CN104250530A

CN104250530A - Adhesive Sheet And Laminating Body

Info

Publication number: CN104250530A
Application number: CN201410302719.0A
Authority: CN
Inventors: 江嶋由多加; 荒井隆行; 所司悟
Original assignee: Lintec Corp
Current assignee: Lintec Corp
Priority date: 2013-06-28
Filing date: 2014-06-27
Publication date: 2014-12-31
Anticipated expiration: 2034-06-27
Also published as: TWI619793B; CN104250530B; KR20210025551A; KR102222199B1; TW201502233A; TWI731223B; TW201819571A; CN110054997B; KR20150002456A; CN110054997A; KR102281764B1; JP6325777B2; JP2015010197A

Abstract

The present invention provides an adhesive sheet possessing an adhesive layer and a laminating body. The adhesive layer is excellent in concave-convex follow performance, at the same time, is excellent in humidity resistance, albefaction resistance and durability. In order to solve the above subject, the adhesive sheet 1 possessing the adhesive layer 11 which is formed by the thermo-crosslinking of the adhesive compositions and of which the thickness is 50-400 micrometers, is provided. The adhesive compositions comprise a (methyl) acrylate copolymer (A), an active energy linear curing component (B) and a cross-linking agent (C), the weight-average molecular weight of the (methyl) acrylate copolymer (A) is 200-900 thousands, and a monomeric unit of forming the polymer contains 5-20% by mass of monomer possessing the carboxyl or 15-30% by mass of the monomer possessing the hydroxy, and the content of the active energy linear curing component (B) is 10-50 parts by mass, relative to 100 parts by mass of the (methyl) acrylate copolymer (A).

Description

Adhesive sheet and duplexer

Technical field

The present invention relates to a kind of adhesive sheet with the bond layer of active energy ray-curable and the duplexer using the bond layer of this adhesive sheet to obtain.

Background technology

The various mobile electronic equipments such as mobile phone in recent years or tablet terminal, possess the indicating meter employing and have the display body assemblies such as liquid crystal cell, photodiode (LED element), organic electroluminescent (organic EL) element.

In such indicating meter, usually, the face side of display body assembly is provided with protection panel.Be provided with space between protection panel and display body assembly, like this when causing protection panel deformation due to external force, make the protection panel of distortion can not encounter display body assembly.

But space as above, if namely gas cloud exists, then the reflection loss of the light that the refringence of protection panel and gas cloud, and the refringence of gas cloud and display body assembly causes is large, has the problem that indicating meter image quality reduces.

Therefore, there is the space researched and proposed by filling up with bond layer between protection panel and display body assembly, improving the image quality of indicating meter.But the display body components side of protection panel, has the situation that frame-shaped printed layers exists with concave-convex form.If bond layer does not chase after from this concavo-convex, then adhesive layer floats near concavo-convex, thus, the reflection loss of light occurs.Therefore, described bond layer is required concavo-convex following.

For solving above-mentioned problem, in patent documentation 1, as filling up the bond layer in space between protection panel and display body assembly, disclose 25 DEG C, storage shear modulus under 1Hz (G ') is 1.0 × 10 ⁵below Pa, and gel fraction is the bond layer of more than 40%.

Prior art document

Patent documentation

Patent documentation 1: Japanese Patent Publication 2010-97070 publication

Summary of the invention

The technical problem to be solved in the present invention

In patent documentation 1, reduce for storage modulus when passing through the normal temperature by bond layer, improve concavo-convex following.But if storage modulus during normal temperature reduced as mentioned above, storage modulus during high temperature can excessively reduce, and has problems under durable condition.Such as, after the hot and humid condition of enforcement, when returning to ambient temperature and moisture, bond layer albefaction can be produced or the problem of generation bubble near concavo-convex.

In addition, as described protection panel, usually use sheet glass, but due to the requirement of filming in recent years, lightweight etc., have the situation using plastic plate.In high temperature environments, the situation producing gas (exhaust) from this plastic plate is had.When using the situation of this plastic plate, due to described exhaust, there is the situation producing bubble or float, peel off (bubble) between plastic plate and bond layer.

The present invention carries out in view of such present situation, and object is to provide a kind of adhesive sheet and the duplexer with bond layer, and the concavo-convex following of described bond layer is excellent, and meanwhile, wet-heat resisting albefaction, weather resistance and water soak resistance are also excellent.

The technique means of technical solution problem

In order to reach above-mentioned purpose, first, the invention provides a kind of adhesive sheet, it has and to be formed by adhesive composition heat cross-linking, thickness is the bond layer of 50 μm ~ 400 μm, described adhesive composition contains (methyl) acrylate copolymer (A), active energy ray-curable composition (B) and linking agent (C), the weight-average molecular weight of described (methyl) acrylate copolymer (A) is 200,000 ~ 900,000, contain 5 quality % ~ 20 quality % as the monomeric unit forming polymkeric substance there is the monomer of carboxyl or there is containing 15 quality % ~ 30 quality % the monomer of hydroxyl, the content of described active energy ray-curable composition (B), relative to described (methyl) acrylate copolymer (A) 100 mass parts, be 10 mass parts ~ 50 mass parts (inventions 1).

In foregoing invention (invention 1), by the adhesive composition heat cross-linking by (methyl) acrylate copolymer that is little containing weight-average molecular weight, that comprise specified amount hydroxyl or carboxyl, obtained bond layer, concavo-convex following and wet-heat resisting albefaction excellence, meanwhile, also there is excellent weather resistance.In addition, described adhesive composition is by containing a large amount of active energy ray-curable composition, thus described bond layer is solidified by the irradiation of active energy ray, the bond layer of so solidification, weather resistance and water soak resistance excellence.

In foregoing invention (invention 1), the content of the described linking agent (C) in described adhesive composition, relative to described (methyl) acrylate copolymer (A) 100 mass parts, be preferably 0.01 mass parts ~ 5 mass parts (invention 2).

Foregoing invention (invention 1, invention 2) in, storage modulus after irradiating active energy ray to described bond layer at 23 DEG C, with irradiates active energy ray to described bond layer before the ratio of storage modulus at 23 DEG C, be preferably 1.1 ~ 10 (inventing 3).

In foregoing invention (invention 1 ~ invention 3), storage modulus after irradiating active energy ray to described bond layer at 85 DEG C, with irradiate active energy ray to described bond layer before the ratio of storage modulus at 85 DEG C, be preferably 1.1 ~ 10 (inventions 4).

In foregoing invention (invention 1 ~ invention 4), described adhesive sheet possesses two panels stripping film, and described bond layer is preferably clamped (inventing 5) by described stripping film in the mode connected with the release surface of described two panels stripping film.

Second, the invention provides a kind of duplexer, it is characterized in that, it possesses two panels hard plate and by the bond layer of described two panels hard plate clamping, described bond layer is irradiated by active energy ray and the bond layer solidification of described adhesive sheet (invention 1 ~ invention 5) formed (invention 6).

In foregoing invention (invention 6), at least one of described hard plate, preferably has concavo-convex (inventing 7) on the face of described bond layer side.

In foregoing invention (invention 7), the described concavo-convex printed layers that is preferably is with or without concavo-convex (invention 8) that cause.

