~ 500 μm.In addition, binder layer both can be individual layer, also can be stacked two-layer more than.

Adherend (pasted objects) for adhesive sheet of the present invention does not have special restriction, but preferably has the acrylic panel of nesa coating, polycarbonate plate, cycloolefin film, glass or polyethylene terephthalate plate.

Adhesive sheet of the present invention is preferably used in the laminating of optics.Optics is also referred to as blooming when being sheet, but specifically, can enumerate light polarizing film, phase retardation film, elliptical polarized light film, anti-reflective film, brightness enhancement film etc.

Be pasted onto on such as liquid crystal cell glass component by the adhesive sheet above-mentioned optics being used in base material, the liquid crystal cell parts of the optics/binder layer/liquid crystal cell glass component having stacked gradually sheet can be obtained.In the present invention, when optics is Polarizer, especially there is application value, and the good layered product of peel resistance can be obtained.

Further, owing to can be used in liquid crystal cell parts, so adhesive sheet of the present invention can be used in the indicating meter of liquid crystal display, plasma display panel (PDP) (PDP) etc.Further, adhesive sheet of the present invention is used in the preferred process these indicating meters being made into touch-screen further.Particularly, on face that be preferably directly pasted onto touch-screen inside, that be formed with nesa coating and conducting wire.Even if in this case, because the step difference tracing ability embedding the step difference of conducting wire is good, therefore the bubble of touch-screen inside can be mixed into and controls in inferior limit.Moreover with regard to adhesive sheet of the present invention, by the various formations of binder layer, even if be placed on high temperature and be also difficult to cause the corrosion of conducting wire in high humidity environment, and the transparency of binder layer is also difficult to suffer damage.Moreover, preferably use adhesive sheet of the present invention when the plastic basis material with the acrylic panel, polycarbonate plate etc. as touch-screen support bonds.Even if in this case, also can suppress the venting of plastic basis material, even and if when being placed in high temperature or hot and humid environment, also can not producing and float or peel off, and high transparent can be maintained.

As mentioned above, except being suitable for as except tackiness agent used for optical part, tackiness agent of the present invention is also very suitable for as general paster label, coating, elasticity materials for wall, coating film waterproof material, flooring material, tackifier, adhesive agent, laminate structures adhesive agent, sealing agent, shaped material, surface modification coating agent, binding agent (magnetic-based storage media, Ink binders, foundry goods binding agent, vitrified brick binding agent, graft materials, microcapsule, glass fiber infiltration agent etc.), polyurethane foam (hard, semi-rigid, soft), urethane RIM, UV/EB cured resin, high solid coating, thermohardening type elastomerics, microcellular foam material, fiber processing agent, softening agent, sound absorbent material, packing, tensio-active agent, gel coat agent, scagliola resin, scagliola shock-resistance imparting agent, resin for printing ink, film (lamination adhesive, protective membrane etc.), laminated glass resin, reactive diluent, various shaped material, spandex fiber, artificial leather, the raw material of synthetic leather etc., or used as various resin additive and raw material thereof.

Embodiment 1

Below, the present invention is done in conjunction with the embodiments and further illustrate, but the present invention is not by the restriction of these embodiments.In addition, in following example, represent " weight part " with " part ", represent " % by weight " with " % " respectively.

< synthesis example 1>

Use and there is the reaction unit of stirrer, reflux cooling pipe, nitrogen conduit, thermometer, dropper, using 50 % by weight of the total amount of monomer each in table 3, appropriate as the azobis isobutyronitrile of initiator, join in reactive tank as the ethyl acetate of solvent.Subsequently, the whole and appropriate ethyl acetate of residual monomer and azobis isobutyronitrile will be with the addition of and the solution mixed by dropper, be added drop-wise in reactive tank with about 2 hours, subsequently in nitrogen environment, about 80 DEG C of polymerizations 5 hours.Cool after reaction terminates, with diluted ethyl acetate, obtain the copolymer solution that non-volatile content is 40%, viscosity is 3000mPa s.Here, the multipolymer obtained is set to multipolymer (A-1).

