KR20110050711A

KR20110050711A - Photocurable resin composition for laminating optically functional material

Info

Publication number: KR20110050711A
Application number: KR1020117007564A
Authority: KR
Inventors: 에이시 카타카미
Original assignee: 교리쯔 가가꾸 산교 가부시키가이샤
Priority date: 2008-09-05
Filing date: 2009-09-04
Publication date: 2011-05-16
Also published as: JP2014095080A; CN103589347A; KR101805275B1; KR20140048346A; TW201026801A; KR101643511B1; CN102144009B; KR101823196B1; WO2010027041A1; KR20150038553A; CN102144009A; JP5563983B2; TWI485214B; JP5947275B2; KR20150038554A; JPWO2010027041A1

Abstract

SUMMARY OF THE INVENTION An object of the present invention is to provide bubbles by providing sufficient adhesiveness when bonding a decorative plate or an icon sheet onto a touch panel, or when bonding a transparent substrate and a transparent plate on which a transparent electrode is formed in a capacitive touch panel. When the photocurable adhesive composition which can be bonded without inclusion or the display body and the optical functional material are bonded together, the photocurable type for bonding the display body and the optical functional material, in which the adhesive surface is not peeled off or the glass of the display is not broken. Provided is a resin composition. The present invention includes (A) a polyisoprene, a polybutadiene or a (meth) acrylate oligomer having a polyurethane in a skeleton, and (B) a softening component, and (C) phenoxyethyl (meth) acrylate, if necessary. , (Meth) acrylate monomers (C1) or thiol compounds selected from phenoxypolyethylene glycol (meth) acrylates, 2-hydroxy-3-phenoxypropyl (meth) acrylates, and cyclohexyl (meth) acrylates; It is the said photocurable resin composition in which the elasticity modulus and the elongation at break of the photocurable adhesive composition and hardened | cured material containing C2) exist in a fixed range.

Description

Photocurable resin composition for bonding optically functional materials {PHOTOCURABLE RESIN COMPOSITION FOR LAMINATING OPTICALLY FUNCTIONAL MATERIAL}

The present invention provides a photocurable adhesive composition for bonding a touch panel comprising a (meth) acrylate oligomer and a softening component having polyisoprene, polybutadiene or polyurethane in a skeleton, the (meth) acrylate oligomer, a softening component and a specific (meth A photocurable adhesive composition comprising an acrylate monomer or a thiol compound, the cured product having a specific elastic modulus and elongation at break, and a touch panel or a display panel bonded thereto.

The touch panel mounted on a display such as an LCD includes a resistive film type, a capacitive type, an electromagnetic induction type, an optical type, and the like. On these touch panels, there may be a case where an icon sheet such as a decorated plate for designing the appearance of the exterior and a designation of a touch position are bonded. In addition, the capacitive touch panel has a structure in which a transparent electrode is formed on a transparent substrate and a transparent plate is bonded thereon.

Conventionally, bonding of the above-mentioned makeup plate and a touch panel, bonding of an icon sheet and a touch panel, and bonding of the transparent substrate and the transparent plate which formed the transparent electrode in the capacitive touch panel using the sheet-shaped double-sided adhesive sheet It carried out by carrying out adhesive processing on one side of a to-be-adhered body. In the technique using such an adhesive material, there existed a problem that adhesiveness was inadequate or a bubble mixed in a joining surface. In particular, when the bonding surface has been printed, there is a problem that bubbles are likely to remain in the stepped portion between the printed portion and the unprinted portion.

In recent years, the glass of display bodies such as LCDs has become thinner. Thinner glass tends to deform the LCD due to external stress. When bonding display bodies, such as LCD of this thin glass, and optical functional materials, such as an acryl plate and a polycarbonate plate, of the difference of linear expansion, such as glass and an acryl, and plastic molding materials, such as an acryl plate and a polycarbonate, Distortion during molding causes relaxation of molding distortion and moisture absorption / drying in the heat resistance test and the moisture resistance test, and changes in surface precision such as dimensional change and warpage occur. In the case of trying to suppress this deformation in the conventional adhesive (for example, patent document 1), there existed a problem that an adhesive surface peeled off, an LCD broke, or the display unevenness of LCD became.