In foregoing invention (invention 6 ~ invention 8), at least one of preferred described hard plate comprises polarized light piece (invention 9).

In foregoing invention (invention 6 ~ invention 9), at least one of preferred described hard plate comprises plastic plate (invention 10).

In foregoing invention (invention 6 ~ invention 8); a slice of preferred described two panels hard plate is display body assembly or its part, and another sheet of preferred described two panels hard plate is on the face of described bond layer side, have the concavo-convex protecting sheet of frame-shaped (invention 11).

In foregoing invention (invention 6 ~ invention 11), total light penetration of described bond layer is preferably more than 80% (invention 12).

Invention effect

The bond layer of adhesive sheet of the present invention, concavo-convex following is excellent, and after active energy ray irradiates, wet-heat resisting albefaction, weather resistance and water soak resistance are also excellent.In the duplexer using such adhesive sheet to obtain, even if bond layer side has concavo-convex, bond layer also can chase after from this concavo-convex, therefore can not produce near concavo-convex and float or bubble etc.In addition, in described duplexer, the postradiation bond layer of active energy ray, wet-heat resisting albefaction, weather resistance and water soak resistance are also excellent.

Accompanying drawing explanation

The sectional view of the adhesive sheet of Fig. 1 involved by an embodiment of the present invention.

The sectional view of the duplexer of Fig. 2 involved by an embodiment of the present invention.

Embodiment

Below, be described about embodiments of the present invention.

(adhesive sheet)

As shown in Figure 1, adhesive sheet 1 described in present embodiment, formed by two panels stripping film 12a, 12b with the bond layer 11 that the mode connected with the release surface of this two panels stripping film 12a, 12b is clamped in this two panels stripping film 12a, 12b.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.

1. bond layer

Described bond layer 11 is that the adhesive composition containing (methyl) acrylate copolymer (A), active energy ray-curable composition (B) and linking agent (C) (is had the situation being called " adhesive composition P " below.) bond layer of active energy ray-curable that forms of heat cross-linking, the weight-average molecular weight of described (methyl) acrylate copolymer (A) is 200,000 ~ 900,000, contains 5 quality % ~ 20 quality % have the monomer (carboxyl group-containing monomer) of carboxyl or have the monomer (hydroxyl monomer) of hydroxyl containing 15 quality % ~ 30 quality % as the monomeric unit forming polymkeric substance.In addition, in this specification sheets, said (methyl) vinylformic acid, refers to both of vinylformic acid and methacrylic acid.Other similar term too.

Adhesive composition P heat cross-linking formed by the bond layer 11 in adhesive sheet 1, and specifically, (methyl) acrylate copolymer (A), by linking agent (C), becomes crosslinked state.On the other hand, active energy ray-curable composition (B) is also uncured, is present in bond layer 11 with the former state state being matched with adhesive composition P.This active energy ray-curable composition (B), when adhesive sheet 1 uses (during laminating adherend), is polymerized when irradiating active energy ray to bond layer 11 thus solidification.

(1) (methyl) acrylate copolymer (A)

(methyl) acrylate copolymer (A) is the bonding host in adhesive composition P.(methyl) acrylate copolymer (A), as the monomeric unit forming this polymkeric substance, the carboxyl group-containing monomer containing 5 quality % ~ 20 quality %, or the hydroxyl monomer containing 15 quality % ~ 30 quality %.The content of carboxyl group-containing monomer or hydroxyl monomer is in above-mentioned scope, then the crosslinking structure formed by (methyl) acrylate copolymer (A) and linking agent (C) becomes good, and bond layer 11 obtains excellent weather resistance.In addition, can be suppressed by the content containing carboxyl group-containing monomer or hydroxyl monomer after this bond layer 11 solidifies at the bond layer 11 that the adhesive composition P of (methyl) acrylate copolymer (A) of above-mentioned scope obtains, implement hot and humid condition (such as, 85 DEG C, under the condition of 85%RH, 240 hours) albefaction afterwards, when returning to ambient temperature and moisture, that is, wet-heat resisting albefaction is excellent.(methyl) acrylate copolymer (A) if contain carboxyl group-containing monomer or hydroxyl monomer as monomeric unit with described amount, then remains carboxyl or the hydroxyl of specified amount in obtained caking agent.Carboxyl and hydroxyl are hydrophilic radical, if this hydrophilic radical is present in caking agent with specified amount by inference, even if under caking agent is placed on hot and humid condition, the moisture of caking agent is immersed when returning to ambient temperature and moisture under this hot and humid condition, easily depart from from caking agent, its result, the albefaction of caking agent is suppressed.

In (methyl) acrylate copolymer (A), as monomeric unit, if the content of carboxyl group-containing monomer is less than 5 quality %, or the content of hydroxyl monomer is less than 15 quality %, then the particularly wet-heat resisting albefaction of bond layer 11 can reduce.On the other hand, if the content of carboxyl group-containing monomer is more than 20 quality %, or the content of hydroxyl monomer is more than 30 quality %, then the coating of adhesive composition P is deteriorated.

Consider from above-mentioned viewpoint, (methyl) acrylate copolymer (A), as the monomeric unit forming this polymkeric substance, be preferably containing 7 quality % ~ 15 quality %, the carboxyl group-containing monomer particularly containing 8 quality % ~ 12 quality %, or containing 17 quality % ~ 28 quality %, the hydroxyl monomer particularly containing 20 quality % ~ 25 quality %.

As carboxyl group-containing monomer, such as, can enumerate the alkene class unsaturated carboxylic acid of vinylformic acid, methacrylic acid, β-crotonic acid, toxilic acid, methylene-succinic acid, citraconic acid etc.Wherein, from the viewpoint of the carboxyl in obtained (methyl) acrylic ester polymer (A) and the reactivity of linking agent (B) and the copolymerizable with other monomers, preferably (methyl) vinylformic acid, is particularly preferably vinylformic acid.These may be used singly or in combination of two or more use.

As hydroxyl monomer, such as, can enumerate (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, from the viewpoint of the hydroxyl in obtained (methyl) acrylic ester polymer (A) and the reactivity of linking agent (B) and the copolymerizable with other monomers, be preferably (methyl) vinylformic acid 2-hydroxyethyl ester.These may be used singly or in combination of two or more use.

(methyl) acrylate copolymer (A), as forming the monomeric unit of this polymkeric substance, the carbonatoms be preferably containing alkyl is (methyl) alkyl acrylate of 1 ~ 20, particularly preferably contains as principal constituent.Thus, the caking agent obtained can show excellent cementability.

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, (methyl) n-butylacrylate and (methyl) 2-ethylhexyl acrylate.And these may be used singly or in combination of two or more use.

(methyl) acrylate copolymer (A), as the monomeric unit forming this polymkeric substance, carbonatoms preferably containing the above alkyl of 50 quality % is (methyl) alkyl acrylate of 1 ~ 20, particularly preferably containing more than 60 quality %, further preferably containing more than 70 quality %.In addition, the carbonatoms of alkyl is the upper limit of the content of (methyl) alkyl acrylate of 1 ~ 20, is preferably the remainder except carboxyl group-containing monomer and hydroxyl monomer.