< synthesis example 2 ~ 36>

Add various raw material by the part by weight of table 3 and table 4, adopt the method synthesizing propylene acid copolymer same with synthesis example 1.Further, the weight-average molecular weight of the acrylic copolymer obtained is shown in table 3, table 4.

[table 3]

[table 4]

The mensuration > of < weight-average molecular weight (Mw)

The mensuration of weight-average molecular weight have employed Shimadzu Seisakusho Ltd. GPC " LC-GPC system ".GPC, for lysed material in solvent (THF: tetrahydrofuran (THF)) to be carried out the liquid chromatography of separation and quantitative by the difference of its molecular size, has carried out polystyrene conversion when determining weight-average molecular weight.

Device name: Inc. of Shimadzu Seisakusho Ltd., LC-GPC system " Prominence "

Chromatographic column: connected 4 Cao Gen Dong Inc. GMHXL and 1 Cao Gen Dong Inc. HXL-H.

Mobile phase solvent: tetrahydrofuran (THF)

Flow velocity: 1.0mL/min

Column temperature: 40 DEG C

< embodiment 1>

Relative to the non-volatile content 100 parts of the copolymer solution obtained by synthesis example 1,50% ethyl acetate solution 1.0 parts of benzene mixed dimethylene diisocyanate trimethylolpropane adduct and chemical company of the KBE-403(SHIN-ETSU HANTOTAI system as silane coupling agent) 0.2 part, thus obtain tackiness agent.

The tackiness agent comma coater obtained is coated on separate-type paper (thickness is 38 μm) go up and make its dry rear thickness reach 25 μm, 100 DEG C of dryings after 2 minutes, paste other separate-type paper over the binder layer, in this condition, in aged at room temperature 7 days, thus obtain casting adhesive sheet.

< embodiment 2 ~ 17,19 ~ 22,24 ~ 34, reference example 18,23,35, comparative example 1 ~ 19>

As shown in table 5 and table 6, except changing the kind of multipolymer and solidifying agent, the kind of silane coupling agent, combined amount, method is similarly to Example 1 adopted to obtain adhesive sheet without base material.In addition, in this manual, embodiment 18,23 and 35 is reference example.

[table 5]

[table 6]

Adopt embodiment 1 ~ 17,19 ~ 22,24 ~ 34, the tackiness agent that obtains in reference example 18,23,35 and comparative example 1 ~ 19 and adhesive sheet, according to method evaluation shown below as coating, bounding force, resistance to foaming/peel resistance, the transparency of basic physical properties.Further, whitening resistance as the thermotolerance of optical characteristics, humidity resistance, releasable, non-aggressive, wet-heat resisting, the gas expansion of resistance to PC, being embedded into property of step difference evaluation has been carried out.Result illustrates in table 7.

< coating > by the tackiness agent comma coater obtained, be coated in separate-type paper with the surface covered of 3m/ minute, carries out visual valuation by following standard.

Zero: the surface smoothing of binder layer.That is, without striped, indenture etc., coated face is level and smooth.

×: the air spots of binder layer is sliding, or has pin hole.

The separate-type paper of the one side of the adhesive sheet obtained is peeled off by < bounding force >, binder layer is pasted onto PET film (Japan textile company A-4300, thickness is 100 μm) upper after be cut into the size of wide 25mm × long 100mm, thus made test adhesive sheet.The separate-type paper of this test adhesive sheet is peeled off, binder layer is pasted onto on sheet glass (thickness is 0.4mm) in the environment of 23 DEG C of-50%RH, carry out pressurized adhesion according to JIS Z-0237 with running roller further subsequently.Self-pressurization has bonded after 24 hours, adopts universal tensile testing machine to determine stripping strength (peel angle is 180 °, peeling rate is 300mm/ minute, unit be that N/25mm is wide).