Japanese Patent Laid-Open No. 2004-77887

Therefore, the subject of this invention is providing sufficient adhesiveness and foaming, when bonding a decorative board and an icon sheet on a touch panel, or when bonding a transparent substrate and a transparent plate which formed the transparent electrode in the capacitive touch panel. Of the adhesive composition which solves the problems of the prior art that it is difficult to bond without including or to the case where the display body and the optically functional material are bonded, whereby the adhesive surface is peeled off or the glass of the display is broken. Is provided.

In the photocurable adhesive composition, the present inventors include a (meth) acrylate oligomer and a softening component having polyisoprene, polybutadiene or polyurethane in the skeleton, or further specific to the (meth) acrylate oligomer and the softening component ( By containing a meth) acrylate monomer or a thiol compound and making the elastic modulus and elongation at break of the hardened | cured material into a specific range, it discovered that the said subject was achieved and completed this invention.

1st this invention is the photocurable adhesive composition for touch panel adhesion | attachment containing the (meth) acrylate oligomer which has (A) polyisoprene, polybutadiene, or polyurethane in frame | skeleton, and (B) softening component.

Moreover, this invention is a bonded body of the transparent substrate in which the transparent electrode in the capacitive touch panel bonded with the above-mentioned photocurable adhesive composition for touch panel adhesion, or a transparent plate, or a bonded body of a touch panel, a sheet | seat or a board is carried out. .

2nd this invention is (A) polyisoprene, polybutadiene, or (meth) acrylate oligomer which has a polyurethane in frame | skeleton, (B) softening component, (C1) phenoxyethyl (meth) acrylate, phenoxy polyethyleneglycol ( Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, nonylphenol EO adduct (meth) acrylate, methoxytriethylene glycol (meth) acrylate And a (meth) acrylate monomer selected from tetrahydrofurfuryl (meth) acrylate, wherein the photocurable resin composition for bonding the indicator to the optically functional material has an elastic modulus of less than 12 kPa and a breakage of the cured product. Time elongation is 300% or more, It is a photocurable resin composition characterized by the above-mentioned.

3rd this invention joins the display body and optical function material containing (A) polyisoprene, polybutadiene, or a (meth) acrylate oligomer which has a polyurethane in frame | skeleton, (B) softening component, and (C2) thiol compound As a photocurable resin composition for following, the elasticity modulus of hardened | cured material is less than 10 kPa, and elongation at break of hardened | cured material is 300% or more, It is a photocurable resin composition characterized by the above-mentioned. The modulus of elasticity of the cured product is preferably 1 kPa or more, and the elongation at break of the cured product is preferably 1000% or less.

Moreover, this invention is a display panel containing the display body and optical functional material bonded by said 2nd or 3rd photocurable resin composition.

According to the first aspect of the present invention, when bonding a decorative plate or an icon sheet onto a touch panel or bonding a transparent substrate and a transparent plate on which a transparent electrode is formed in a capacitive touch panel, bubbles are not included with sufficient adhesive force. It can be joined without.

According to the second and third inventions, when the display body and the optical functional material are bonded together, the adhesive surface is not peeled off or the glass of the display body is broken.

First invention

Component (A) of the present invention is a (meth) acrylate oligomer having polyisoprene, polybutadiene or polyurethane in the skeleton. These (meth) acrylate oligomers can use 1 type (s) or 2 or more types.

The (meth) acrylate oligomer which has polyisoprene in frame | skeleton is also called (meth) acryl modified polyisoprene, Preferably it has a molecular weight of 1000-100000, More preferably, it is 100000-500000. As a commercial item, there exists "UC-1" (molecular weight 25000) by Kuraray Corporation, for example.

The (meth) acrylate oligomer having polybutadiene in the skeleton is also called (meth) acryl modified polybutadiene, and preferably has a molecular weight of 500 to 100000, more preferably 1000 to 30000. As a commercial item, there exists "TE2000" (molecular weight 2000) by the Nippon Seki-Yu company.