(methyl) acrylate copolymer (A), as the monomeric unit forming this polymkeric substance, as required, also can containing other monomer.As other monomer, even in order to not hinder the effect of carboxyl group-containing monomer or hydroxyl monomer, preferably should not comprise the monomer with reactive functional groups yet.As such monomer, such as, (methyl) alkoxyalkyl acrylate of (methyl) methoxyethyl ethyl ester, (methyl) ethioxy ethyl ester etc. can be listed; (methyl) acrylate with aliphatics ring of (methyl) cyclohexyl acrylate 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, vinylbenzene etc.These may be used singly or in combination of two or more use.

The polymerization methods of (methyl) acrylate copolymer (A) can be random copolymers, also can be segmented copolymer.

The weight-average molecular weight of (methyl) acrylate copolymer (A) is 200,000 ~ 900,000, is preferably 250,000 ~ 700,000.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.

As the weight-average molecular weight of (methyl) acrylate copolymer (A) of the principal constituent of adhesive composition P, less as mentioned above, thus the bond layer 11 that this adhesive composition P heat cross-linking obtains is had excellent concavo-convex following.(methyl) acrylate copolymer (A) if weight-average molecular weight more than 900,000, then concavo-convex following is poor.On the other hand, (methyl) acrylate copolymer (A) if weight-average molecular weight be less than 200,000, then the poor durability of the postradiation bond layer 11 of active energy ray.Except above-mentioned viewpoint, consider from concavo-convex following, weather resistance viewpoint, the weight-average molecular weight of (methyl) acrylate copolymer (A), be particularly preferably 300,000 ~ 500,000, from the viewpoint of water soak resistance, the weight-average molecular weight of (methyl) acrylate copolymer (A), is particularly preferably 500,000 ~ 700,000.

In addition, in adhesive composition P, (methyl) acrylate copolymer (A) can be used alone one, also can be used in combination of two or more.

(2) active energy ray-curable composition (B)

By making adhesive composition P contain active energy ray-curable composition (B), thus the bond layer 11 formed becomes the bond layer of active energy ray-curable.This bond layer 11, by containing active energy ray-curable composition (B), thus concavo-convex following and excellent in te pins of durability.

Active energy ray-curable composition (B), as long as be the composition not hindering effect of the present invention, solidified by the irradiation of active energy ray, just have no particular limits, can be any one in monomer, oligopolymer or polymkeric substance, also can be their mixture.Wherein, can preferably list with the excellent compatibility of (methyl) acrylate copolymer (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 enumerate 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, 6-caprolactone modification three-(2-(methyl) 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.

As active energy ray-curable composition (B), the acrylate quasi-oligomer of active energy ray-curable also can be utilized.This acrylate quasi-oligomer, is preferably weight-average molecular weight 50, less than 000 person.As such 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 make to be obtained by the polycondensation of polycarboxylic acid and polyvalent alcohol 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 made and obtains.Epoxy Acrylates oligopolymer, such as, can by the oxyethane ring of bisphenol-type epoxy resin or phenolic resin varnish type epoxy resin, make that (methyl) vinylformic acid reacts, 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, make the urethane oligomer esterification that obtained by the reaction of 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 (B), also can be used in side chain and import adding and acrylic polymer of the group gained with (methyl) acryl.Adding and acrylic polymer like this; 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, preferably containing being selected from least one of hydroxyl, carboxyl, amino and amide group as functional 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 N hydroxymethyl acrylamide 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 the compound of the group that there is (methyl) acryl and react with 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-acrylyl oxy-ethyl succinate, 2-acrylyl oxy-ethyl hexahydrophthalic phthalimide, ω-carboxyl-polycaprolactone single-acrylate, phthalic acid monohydroxy ethyl propylene acid esters, 2-hydroxyl-3-phenoxypropylacrylate etc.These compounds may be used singly or in combination of two or more use.

Describedly add the weight-average molecular weight with acrylic polymer, be preferably 50,000 ~ about 900,000, be particularly preferably 100,000 ~ about 300,000.

Active energy ray-curable composition (B), both and can add with acrylic polymer from described polyfunctional acrylic ester class monomer, acrylate quasi-oligomer, select a kind of use, 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 (B) in adhesive composition P, relative to (methyl) acrylate copolymer (A) 100 mass parts, be required to be 10 mass parts ~ 50 mass parts, be preferably 15 mass parts ~ 45 mass parts, be particularly preferably 25 mass parts ~ 40 mass parts.The content of active energy ray-curable composition (B) is more than 10 mass parts, the then postradiation bond layer 11 of active energy ray, cohesive force improves, even if produce exhaust by plastic plate in high temperature environments, the generation that also can suppress bubble or float, peel off, water soak resistance is excellent.That is, active energy ray-curable composition (B) if content be less than 10 mass parts, then cannot obtain active energy ray irradiate after the water soak resistance of excellence of bond layer 11.On the other hand, active energy ray-curable composition (B) if content more than 50 mass parts, then the bonding force of the bond layer 11 of active energy ray pre-irradiation becomes too high, become and be difficult to from bond layer 11, stripping film 12a, 12b be peeled off smoothly, when peeling off stripping film 12a, 12b, bond layer 11 has damaged possibility.In addition, the postradiation bond layer 11 of active energy ray, by having the bonding force (to glass substrate) of more than 10N/25mm, therefore can keep the fit-state between hard plate securely.

(3) linking agent (C)

Adhesive composition P, by containing linking agent (C), is cross-linked (methyl) acrylate copolymer (A), forms three-dimensional net structure, improve the cohesive force of the caking agent obtained.In addition, after irradiating active energy ray, this caking agent also has and can be endowed weather resistance.

As linking agent (C), as long as the reactive group (carboxyl or hydroxyl) had for (methyl) acrylate copolymer (A) has reactive linking agent, such as, can list isocyanates linking agent, epoxies linking agent, amine cross-linking agent, melamine class linking agent, aziridines linking agent, hydrazine class linking agent, aldehyde crosslinking agent, oxazoline class linking agent, metal alkoxide class linking agent, metallo-chelate class linking agent, metallic salt linking agent, ammonium salt class linking agent etc.Linking agent (C) can be used alone one, or also can be used in combination of two or more.

During the situation of (methyl) acrylate copolymer (A) containing carboxyl group-containing monomer, preferred use is selected from at least one in the epoxies linking agent of the reactivity excellence of carboxyl and isocyanates linking agent as linking agent (C), particularly preferably uses epoxies linking agent.During the situation of (methyl) acrylate copolymer (A) containing hydroxyl monomer, preferably use the isocyanates linking agent with the reactivity excellence of hydroxyl.

As epoxies linking agent, such as can enumerate 1, two (the N of 3-, N '-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group MXDP, ethylene glycol diglycidylether, 1,6-hexanediol diglycidyl ether, TriMethylolPropane(TMP) diglycidylether, 2-glycidyl aniline, 2-glycidyl amine etc.

Isocyanates linking agent is the linking agent at least containing polyisocyanate compound.As polyisocyanate compound, such as, can enumerate the aromatic polyisocyanate of tolylene diisocyanate, '-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; Adding and object etc. as the reactant containing low molecule active dydrogen compounds with ethylene glycol, propylene glycol, neopentyl glycol, TriMethylolPropane(TMP), castor-oil plant wet goods can be enumerated further.