The resistance to foaminess of < and peel resistance >

The separate-type paper of the one side of the adhesive sheet obtained is peeled off, binder layer is pasted onto the size being cut into wide 100mm × long 100mm after in PET film (Japan textile company A-4300, thickness is 100 μm), thus has made test adhesive sheet.The separate-type paper of this test adhesive sheet is peeled off, binder layer is pasted on a glass, place 240 hours in the environment of 85 DEG C.Subsequently, cool after 24 hours in the environment of 23 DEG C of-50%RH, according to following condition the bubble of binder layer occurred and the floating or peel off and carried out visual valuation of adhesive sheet.

Zero: do not find bubble completely, float and peel off.

△: find a small amount of bubble, float and peel off.

×: find a large amount of bubbles, float and peel off.

The separate-type paper of the one side of the adhesive sheet obtained is peeled off by < transparency >, binder layer is pasted onto PET film (Japan textile company A-4300, thickness is 100 μm) upper after be cut into the size of wide 25mm × long 100mm, thus made test adhesive sheet.

Peel off the separate-type paper of this test adhesive sheet, paste on a glass with laminating machine in the environment of 23 DEG C of-50%RH, determine HAZE subsequently.In addition, HAZE adopts the Turbidimeter NDH5000W of Japanese electricity Se industrial to measure.Judgement criteria as shown below.

Zero: HAZE is less than the 1.0(transparency well).

×: HAZE is (transparency is bad) more than 1.0.

< is for the adaptability > of Polarizer

1. the making of sample

Prepare (following for the two sides of polyvinyl alcohol (PVA) class polaroid tri acetyl cellulose class protective membrane; be referred to as " TAC film ") light polarizing film of multilayered structure that clamps, the binder layer after its one side being peeled off with the separate-type paper of the one side by the adhesive sheet obtained is pasted.Thus obtain the layered product A be made up of " separate-type paper/binder layer/TAC film/PVA/TAC film ".

Subsequently, above-mentioned layered product A is cut into the size of 150mm × 80mm, after peeling off separate-type paper, is pasted onto with laminating machine the two sides that thickness is the sheet glass of 1.1mm, and the absorption axes of each Polarizer is intersected vertically.Subsequently, the sheet glass being pasted with this layered product is kept 20 minutes in the autoclave of 50 DEG C, 5 atmospheric pressure, thus make this layered product and sheet glass closely sealed, thus obtain the evaluation layered product B of layered product and sheet glass.

2. heating is evaluated

After the evaluation layered product B obtained is placed 1000 hours in the environment of 120 DEG C, visual observation evaluation layered product B, thus the presence or absence that confirmation is floated and peeled off.Further, make light transmission evaluation layered product B, thus (being also referred to as " showing money or valuables one carries unintentionally ") is revealed to the light from evaluation layered product B confirm with visual.

3. heating and humidification evaluation

After the evaluation layered product B obtained is placed 1000 hours in the environment of 80 DEG C of-90%RH, visual observation evaluation layered product B, thus the presence or absence that confirmation is floated and peeled off.Further, make light transmission evaluation layered product B, thus (being also referred to as " showing money or valuables one carries unintentionally ") is revealed to the light from evaluation layered product B confirm with visual.

4. judgement criteria

Heating is evaluated, heat and humidification evaluation all adopts following standard to evaluate.

◎: do not float completely, peel off and show money or valuables one carries unintentionally, excellent performance.

Zero: occur on a small quantity floating, peel off and showing money or valuables one carries unintentionally, practicality does not have problems.

△: occur in a large number floating, peel off and showing money or valuables one carries unintentionally, practicality has problems.

×: floating, peeling off and showing money or valuables one carries unintentionally appears in entirety, cannot be practical.

< releasable (re-workability) >

The layered product A obtained is cut into the size of 25mm × 150mm, after peeling off separate-type paper, is pasted onto on the sheet glass that thickness is 1.1mm with laminating machine.Subsequently, keep 20 minutes in the autoclave of 50 DEG C, 5 atmospheric pressure, thus make it on a glass closely sealed.After this test film is placed one week in the environment of 23 DEG C of-50%RH, carry out from test film with 180 ° of stripping tests of the speed peeling laminated body A of 180 degree of directions, 300mm/ minute.The blackening that visual observation is produced by the tackiness agent remained on the glass surface after stripping, and adopt following standard to evaluate.