The (meth) acrylate oligomer which has a polyurethane in frame | skeleton is also called a (meth) acryl modified polyurethane, Preferably it has a molecular weight of 1000-100000, More preferably, 10000-50000. As a commercial item, the light chemical company "UA-1" is mentioned, for example.

As the (meth) acrylate oligomer of component (A), the (meth) acrylate oligomer which has polyisoprene in frame | skeleton is especially preferable.

Component (B) of the present invention is a softening component. Examples of the softening component include polymers, oligomers, phthalic acid esters, castor oils, and the like that are compatible with the component (A). As an oligomer or a polymer, polyisoprene type, polybutadiene type, or xylene type oligomer or polymer can be illustrated. These softening components are commercially available as LIR series by Kuraray and polyyl series by Degussa. These softening components can use 1 type (s) or 2 or more types.

In the photocurable adhesive composition for touch panel bonding of the present invention, with respect to 100 parts by mass of the component (A), the component (B) is preferably 10 to 400 parts by mass, more preferably 50 to 300 parts by mass, most preferably Is 100 to 300 parts by mass.

It is preferable that the photocurable adhesive composition for touch panel adhesion of this invention contains (C) specific (meth) acrylate monomer (C1) or thiol compound (C2) further.

Specific (meth) acrylate monomer (C1) is phenoxyethyl (meth) acrylate (PO), phenoxy polyethylene glycol (meth) acrylate, 2-hydroxy-3- phenoxypropyl (meth) acrylate, Cyclohexyl (meth) acrylate (CH), nonylphenol EO adduct (meth) acrylate, methoxytriethylene glycol (meth) acrylate and tetrahydrofurfuryl (meth) acrylate. These (meth) acrylate monomers can use 1 type (s) or 2 or more types. Component (C1) is a component for imparting elongation to the cured product.

Component (C2) of the present invention is a thiol compound. As a thiol compound, For example, tricapsyl mercaptopropionate, methoxy butyl mercaptopropionate, octyl mercaptopropionate, trimethylol propane tristyoprioionionate, pentaerythritol tetrakistyropropionate, dipentaerythritol hexakiss (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate, 3-mercaptobutyrate derivative, etc. can be illustrated. These thiol compounds can use 1 type (s) or 2 or more types.

Component (C2) is preferably a 3-mercaptobutyrate derivative, for example 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxy Ethyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate), trimethylolpropanetris (3-mer Captopropionate), and the like. These thiol compounds are commercially available from Showa Denko Co., Ltd. under the trade names: TMMP, from Carens MT BD1, from Carenz MT PE1, from Carenz MT NR1, and from Kagaku Corporation.

In the photocurable adhesive composition for touch panel bonding of the present invention, the component (C1) is preferably 1 to 100 parts by mass, and more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the component (A). The component (C2) is preferably 0.05 to 100 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A).

The photocurable adhesive composition for touch panel adhesion of the present invention may contain a general (meth) acrylate monomer other than component (C1) as a reaction diluent when the compatibility of the component is poor or when the viscosity is high and the workability is poor. Can be. As a general (meth) acrylate monomer, For example, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, la Uryl (meth) acrylate, alkyl (meth) acrylate, methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, hydroxide Oxyethyl (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6- Hexanedioldi (meth) acrylate, dicyclopentenyloxyethyl (meth) There can be mentioned a methacrylate, norbornene (meth) acrylate. These (meth) acrylates can use 1 type (s) or 2 or more types.