The content of linking agent (C) in adhesive composition P, relative to (methyl) acrylate copolymer (A) 100 mass parts, is preferably 0.01 mass parts ~ 5 mass parts, is particularly preferably 0.05 mass parts ~ 1 mass parts.Linking agent (C) if content be more than 0.01 mass parts, then the postradiation caking agent of active energy ray, can give weather resistance improve effect.Linking agent (C) if content more than 5 mass parts, then crosslinked degree is excessive, and the concavo-convex following of the caking agent obtained likely reduces.In addition, the carboxyl of (methyl) acrylate copolymer (A) or hydroxyl are a large amount of to react with linking agent (C), the carboxyl remained in caking agent or the quantitative change of hydroxyl few, described wet-heat resisting albefaction likely reduces.Except above-mentioned viewpoint, from the viewpoint of making weather resistance the best, the content of linking agent (C) is preferably 0.05 mass parts ~ 0.4 mass parts, and from the viewpoint of making water soak resistance the best, the content of linking agent (C) is preferably 0.3 mass parts ~ 1 mass parts.

(4) Photoepolymerizationinitiater initiater (D)

As the active energy ray irradiated bond layer 11, when using ultraviolet situation, adhesive composition P is preferably further containing Photoepolymerizationinitiater initiater (D).Like this by containing Photoepolymerizationinitiater initiater (D), active energy ray-curable composition (B) effectively can be made to solidify, and the irradiation dose of polymerizing curable time and active energy ray can be reduced.

As such Photoepolymerizationinitiater initiater (D), 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) phenyl] acetone], 2,4,6-trimethylbenzoy-dipheny-phosphine oxide etc.These may be used singly or in combination of two or more use.

Photoepolymerizationinitiater initiater (D), relative to active energy ray-curable composition (B) 100 mass parts, is preferably 2 mass parts ~ 15 mass parts, particularly preferably uses with the amount of 4 mass parts ~ 12 mass parts scopes.

(5) various additive

Adhesive composition P, as required, normally used various additive, such as silane coupling agent, antistatic agent, tackifier, antioxidant, UV light absorber, photostabilizer, softening agent, weighting agent, refractive index adjusters etc. in acrylic-based adhesives can be added on.

Particularly from the viewpoint of improving weather resistance, preferably in adhesive composition P, add silane coupling agent as additive.As silane coupling agent, at least having the silicoorganic compound of an alkoxysilyl in molecule, be preferably the good person of consistency with (methyl) acrylate copolymer (A).In addition, during the situation of adhesive sheet 1 for optical applications, preferably there is the silane coupling agent of photopermeability.

As described silane coupling agent, such as, vinyltrimethoxy silane can be listed, vinyltriethoxysilane, the silicon compound containing polymerizability unsaturated group of methyl allyl acyloxypropyl trimethoxysilane etc., 3-(2,3-glycidoxy) propyl trimethoxy silicane, the silicon compound with epoxy construction of 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane etc., 3-mercaptopropyi Trimethoxy silane, 3-Mercaptopropyltriethoxysilane, the silicon compound containing sulfydryl of 3-mercaptopropyi dimethoxymethylsilane etc., 3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330, the silicon compound containing amino of N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane etc., 3-r-chloropropyl trimethoxyl silane, 3-isocyanic ester propyl-triethoxysilicane, or at least one in these and Union carbide A-162, ethyl triethoxysilane, methyltrimethoxy silane, the condenses etc. of the silicon compound containing alkyl of ethyl trimethoxy silane etc.These can be used alone one, also can be used in combination of two or more.

The addition of silane coupling agent, relative to (methyl) acrylate copolymer (A) 100 mass parts, is preferably 0.01 mass parts ~ 1.0 mass parts, is particularly preferably 0.05 mass parts ~ 0.5 mass parts.

(6) manufacture of adhesive composition

Adhesive composition P can by manufacturing (methyl) acrylate copolymer (A), obtained (methyl) acrylate copolymer (A), active energy ray-curable composition (B) are mixed with linking agent (C), simultaneously, as required, interpolation Photoepolymerizationinitiater initiater (D) and/or additive manufacture.

(methyl) acrylate copolymer (A), can by manufacturing by the polymerization of mixtures of common radical polymerization by the monomer forming polymkeric substance.The polymerization of (methyl) acrylate copolymer (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 be used together two or more.

As polymerization starter, can azo compound, organo-peroxide etc. be enumerated, can use two or more simultaneously.As azo compound, can 2 be enumerated, 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, isopropyl benzene hydroperoxide, 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) acrylate copolymer (A), in the solution of (methyl) acrylate copolymer (A), add active energy ray-curable composition (B), linking agent (C) and add Photoepolymerizationinitiater initiater (D), additive as required, fully mix, obtain adhesive composition P.

(7) formation of bond layer

Bond layer 11 formed by adhesive composition P heat cross-linking.That is, the crosslinked of adhesive composition P is undertaken by heat treated.In addition, this heat treated also can be also used as adhesive composition P be coated with after drying treatment.

The Heating temperature of heat treated 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, be particularly preferably 50 seconds ~ 2 minutes.After heat treated, can as required, during under normal temperature (such as, 23 DEG C, 50%RH), the maturation of about 1 ~ 2 week is set.During situation during needing maturation, after during maturation, form bond layer; During situation during not needing maturation, heat treated terminates rear formation bond layer.

By above-mentioned heat treated (and maturation), via linking agent (C), (methyl) acrylate copolymer (A) is cross-linked well.

The thickness (value based on JIS K7130 measures) of the bond layer 11 formed is 50 μm ~ 400 μm, is preferably 70 μm ~ 300 μm, is particularly preferably 90 μm ~ 250 μm.In addition, bond layer 11 can be formed by individual layer, also can by multilayer laminated and formed.

If the thickness of bond layer 11 is less than 50 μm, then cannot obtain sufficient concavo-convex following, if the thickness of bond layer 11 is more than 400 μm, then processibility reduces.

2. stripping film

As stripping film 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.

In the release surface (face particularly contacted with bond layer 11) of described stripping film 12a, 12b, preferably implement 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.In addition, in stripping film 12a, 12b, be preferably using the stripping film of side as the exfoliated stripping film of the weight that peeling force is large, the stripping film of opposite side is as the little light exfoliated stripping film of peeling force.

About the thickness of stripping film 12a, 12b, have no particular limits, but be generally 20 μm ~ about 150 μm.

3. the manufacture of adhesive sheet

As the example manufacturing adhesive sheet 1, in the release surface of a stripping film 12a (or 12b), be coated with the coating fluid of above-mentioned adhesive composition P, carry out heat treated, by adhesive composition P heat cross-linking, after forming coating layer, on this coating layer, the release surface of another stripping film 12b (or 12a) is overlapping.During situation during needing maturation, during maturation is set; During situation during not needing maturation, above-mentioned coating layer directly becomes bond layer 11.Thus, described adhesive sheet 1 is obtained.In addition, at this one-phase, active energy ray is not irradiated.