Zero: there is no blackening completely, excellent performance.

△: visible a small amount of blackening, practicality does not have problems.

×: binder layer remains in glass surface, cannot be practical.

< non-aggressive >

The separate-type paper of the one side of the adhesive sheet obtained is peeled off, binder layer is bonded in after in PET film (Japan textile company A-4300, thickness is 100 μm), is cut into the size of wide 40mm × long 100mm, thus has made test adhesive sheet.

The separate-type paper of stripping test adhesive sheet, in 23 DEG C of-50%RH environment, is pasted onto binder layer on the nesa coating of the film (wide 40mm × long 160mm) defining ITO nesa coating with laminating machine, thus obtains test sample.This test sample is placed 1000 hours in the environment of 85 DEG C of-90%RH, measures the resistance value after just pasting and the resistance value after placing, according to the velocity of variation of the resistance value before and after placing to the corrosion of nesa coating with or without evaluating.In addition, resistance value adopts the LORESTA GP(MCP-T600 type of Mitsubishi Chemical Ind) measure.Judgement criteria is as follows.

Zero: the velocity of variation of resistance value is less than 150%, and non-aggressive is good.

×: the velocity of variation of resistance value is more than 150%, and non-aggressive is bad.

The non-whitening resistance > of <

The separate-type paper of the one side of the adhesive sheet obtained is peeled off, binder layer is bonded in after in PET film (Japan textile company A-4300, thickness is 100 μm), is cut into the size of wide 25mm × long 80mm, thus has made test adhesive sheet.Subsequently, after the separate-type paper of stripping test adhesive sheet, be pasted onto with laminating machine in the environment of 23 DEG C of-50%RH on the nesa coating of the film (wide 40mm × long 160mm) defining above-mentioned same nesa coating.It is placed 1000 hours in the environment of 85 DEG C of-90%RH, after 23 DEG C of-50%RH cool 3 hours, HAZE is measured.In addition, HAZE adopts the Turbidimeter NDH5000W of Japanese electricity Se industrial to measure.Judgement criteria is as follows.

◎: HAZE is less than 1.2, non-whitening resistance excellence.

Zero: HAZE is less than 8.0 more than 1.2, non-ly whitening resistancely not to have problems in practical.

×: HAZE more than 8.0, non-whitening resistance difference.

> is evaluated in < venting

The separate-type paper of the one side of the adhesive sheet obtained is peeled off, binder layer is bonded in after in PET film (Japan textile company A-4300, thickness is 100 μm), is cut into the size of wide 25mm × long 100mm, thus has made test adhesive sheet.Subsequently, be bonded on polycarbonate (PC) plate that thickness is 5mm after the separate-type paper of stripping test adhesive sheet.It applied in the environment of 50 DEG C the pressure of 0.5MPa subsequently and keep 20 minutes, thus having made the test film stacking gradually PET film/binder layer/PC plate this test film is placed 24 hours in 80 DEG C of baking ovens.Subsequently, in the environment of 23 DEG C, place the state at the interface of visual observation binder layer and PC plate after 24 hours, and adopt following standard to evaluate.

◎: the state at interface does not change, excellent performance.

Zero: occur floating of bubble or binder layer in interface on a small quantity, practicality does not have problems.

×: there is floating of bubble or binder layer in interface in a large number, cannot be practical.

< step difference tracing ability >

The separate-type paper of the one side of the adhesive sheet obtained is peeled off, binder layer is bonded in after in PET film (Japan textile company A-4300, thickness is 100 μm), is cut into the size of wide 25mm × long 100mm, thus has made test adhesive sheet.

On the other hand, in the PET film prepared separately by screen printer print live width is 1cm, line is spaced apart 1cm, thickness is the silver-colored ink of 10 μm line pattern.