The photocurable adhesive composition for adhesion of a touch panel of the present invention may further include a photoinitiator. As a photoinitiator, a general initiator can be used, for example, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-hydrate Oxycyclohexyl-phenyl-ketone, benzophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6 -Trimethylbenzoylphenylethoxyphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1-phenyl-propane-1 -One, 2-methyl-1- [4-methylthio] phenyl] -2-morpholinopropane-1-one, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether , Bis (2,4,6-trimethylbenzoyl) -phenylphosphineoxide, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, 2-hydroxy-2-methyl-1-phenyl-1-propanone, isopropyl thioxanthone, o Methyl benzoylbenzoate, [4- (methylphenylthio) phenyl] phenylmethane, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, benzophenone, ethyl anthraquinone, benzophenone ammonium salt, thioxanthone ammonium salt, Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphineoxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2, 4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4'-bisdiethylaminobenzophenone, 1,4-dibenzoylbenzene, 10-butyl-2-chloroacridone, 2,2 'bis (o-chlorophenyl) 4,5,4 ', 5'-tetrakis (3,4,5-trimethoxyphenyl) 1,2'-biimidazole, 2,2'-bis (o-chlorophenyl 4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyldiphenyl ether, acrylated benzophenone, bis (η 5-2 , 4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, o-methylbenzoylbenzoate, p-dimethylaminobenzo Examples thereof include ethyl ester, p-dimethylaminobenzoic acid isoamyl ethyl ester, active tertiary amine, carbazole-phenone photopolymerization initiator, acridine photopolymerization initiator, triazine photopolymerization initiator, benzoyl photopolymerization initiator and the like. Can be. One kind or two or more kinds of these photoinitiators can be used. The quantity of a photoinitiator is 0.1-10 mass parts with respect to 100 mass parts of component (A).

In the present invention, preferred photoinitiators include 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide and 1-hydroxycyclohexyl-phenyl-ketone, each of which may be used alone or in combination. It may be.

The photocurable adhesive composition of the present invention may further contain a tackifier. As the tackifier, a silane coupling agent such as vinyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy Propylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N- 2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane , 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasul Feed, 3-isocyanate propyl triethoxysilane, etc. can be illustrated. One kind or two or more kinds of these tackifiers can be used. The quantity of a tackifier is 0.01-10 mass parts with respect to 100 mass parts of components (A), Preferably it is 0.5-5 mass parts.

The photocurable adhesive composition of this invention may contain antioxidant further. Antioxidants include BHT, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, penta Eritrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di- t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexane Diol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamid), 1,3,5-trimethyl-2,4,6-tris ( 3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, octylated diphenylamine, 2, 4, -bis [(octylthio) methyl] -O-cresol, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, dibutylhydroxy Cytoluene can be illustrated. These antioxidants can be used by 1 type, or 2 or more types. The quantity of antioxidant is 0.01-10 mass parts with respect to 100 mass parts of components (A), Preferably it is 0.5-5 mass parts.

When light does not reach a part of the adhesive composition apply | coated to the adhesive surface by the structure of an optical function material, the photocurable adhesive composition of this invention hardens the place where light reached by light, and light does not reach The place can be made into the adhesive composition of the combined type of photocuring and thermosetting which adds an organic peroxide and hardens | cures by heat. Examples of the organic peroxides include ketone peroxides, peroxy ketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like. These organic oxides may be used alone or in combination of two or more. These organic oxides can be used 1 type, or 2 or more types, and the quantity is 0.1-10 mass parts with respect to 100 mass parts of component (A), Preferably it is 1-5 mass parts.

Moreover, as a hardening accelerator of these organic peroxides, a naphthenate metal complex, dimethylaniline, a quaternary ammonium salt, and phosphate ester can be used.

It is preferable that the photocurable adhesive composition of this invention is an adhesive agent for bonding the transparent substrate in which a transparent electrode is formed, and a transparent plate in a capacitive touch panel. The material of a transparent substrate is glass, PC, PMMA, the composite of PC and PMMA, COC, COP, for example. The material of a transparent plate is glass, PC, PMMA, the composite of PC and PMMA, COC, COP, for example.

It is preferable that the photocurable adhesive composition of this invention is an adhesive agent for bonding a touch panel and a sheet or a plate thereon. Examples of the sheet include an icon sheet, a protective sheet, and a makeup sheet, and the materials thereof are, for example, PET, PC, COC, and COP. As a board | plate, there are a makeup plate and a protective plate, for example, The material is PET, glass, PC, PMMA, the composite of PC and PMMA, COC, COP, for example. The material of the touch panel surface to be bonded to the sheet or plate is, for example, glass, PET, PC, PMMA, a composite of PC and PMMA, COC, and COP.

The present invention also relates to a bonded body of a transparent substrate and a transparent plate, or a bonded body of a touch panel and a sheet or a plate, on which a transparent electrode in a capacitive touch panel bonded with the photocurable adhesive composition described above is formed.