As another example manufacturing adhesive sheet 1, in the release surface of a stripping film 12a, be coated with the coating fluid of above-mentioned adhesive composition P, carry out heat treated, by adhesive composition P heat cross-linking, form coating layer, obtain the stripping film 12a with coating layer.In addition, in the release surface of another stripping film 12b, be coated with the coating fluid of above-mentioned adhesive composition P, carry out heat treated, by adhesive composition P heat cross-linking, form coating layer, obtain the stripping film 12b with coating layer.Afterwards, the stripping film 12a with coating layer is fitted with the mode that the stripping film 12b with coating layer contacts with each other with two coating layers.During situation during needing maturation, during maturation is set; During situation during not needing maturation, above-mentioned stacked coating layer directly becomes bond layer 11.Thus, described adhesive sheet 1 is obtained.According to this Production Example, when the situation that bond layer 11 is thicker, also manufacture can be stablized.

As the method for the coating fluid of the above-mentioned adhesive composition P 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.

4. physical property

Storage modulus after irradiating active energy ray to bond layer 11 at 23 DEG C, with the ratio (storage modulus of active energy ray postradiation storage modulus/active energy ray pre-irradiation) of the storage modulus of irradiating to bond layer 11 at first 23 DEG C of active energy ray, be preferably 1.1 ~ 10, be particularly preferably 1.2 ~ 7.In addition, the storage modulus in this specification sheets is based on JIS K7244-6, under mensuration frequency is 1Hz, by turning round the value that method of cutting measures.

As mentioned above, after active energy ray irradiates (after solidification), the storage modulus of bond layer 11 at 23 DEG C rises, then weather resistance and the concavo-convex following of the bond layer 11 solidified are all excellent.In addition, except described viewpoint, from the viewpoint of water soak resistance, the ratio of described storage modulus is particularly preferably 3 ~ 7.

In addition, storage modulus after irradiating active energy ray to bond layer 11 at 85 DEG C, with the ratio (storage modulus of active energy ray postradiation storage modulus/active energy ray pre-irradiation) of the storage modulus of irradiating to bond layer 11 at first 85 DEG C of active energy ray, be preferably 1.1 ~ 10, be particularly preferably 1.3 ~ 7.In addition, except described viewpoint, from the viewpoint of water soak resistance, the ratio of described storage modulus is particularly preferably 3 ~ 7.

As mentioned above, after active energy ray irradiates (after solidification), the storage modulus of bond layer 11 at 85 DEG C rises, even if the bond layer then solidified 11 at high temperature, weather resistance is also excellent.

If the ratio of the described storage modulus at 23 DEG C or 85 DEG C is less than 1.1, then has and cannot obtain the situation that weather resistance as above improves effect.On the other hand, if the ratio of the storage modulus at 23 DEG C or 80 DEG C is more than 10, then the bonding force of the bond layer 11 solidified reduces, and likely cannot obtain sufficient weather resistance.

The storage modulus of bond layer 11 at 23 DEG C of active energy ray pre-irradiation, is preferably 0.01MPa ~ 0.2MPa, is particularly preferably 0.04MPa ~ 0.15MPa, more preferably 0.07MPa ~ 0.1MPa.In addition, the storage modulus of bond layer 11 at 85 DEG C of active energy ray pre-irradiation, is preferably 0.01MPa ~ 0.1MPa, is particularly preferably 0.01MPa ~ 0.06MPa, more preferably 0.02MPa ~ 0.04MPa.The bond layer 11 of active energy ray pre-irradiation, by having storage modulus as above, concavo-convex following is excellent.

The storage modulus of the postradiation bond layer 11 of active energy ray at 23 DEG C, is preferably 0.02MPa ~ 2MPa, is particularly preferably 0.05MPa ~ 1MPa, more preferably 0.1MPa ~ 0.6MPa.In addition, the storage modulus of the postradiation bond layer 11 of active energy ray at 85 DEG C, is preferably 0.02MPa ~ 0.5MPa, is particularly preferably 0.02MPa ~ 0.2MPa, more preferably 0.03MPa ~ 0.1MPa.The postradiation bond layer 11 of active energy ray, by having storage modulus as above, weather resistance and water soak resistance excellence.

Above adhesive sheet 1, because the concavo-convex following of the bond layer 11 of active energy ray pre-irradiation is excellent, therefore in the irregular situation of adherend, be also difficult to occur space or bubbling between this concavo-convex and bond layer 11, bond layer 11 can fill up that this is concavo-convex.In addition, bond layer 11 is solidified by the irradiation of active energy ray, thus wet-heat resisting albefaction, weather resistance and water soak resistance are excellent.

The bond layer 11 of adhesive sheet 1 described in present embodiment, as described later, is preferably for by bonded to each other for two panels hard plate.

(duplexer)

As shown in Figure 2, duplexer 2 described in present embodiment, is made up of the 1st hard plate 21, the 2nd hard plate 22 and the bond layer 11 clamped by the 1st hard plate 21 and the 2nd hard plate 22 between them.In addition, in duplexer 2 described in present embodiment, the 1st hard plate 21 has concavo-convex on the face of bond layer 11 side, and specifically, it is concavo-convex that the presence or absence with printed layers 3 causes.

1st hard plate 21 and the 2nd hard plate 22, as long as be the material that bond layer 11 can be bonding, then have no particular limits.In addition, the 1st hard plate 21 and the 2nd hard plate 22 can be same material, also can be differing materials.

As the 1st hard plate 21 and the 2nd hard plate 22, such as, except sheet glass, plastic plate, metal sheet, semiconductor board etc., also can enumerate the hard product etc. of these duplexer or the tabular of display body assembly, solar module etc.Bond layer 11 in present embodiment, because water soak resistance is excellent, at least one of therefore preferably the 1st hard plate 21 and the 2nd hard plate 22 comprises plastic plate.

As described sheet glass, have no particular limits, such as, can enumerate chemically reinforced glass, non-alkali glass, silica glass, soda-lime glass, barium strontium glass, alumina silicate glass, lead glass, borosilicate glass, barium borosilicate glass etc.The thickness of sheet glass has no particular limits, but is generally 0.1mm ~ 5mm, is preferably 0.2mm ~ 2mm.

As described plastic plate, have no particular limits, such as, can enumerate acrylic board, polycarbonate plate etc.The thickness of plastic plate has no particular limits, but is generally 0.2mm ~ 5mm, is preferably 0.4mm ~ 3mm.

In addition, the one or both sides of described sheet glass or plastic plate, can arrange various functional layer (nesa coating, metal level, silicon dioxide layer, hard coat, anti-dazzle photosphere etc.), also can be formed with metal wiring, can also be laminated with optical component.

As described optical component, such as, can enumerate polarized light piece (polarizing film), polarizer, polarizer (phase-contrast film), field angle compensation film, improve brightness film, improve contrast gradient film, liquid crystal polymer film, diffusion film, hard coating film, semi-transparent semi-reflecting film etc.

In addition, as described display body assembly, such as, can enumerate liquid crystal (LCD) assembly, photodiode (LED) assembly, organic electroluminescent (organic EL) assembly, Electronic Paper etc.In addition, in these display body assemblies, described sheet glass, plastic plate, optical component etc. are usually laminated with.Such as, be laminated with polarized light piece in LCD assembly, this polarized light piece forms a side surface of LCD assembly.