Subsequently, in 23 DEG C of-50%RH environment, be pasted onto on this line pattern with laminating machine after the separate-type paper of stripping test adhesive sheet.Subsequently, further by its in autoclave with the condition process of 50 DEG C of-0.5MPa after 20 minutes, place 24 hours in 23 DEG C of-50%RH environment further, subsequently visual observation is carried out to the step difference whether binder layer can follow line pattern, and adopt following standard to evaluate.

◎: after pasting with laminating machine, step difference immediately bonded oxidant layer is embedded into.

Zero: after autoclave process, step difference immediately bonded oxidant layer is embedded into.

△: after carrying out autoclave treated 24 hours, the bonded oxidant layer of step difference is embedded into.

×: even if after carrying out autoclave treated 24 hours, step difference does not have bonded oxidant layer to be embedded into yet.

[table 7]

As shown in table 7, comparative example 1 ~ 19 can not meet that coating, bounding force, resistance to foaming/peel resistance, the transparency, thermotolerance, humidity resistance, releasable, non-aggressive, wet-heat resisting are whitening resistance, all properties of the gas expansion of resistance to PC, being embedded into property of step difference.

On the other hand, embodiment 1 ~ 35 has excellent coating, bounding force, resistance to foaming/peel resistance, the transparency, and, resistance to PC gas expansion whitening resistance at thermotolerance, humidity resistance, releasable, non-aggressive, wet-heat resisting and being embedded into property of step difference obtain excellent result.

Tackiness agent of the present invention and adhesive sheet not only have excellent coating, binding property, resistance to foaming/peel resistance, the transparency, also, resistance to PC gas expansion, step difference being embedded into property whitening resistance with higher non-aggressive, wet-heat resisting, be suitable for directly pasting and using in the bonding purposes of the optics of the purposes of fixing etc. on the metallic film of indicating meter or touch-screen etc.

Claims (6)

1. a tackiness agent, wherein, containing acrylic copolymer (A), polymeric polyisocyanate class solidifying agent (B) and silane coupling agent (C),

Described acrylic copolymer (A) be more than 8 by radical polymerization SP value and be less than 9.00 the ethylene unsaturated monomer (A1) 20 ~ 90 % by weight with alkyl and SP value be less than more than 9.00 15 the ethylene unsaturated monomer (A2) 10 ~ 80 % by weight with polar group formed, and for weight-average molecular weight be the polymkeric substance of 200,000 ~ 1,000,000

The described ethylene unsaturated monomer (A2) with polar group has more than one polar groups in the group selecting free hydroxyl (a1), amide group (a2), amino (a3) and itrile group (a4) to form, and the second-order transition temperature of homopolymer (Tg) is more than-40 DEG C less than 120 DEG C.

2. tackiness agent as claimed in claim 1, it is characterized in that, described acrylic copolymer (A) be more than 8 by radical polymerization SP value and be less than 9.00 be less than more than 9.00 15 containing the ethylene unsaturated monomer (A1) 40 ~ 80 % by weight of alkyl and SP value the ethylene unsaturated monomer (A2) 20 ~ 60 % by weight containing polar group is formed.

3. tackiness agent as claimed in claim 1 or 2, it is characterized in that, described polymeric polyisocyanate class solidifying agent (B) is for being selected from more than one compounds in the group that is made up of aromatic-aliphatic class polymeric polyisocyanate, aliphatic category polymeric polyisocyanate and alicyclic polymeric isocyanate, or the modifier of these compounds.

4. tackiness agent as claimed in claim 1 or 2, it is characterized in that, described silane coupling agent (C) has alkoxyl group and alicyclic epoxy group as reactive functional groups, or only has alkoxyl group.

5. an adhesive sheet, wherein, at least has the binder layer formed by the tackiness agent in Claims 1 to 4 described in any one.

6. an indicating meter, wherein, at least has the binder layer formed by the tackiness agent in Claims 1 to 4 described in any one.