2nd invention

Specific examples of component (A), component (B) and component (C1) of the present invention are as described in the first invention.

The photocurable resin composition of this invention is for bonding a display body and an optical function material. As a display body, display elements, such as LCD, an EL display, EL illumination, an electronic paper, and a plasma display with a polarizing plate attached to glass, are mentioned. Optically functional materials include acrylic plates (may be treated with one or two-sided hard coating or AR coating), polycarbonate plates, PET plates, and PEN plates for the purpose of improving visibility and preventing cracking of display elements from external impacts. Transparent plastic boards, such as tempered glass (the shatterproof film may be attached), a touch panel input sensor, etc. are mentioned.

In the photocurable resin composition of this invention, the elasticity modulus of the hardened | cured material is less than 12 kPa, and elongation at the time of breaking of hardened | cured material is 300% or more. When the cured product has such an elastic modulus and elongation at break, the photocurable resin composition of the present invention, when the display body and the optical functional material are bonded together, the adhesive surface is peeled off, the glass of the display is broken, or the display is uneven. There is no case. The elastic modulus and elongation at break of the cured product can be measured by the method described in Examples described later.

In this invention, it is preferable that the elasticity modulus of hardened | cured material is 1 kPa or more and less than 12 kPa, and it is preferable that elongation at the time of breaking of hardened | cured material is 300% or more and 700% or less.

In the photocurable resin composition of the present invention, the initial transmittance of light of 400 to 800 nm in the cured product is 95% or more, the transmittance is 70% or more after standing at 60 ° C. and 90% humidity for 500 hours, and at 500 ° C. at 500 ° C. It is preferable that the transmittance is 90% or more after standing for a time.

It is preferable that the refractive index of the hardened | cured material of the photocurable resin composition of this invention is 1.45-1.55.

In the photocurable resin composition of the present invention, when the amount ratio of the component (C1) to the component (A) is increased, the elastic modulus of the cured product can be lowered, the elongation at break of the cured product can be increased, and the Increasing the amount ratio can lower the elastic modulus of the cured product. Therefore, by adjusting the compounding ratio of component (A), component (B), and component (C1), desired elastic modulus and elongation at break can be provided to hardened | cured material.

The photocurable resin composition of the present invention is preferably 100 parts by mass of the (meth) acrylate oligomer of (A), 100 to 400 parts by mass of the softening component of (B), preferably 100 to 300 parts by mass and ( 1 to 100 parts by mass, preferably 5 to 50 parts by mass of the (meth) acrylate monomer of C1).

More preferably, the photocurable resin composition of this invention uses polyisoprene methacrylate oligomer (100 mass parts) as an oligomer of component (A), and liquid polybutadiene (10-300 mass parts) as a softening component of component (B). , Preferably 50 to 200 parts by mass) and / or polyisoprene (10 to 300 parts by mass, preferably 50 to 200 parts by mass) and cyclohexyl methacrylate (1) as the (meth) acrylic monomer of component (C1) To 100 parts by mass, preferably 5 to 50 parts by mass) and / or phenoxyethyl methacrylate (1 to 100 parts by mass, preferably 5 to 50 parts by mass).

The photocurable resin composition of this invention is a general (meth) acrylate other than component (C1) as a reaction diluent, when the compatibility of a component (A) and a component (C1) is bad, or a viscosity is high and workability is bad. It may include a monomer. As a general (meth) acrylate monomer, For example, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, la Uryl (meth) acrylate, alkyl (meth) acrylate, methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, hydroxide Oxyethyl (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6- Hexanedioldi (meth) acrylate, dicyclopentenyloxyethyl (meth) There can be mentioned a methacrylate, norbornene (meth) acrylate. These (meth) acrylates can use 1 type (s) or 2 or more types.

The photocurable resin composition of this invention can contain a photoinitiator further. As the photoinitiator, the photoinitiator described in the first invention can be used. The quantity of a photoinitiator is 0.1-10 mass parts with respect to 100 mass parts of component (A).