In duplexer 2 described in present embodiment, preferably at least one of the 1st hard plate 21 and the 2nd hard plate 22 has polarized light piece.In addition, in duplexer 2 described in preferred present embodiment, the 2nd hard plate 22 is display body assembly or its part (such as, the optical component of polarized light piece etc.), and the 1st hard plate 21 is the protecting sheet be made up of plastic plate etc.Now printed layers 3 forms frame-shaped in bond layer 11 side of the 1st hard plate 21 usually.

The material forming printed layers 3 has no particular limits, and uses the known materials of printing.The thickness of printed layers 3, namely concavo-convex height is preferably 3 μm ~ 45 μm, is particularly preferably 5 μm ~ 35 μm, more preferably 7 μm ~ 25 μm, more preferably 7 μm ~ 15 μm.

In addition, the thickness (concavo-convex height) of printed layers 3, is preferably 3% ~ 30% of the thickness of bond layer 11, is particularly preferably 3.2% ~ 20%, more preferably 3.5% ~ 15%.Thus, bond layer 11 can really chase after from printed layers 3 cause concavo-convex, can not float near concavo-convex or bubble etc.

The bond layer 11 of duplexer 2 described in present embodiment, for by the bond layer 11 in above-mentioned adhesive sheet 1 by the irradiation of active energy ray solidification person.Here active energy ray refers to, hertzian wave or the intrafascicular person that has the quanta of energy of charged particle, specifically, can enumerate ultraviolet and electron beam etc.Also the ultraviolet handled particularly preferably is easy in active energy ray.

Ultraviolet irradiation is undertaken by high pressure mercury vapour lamp, Fusion H lamp, xenon lamp etc., and the preferred illumination of ultraviolet irradiation amount is 50mW/cm ²~ 1000mW/cm ²left and right.In addition, light quantity is preferably 50mJ/cm ²~ 10000mJ/cm ², particularly preferably 80mJ/cm ²~ 5000mJ/cm ², preferred 200mJ/cm further ²~ 2000mJ/cm ².On the other hand, the irradiation of electron beam is undertaken by electron-beam accelerator etc., and the irradiation dose of electron beam is preferably about 10krad ~ 1000krad.

Bond layer 11 to adhesive sheet 1 irradiates active energy ray, then active energy ray-curable composition (B) polymerizing curable.The bond layer 11 solidified by the irradiation of active energy ray, weather resistance, wet-heat resisting albefaction and water soak resistance are excellent.

When manufacturing described duplexer 2, as an example, first, peeled off by a slice stripping film 12a (or 12b) of adhesive sheet 1, the bond layer 11 adhesive sheet 1 exposed and the 1st hard plate 21 (or the 2nd hard plate 22) are fitted.Then, from the bond layer 11 of adhesive sheet 1, peeled off by another sheet stripping film 12b (or 12a), the bond layer 11 adhesive sheet 1 exposed and the 2nd hard plate 22 (or the 1st hard plate 21) are fitted.

Fit in above-mentioned operation bond layer 11 and the 1st hard plate 21 time, bond layer 11 due to concavo-convex following excellent, be difficult to produce space between the concavo-convex and bond layer 11 that printed layers 3 causes, bond layer 11 can fill up that this is concavo-convex.

Then, from the 1st hard plate 21 or the 2nd hard plate 22, any side, irradiates active energy ray to bond layer 11, bond layer 11 is solidified.Now, the hard plate irradiating active energy ray side is required to be active energy ray perviousness.

In above-mentioned duplexer 2, the concavo-convex following of the bond layer 11 due to active energy ray pre-irradiation is excellent, is difficult to produce space or bubble between the concavo-convex and bond layer 11 that printed layers 3 causes.In addition, the bond layer 11 solidified by the irradiation of active energy ray, the albefaction implementing after hot and humid condition, when returning to normal temperature is suppressed, and wet-heat resisting albefaction is excellent.In addition, irradiating this bond layer 11 of active energy ray, even if when implementing the situation of hot and humid condition, also can prevent concavo-convex neighbouring bubbling etc., excellent in te pins of durability.In addition, when at least one of 1st hard plate 21 and the 2nd hard plate 22 comprises plastic plate, even if this plastic plate is vented under the high temperature conditions, irradiate this bond layer 11 of active energy ray, water soak resistance is also excellent, the generation that therefore can suppress bubble or float, peel off.

For the wet-heat resisting albefaction of the excellence of the bond layer 11 solidified by irradiating active energy ray, can according to evaluating as follows.Such as, by the two sides of bond layer 11, clamp with the non-alkali glass that two panels thickness is 1.1mm, cross this non-alkali glass, at least irradiate the active energy ray of above-mentioned illumination and light quantity in side, obtain duplexer.By this duplexer 85 DEG C, keeping after 240 hours under the condition (wet heat condition) of 85%RH, 23 DEG C, take out under the ambient temperature and moisture of 50%RH.Now, the albefaction degree that can confirm described bond layer 11 is little.

The degree of described albefaction, carries out quantitative evaluation by haze value.Specifically, can according to the haze value (%) after the wet heat condition of described duplexer (based on the value that JIS K7136:2000 measures.As follows) deduct wet heat condition before the value (haze value rise) after wet heat condition of haze value (%) evaluate.Haze value after wet heat condition rises, and is preferably less than 5.0 points, is particularly preferably and is less than 1.0 points.In addition, in above-mentioned evaluation, as described non-alkali glass, haze value is preferably utilized to be almost 0%.In addition, the haze value of the bond layer after described wet heat condition, is preferably less than 1.0%, is particularly preferably less than 0.9%, more preferably less than 0.8%.

In addition, described bond layer 11 preferably total light penetration (value based on JIS K7361-1:1997 measures) is more than 80%, is particularly preferably more than 90%, more preferably more than 99%.If total light penetration is more than 80%, then transparent high, suitable to optical applications.In addition, total light penetration of bond layer 11 is usually almost constant after active energy ray pre-irradiation.

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 or equipollent that belong to technical scope of the present invention.

Such as, any one in stripping film 12a, 12b of adhesive sheet 1 can be omitted.In addition, the 1st hard plate 21, what can have beyond printed layers 3 is concavo-convex, also can not have concavo-convex.In addition, being not only the 1st hard plate the 21,2nd hard plate 22 also can have concavo-convex in bond layer 11 side.

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) acrylate copolymer

By 2-ethylhexyl acrylate 60 mass parts, methyl methacrylate 20 mass parts and the copolymerization of vinylformic acid 2-hydroxyethyl ester 20 mass parts, modulation (methyl) acrylate copolymer (A).Measure the molecular weight being somebody's turn to do (methyl) acrylate copolymer (A) by aftermentioned method, its result weight-average molecular weight is 600,000.

2. the modulation of adhesive composition

(methyl) acrylate copolymer (A) 100 mass parts (solids component scaled value that will obtain in above-mentioned operation (1), as follows), as polyethyleneglycol diacrylate (chemical company of the Xin Zhong village system of active energy ray-curable composition (B), trade(brand)name " NK ESTER A-400 ") 25 mass parts, as TriMethylolPropane(TMP) modified toluene vulcabond (the Japanese polyurethane industrial system of isocyanates linking agent (C), trade(brand)name " CORONATE L ") 0.23 mass parts, as the 3-(2 of silane coupling agent, 3-glycidoxy) propyl trimethoxy silicane (chemical industrial company of SHIN-ETSU HANTOTAI system, trade(brand)name " KBM-403 ") 0.2 mass parts, as 1-hydroxycyclohexylphenylketone (BASF AG's system of Photoepolymerizationinitiater initiater (D), trade(brand)name " IRUGACURE184 ") 0.5 mass parts mixing, stir fully, by diluting with methyl ethyl ketone, obtain the coating solution that solid component concentration is the adhesive composition of 33 quality %.

At this, the proportioning 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) acrylate copolymer]

2EHA: 2-ethylhexyl acrylate

BA: n-butylacrylate

MMA: methyl methacrylate

HEA: vinylformic acid 2-hydroxyethyl ester

AA: vinylformic acid

[active energy ray-curable composition]

A400: polyethyleneglycol diacrylate (chemical company of Xin Zhong village system, trade(brand)name " NK ESTER A-400 ")

A9300-1CL: 6-caprolactone modification three-(2-acryloyl-oxyethyl) isocyanuric acid ester (chemical company of Xin Zhong village system, trade(brand)name " A-9300-1CL ")

[linking agent]

TDI: TriMethylolPropane(TMP) modified toluene vulcabond (Japanese polyurethane industrial system, trade(brand)name " CORONATE L ")

Epoxy: 1,3-pair (N, N '-diglycidyl amino methyl) hexanaphthene (gas chemical company of Mitsubishi system, trade(brand)name " TETRAD-C ")

3. the manufacture of adhesive sheet

By the coating solution of obtained adhesive composition, by pet film face, the exfoliated stripping film of weight (the Lin get Ke Inc. of lift-off processing has been carried out with silicone stripper, trade(brand)name " SP-PET752150 ") lift-off processing face on, be coated with Scraper applicator, make dried thickness be after 100 μm, at 100 DEG C, carry out 4 minutes heat treated and form coating layer.Equally, by the coating solution of obtained adhesive composition, by pet film face, light exfoliated stripping film (the Lin get Ke Inc. of lift-off processing has been carried out with silicone stripper, trade(brand)name " SP-PET382120 ") lift-off processing face on, be coated with Scraper applicator, make dried thickness be after 100 μm, at 100 DEG C, carry out 4 minutes heat treated and form coating layer.

Then, the mode that the exfoliated stripping film of weight with coating layer obtained above and the light exfoliated stripping film having coating layer obtained above contact with each other according to both sides coating layer is fitted, 23 DEG C, carry out maturation in 7 days under the condition of 50%RH, manufacture and form formed adhesive sheet by heavy exfoliated stripping film/bond layer (thickness: 200 μm)/light exfoliated stripping film.In addition, the thickness of bond layer is based on JIS K7130, uses level pressure thickness tester (TECLOCK Inc., trade(brand)name " PG-02 ") to carry out the value measured.

(embodiment 2 ~ 4, comparative example 1 ~ 3)

Except the use level of the kind of the ratio of each monomer by forming (methyl) acrylate copolymer (A), the weight-average molecular weight of (methyl) acrylate copolymer (A), the kind of active energy ray-curable composition (B) and use level, linking agent (C) and use level, Photoepolymerizationinitiater initiater (D), the use level of silane coupling agent and the thickness of bond layer change according to table 1, operate similarly to Example 1, manufacture adhesive sheet.

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

■ measures solvent: tetrahydrofuran (THF)

■ measures temperature: 40 DEG C

(test example 1) (mensuration of storage modulus)

In the adhesive sheet obtained from embodiment or comparative example, light exfoliated stripping film and heavy exfoliated stripping film are peeled off, carries out multilayer laminated, make the thickness of bond layer be 0.6mm.From the duplexer of obtained bond layer, stamp out the right cylinder (highly: 0.6mm) that diameter is 8mm, it can be used as sample (sample before uviolizing).

For above-mentioned sample, based on JIS K7244-6, using determination of viscoelasticity device (Physica Inc., MCR300), measuring storage modulus (MPa) under the following conditions according to turning round the method for cutting.

Measure frequency: 1Hz

Measure temperature: 23 DEG C, 85 DEG C

In addition, to sample same as described above, by using UV irradiation equipment (EYE GRAPHIC Inc., trade(brand)name " EYE GRANTAGE ECS-401GX type "), irradiation ultraviolet radiation under the following conditions, solidifies bond layer, obtains the sample after uviolizing.To the sample after obtained uviolizing, operate in the same manner as the sample before uviolizing, measure storage modulus (MPa).

[uviolizing condition]

■ light source: high pressure mercury vapour lamp

■ light quantity: 1000mJ/cm ²

■ illumination: 200mW/cm ²

By said determination result, calculate respectively at 23 DEG C and 85 DEG C, the storage modulus after uviolizing, with the ratio (storage modulus before the storage modulus/uviolizing after uviolizing) of the storage modulus before uviolizing.These measurement results and calculation result are shown in table 2.

(test example 2) (processibility evaluation)

In the adhesive sheet obtained from embodiment or comparative example, light exfoliated stripping film is peeled off, the stripping situation of now light exfoliated stripping film is evaluated with the form of processibility.By light exfoliated stripping film from bond layer smoothly stripping person be evaluated as processibility good (zero), processibility bad (×) will be evaluated as with bond layer breakage person during light exfoliated stripping film stripping.Show the result in table 2.

(test example 3) (wet-heat resisting albefaction evaluation)

By the bond layer of adhesive sheet obtained in embodiment or comparative example, clamp with the non-alkali glass that two panels thickness is 1.1mm, cross the glass of side, with the uviolizing condition of test example 1, irradiation ultraviolet radiation, obtains duplexer.To this duplexer, use haze measurement meter (Japanese electricity Se industrial system, trade(brand)name " NDH2000 "), measure haze value (%) based on JIS K7136:2000.

Then, by described duplexer 85 DEG C, keeping 240 hours under the wet heat condition of 85%RH.Afterwards, return to 23 DEG C, the ambient temperature and moisture of 50%RH, to this duplexer, use haze measurement meter (Japanese electricity Se industrial system, trade(brand)name " NDH2000 "), measure haze value (%) based on JISK7136:2000.In addition, measure within after duplexer is returned to ambient temperature and moisture 30 minutes of this haze value.

According to the above results, from the haze value after wet heat condition, deduct the haze value before wet heat condition, calculate the haze value after wet heat condition and rise (counting).Haze value after wet heat condition is risen be less than 1.0 be evaluated as wet-heat resisting albefaction good (zero), wet heat condition after haze value rise be greater than 1.0 be less than 5.0 be evaluated as wet-heat resisting albefaction in appropriate value after (Δ), wet heat condition haze value be increased beyond 5.0 be evaluated as wet-heat resisting albefaction bad (×).Show the result in table 2.