The photocurable resin composition of this invention can contain a tackifier further. As the adhesion imparting agent, those described in the first invention can be used. The quantity of a tackifier is 0.01-10 mass parts with respect to 100 mass parts of components (A), Preferably it is 0.5-5 mass parts.

The photocurable resin composition of this invention can contain antioxidant further. As antioxidant, the thing described by 1st invention can be used. The quantity of antioxidant is 0.01-10 mass parts with respect to 100 mass parts of components (A), Preferably it is 0.5-5 mass parts.

The photocurable resin composition of this invention can be made into the resin composition of the combined type of photocuring and thermosetting similarly to 1st invention. The amount of the organic peroxide is 0.1 to 10 parts by mass, preferably 1 to 5 parts by mass with respect to 100 parts by mass of the component (A).

In addition, naphthenic acid metal complexes, dimethylaniline, quaternary ammonium salts, and phosphate esters can be used as curing accelerators of organic peroxides.

The present invention is a display panel comprising a display body and an optically functional material bonded to the photocurable resin composition described above, which can be incorporated into electronic devices such as televisions, digital cameras, mobile phones, personal computers, monitors, and the like. have.

Third invention

3rd this invention joins the display body and optical function material containing (A) polyisoprene, polybutadiene, or a (meth) acrylate oligomer which has a polyurethane in frame | skeleton, (B) softening component, and (C2) thiol compound As a photocurable resin composition for following, the elasticity modulus of hardened | cured material is less than 10 kPa, and elongation at break of hardened | cured material is 300% or more, It is a photocurable resin composition characterized by the above-mentioned.

Specific examples of the component (A), the component (B) and the component (C2) of the present invention are as described in the first invention.

The photocurable resin composition of this invention is for bonding a display body and an optical function material. As a display body, display elements, such as LCD, an EL display, EL illumination, an electronic paper, and a plasma display with a polarizing plate attached to glass, are mentioned. Optical functional materials include acrylic plates (may be coated with one or both hard coatings or AR coatings), polycarbonate plates, PET plates, and PEN for the purpose of improving visibility and preventing cracking of display elements from external impacts. Transparent plastic plates, such as a board, tempered glass (the shatterproof film may be attached), a touch panel input sensor, etc. are mentioned.

In the photocurable resin composition of this invention, the elasticity modulus of the hardened | cured material is less than 10 kPa, and elongation at the time of breaking of hardened | cured material is 300% or more. By having such elastic modulus and elongation at break of the cured product, when the photocurable resin composition of the present invention bonds the display body and the optical functional material, the adhesive surface is peeled off, the glass of the display is broken, or the display is uneven. There is no. The elastic modulus and elongation at break of the cured product can be measured by the method described in Examples described later.

In this invention, it is preferable that the elasticity modulus of hardened | cured material is 1 kPa or more and less than 10 kPa, It is preferable that elongation at the time of breaking of hardened | cured material is 300% or more and 700% or less, It is more preferable that it is 350% or more and 600% or less.

In the photocurable resin composition of the present invention, the initial transmittance of 400 to 800 nm light in the cured product is 95% or more, the transmittance is 70% or more after 500 hours at 60 ° C and 90% humidity for 500 hours at 85 ° C. It is preferable that the transmittance | permeability is 90% or more after leaving for a while.

In the photocurable resin composition of the present invention, when the amount ratio of the component (C2) to the component (A) is increased, the elastic modulus of the cured product can be lowered, the elongation at break of the cured product can be increased, and the Increasing the amount ratio can lower the elastic modulus of the cured product. Therefore, by adjusting the compounding ratio of component (A), component (B), and component (B), a desired elastic modulus and elongation at break can be imparted to the cured product.

As for the photocurable resin composition of this invention, 100 mass parts of the (meth) acrylate oligomer of (A), and the softening component of (B), Preferably it is 10-300 mass parts, More preferably, it is 100-200 mass parts, The thiol compound of (C2) is preferably 0.05 to 100 parts by mass, more preferably 0.1 to 10 parts by mass.