(test example 4) (concavo-convex following ■ endurance test)

The making of (a) sample for evaluation

In sheet glass (NSG PRECISION Inc., trade(brand)name " corning; EAGLE XG ", longitudinal 90mm × horizontal 50mm × thickness 0.5mm) surface, by ultraviolet hardening ink (ink Inc. of kingdom, trade(brand)name " POS-911 ink ") silk screen printing is frame-shaped (profile: longitudinal 90mm × horizontal 50mm, width 5mm), makes coating thickness be 8 μm and 15 μm.Then, irradiation ultraviolet radiation (80W/cm ²metal halide lamp 2, lamp height 15cm, belt speed 10m/ minute ~ 15m/ minute), by the above-mentioned ultraviolet hardening ink solidification of printing, make the attached irregular sheet glass having and print concavo-convex (the concavo-convex height: 8 μm and 15 μm) that cause.

By the adhesive sheet obtained in embodiment or comparative example, be cut into the shape of longitudinal 90mm × horizontal 50mm, by light exfoliated stripping film removing, expose bond layer.Then, use laminating machine (Fujipla Inc., trade(brand)name " LPD3214 "), according to the mode making bond layer cover whole for the printing of frame-shaped, and adhesive sheet is pressed on attached irregular sheet glass.

After above-mentioned lamination, exfoliated stripping film will be weighed peel off, in the caking agent aspect exposed, by sheet glass (NSG PRECISION Inc., trade(brand)name " corning, EAGLE XG ", longitudinal 90mm × horizontal 50mm × thickness 0.5mm), use described laminating machine laminating, make sample for evaluation.

B () concavo-convex following (initial stage) is evaluated

By the sample for evaluation obtained, with the autoclave of Li Yuan manufacturing company, in 0.5MPa, pressurization 30 minutes at 50 DEG C.Then, visual confirmation bond layer (particularly printed layers cause concavo-convex near) whether have bubble.Its result, will not have the alveolate ◎ of being evaluated as completely, almost and be not alveolately evaluated as zero, be alveolately evaluated as × (the concavo-convex following evaluation at initial stage).Show the result in table 2.

C () weather resistance (resistance to concavo-convex following long afterwards) is evaluated

Then, by described sample for evaluation (1) and (2), 85 DEG C, keeping 240 hours under the wet heat condition of 85%RH.Afterwards, visual confirmation bond layer (particularly printed layers cause concavo-convex near) on whether have bubble.Its result, will not have the alveolate ◎ of being evaluated as completely, almost and be not alveolately evaluated as zero, be alveolately evaluated as × (weather resistance (resistance to concavo-convex following long afterwards) evaluation).Show the result in table 2.

(test example 5) (total light penetration mensuration)

The bond layer of the adhesive sheet obtained in embodiment or comparative example is fitted in glass, it can be used as test sample.After glass carries out background detection, to said determination sample, based on JIS K7361-1:1997, use haze measurement meter (Japanese electricity Se industrial system, NDH-2000), total light penetration (%) is measured.Show the result in table 2.

(test example 6) (water soak resistance evaluation)

Prepare by sputtering be provided with on one face the nesa coating be made up of tin-doped indium oxide (ITO), thickness is the pet film (tail vat industrial system, ito thin film) of 125 μm.

By the bond layer of adhesive sheet obtained in embodiment or comparative example, by polycarbonate plate (gas chemical company of the Mitsubishi system that the nesa coating of described ito thin film and thickness are 1mm, trade(brand)name " IUPILON ■ SHEET MR58 ") clamping, through polycarbonate plate, irradiation ultraviolet radiation under the uviolizing condition of test example 1, obtains duplexer.

By the duplexer obtained, 50 DEG C, carry out the autoclaving process of 30 minutes under the condition of 0.5MPa after, place 15 hours.Then, 85 DEG C, keeping 72 hours under the durable condition of 85%RH.Afterwards, whether visual confirmation bond layer there is bubble or float, peel off.Its result, by there is no bubble completely or float, peel off be evaluated as ◎, almost there is no bubble or float, peel off be evaluated as zero, bubbling or float, peel off be evaluated as ×.(water soak resistance evaluation).Show the result in table 2.

[table 1]

[table 2]

As shown in Table 2, adhesive sheet obtained in an embodiment, excellent in workability.In addition, bond layer obtained in an embodiment, before uviolizing, concavo-convex following is excellent, and after uv irradiation, wet-heat resisting albefaction, weather resistance and water soak resistance are also excellent.

Industrial utilizability

Adhesive sheet of the present invention is suitable for and such as display body assembly, the irregular protecting sheet of tool, particularly with the laminating of plastic plate.

Nomenclature

1 ... adhesive sheet

11 ... bond layer

12a, 12b ... stripping film

2 ... duplexer

21 ... 1st hard plate

22 ... 2nd hard plate

3 ... printed layers

Claims

1. an adhesive sheet, it has and to be made up of adhesive composition heat cross-linking, thickness is the bond layer of 50 μm ~ 400 μm, described adhesive composition contains (methyl) acrylate copolymer (A), active energy ray-curable composition (B) and linking agent (C), the weight-average molecular weight of described (methyl) acrylate copolymer (A) is 200,000 ~ 900,000, contain 5 quality % ~ 20 quality % as forming the monomeric unit of polymkeric substance there is the monomer that the monomer of carboxyl or 15 quality % ~ 30 quality % have hydroxyl, and the content of described active energy ray-curable composition (B) relative to described (methyl) acrylate copolymer (A) 100 mass parts be 10 mass parts ~ 50 mass parts.

2. adhesive sheet according to claim 1, it is characterized in that, in described adhesive composition, the content of described linking agent (C), relative to described (methyl) acrylate copolymer (A) 100 mass parts, it is 0.01 mass parts ~ 5 mass parts.

3. adhesive sheet according to claim 1, is characterized in that, the storage modulus after irradiating active energy ray to described bond layer at 23 DEG C, with irradiate active energy ray to described bond layer before the ratio of storage modulus at 23 DEG C be 1.1 ~ 10.

4. adhesive sheet according to claim 1, is characterized in that, the storage modulus after irradiating active energy ray to described bond layer at 85 DEG C, with irradiate active energy ray to described bond layer before the ratio of storage modulus at 85 DEG C be 1.1 ~ 10.

5. adhesive sheet according to claim 1, is characterized in that, described adhesive sheet possesses two panels stripping film, and described bond layer is clamped by described stripping film in the mode connected with the release surface of described two panels stripping film.

6. a duplexer, it is characterized in that, it possesses two panels hard plate and by the bond layer of described two panels hard plate clamping, and the solidification of the bond layer of the adhesive sheet in Claims 1 to 5 described in any one forms for the irradiation by active energy ray by described bond layer.

7. duplexer according to claim 6, is characterized in that, at least one of described hard plate, the face of described bond layer side has concavo-convex.

8. duplexer according to claim 7, is characterized in that, described concavo-convex for printed layers concavo-convex with or without what cause.

9. duplexer according to claim 6, is characterized in that, at least one of described hard plate comprises polarized light piece.

10. duplexer according to claim 6, is characterized in that, at least one of described hard plate comprises plastic plate.

11. duplexers according to claim 6, is characterized in that, a slice of described two panels hard plate is display body assembly or its part, and another sheet of described two panels hard plate is on the face of described bond layer side, have the concavo-convex protecting sheet of frame-shaped.

12. duplexers according to claim 6, is characterized in that, total light penetration of described bond layer is more than 80%.