The photocurable resin composition of the present invention is particularly preferably polyisoprene methacrylate (100 parts by mass) as an oligomer of component (A), or liquid polybutadiene (10 to 300 parts by mass, preferably as a softening component of component (B). Preferably pentaerythritol tetrakis (3-mercaptobutyrate) as a thiol compound of 100 to 200 parts by mass) and / or liquid polyisoprene (10 to 300 parts by mass, preferably 100 to 200 parts by mass) and component (C2) ) (0.05 to 100 parts by mass, preferably 0.1 to 10 parts by mass).

The photocurable resin composition of this invention can contain a (meth) acrylate monomer in the case of poor compatibility or in order to improve workability. As the (meth) acrylate monomer, those described in the first invention can be used. The addition amount of a thiol compound and a softening component can be adjusted by addition of a (meth) acrylate monomer. Although an acrylate monomer is added in the range which can provide desired compatibility, Preferably it is 1-100 mass parts with respect to 100 mass parts of component (A), More preferably, it is 10-50 mass parts.

The photocurable resin composition of this invention can contain a photoinitiator further. As a photoinitiator, what was described in 1st invention can be used. The quantity of a photoinitiator is 0.1-10 mass parts with respect to 100 mass parts of component (A).

The photocurable resin composition of this invention can contain a tackifier further. As the adhesion imparting agent, those described in the first invention can be used. The amount of the tackifier is 0.01 to 20 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the component (A).

The present invention is a display panel comprising a display body bonded to the above-mentioned photocurable resin composition and an optically functional material, which is to be incorporated into electronic equipment such as televisions, digital cameras, mobile phones, personal computers, monitors, and televisions. Can be.

Although this invention is demonstrated by the following Example, this invention is not limited to these Examples.

(Example 1)

The components shown in following Tables 1 and 2 were blended in the amounts (mass parts) shown in Tables 1 and 2 to obtain the photocurable resin compositions of Examples A to I.

UC-1: polyisoprene methacrylate oligomer (molecular weight 25000)

QM657: dicyclopentenyloxyethyl methacrylate

LA: lauryl acrylate

CH: cyclohexyl methacrylate

PO: phenoxyethyl methacrylate

AMP-20GY: phenoxy polyethylene glycol acrylate

702A: 2-hydroxy-3-phenoxypropylacrylate

THF: tetrahydrofurfuryl methacrylate

NP-4EA: Nonylphenol EO Adduct Acrylate

MTG-A: methoxy triethylene glycol acrylate

Lucirin TPO: 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide

Irgacure 184: 1-hydroxy-cyclohexyl-phenyl-ketone

Polyyl 110: liquid polybutadiene

L-LIR: Liquid Polyisoprene

Irganox 1010: Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]

(Test Example 1)

Using the photocurable resin composition of Examples A-I manufactured in Example 1, the characteristic value was analyzed by the following various tests. The results are shown in Tables 3 to 5 below. In neither of Examples A to I, bubbles were present in the heat shock test, the heat test and the moisture test.

Elastic modulus and elongation at break measured JISZ1702 No. 3 dumbbell test piece (thickness 1mmt) by the speed | rate of 10 m / min using the Shimadzu Corporation Corporation Autograph. In addition, the dumbbell test piece was hardened by accumulated light quantity 6000mJ / cm <2> using the diffuser metal halide lamp with a conveyor.

Shrinkage was measured according to JIS-K-6833 and the specific gravity of liquid and specific gravity of hardened | cured material were measured, and it computed from the volume ratio of both.

The transmittance was 400 nm to 800 nm using a UV visible spectrometer manufactured by Nihon Bunk Co., Ltd. Measured by wavelength. The transmittance | permeability was similarly measured also after 500 hours of 85 degreeC and after 500 hours of 60 degreeC / 90%.

The refractive index was measured with the ABE refractive index meter (D line | wire, 25 degreeC) manufactured by Atago which produced the test piece manufactured in the sheet form of thickness 300micrometer.

The heat shock test was performed by bonding a 0.8 mm thick acrylic plate (MR-200 manufactured by Mitsubishi Rayon Co., Ltd.) and a 0.8 mm thick glass plate (30 × 40 mm) to a curing thickness of 100 μm using a photocurable resin composition (glass / Acrylic test piece) or a 0.8 mm thick glass plate and a 0.7 mm thick glass plate (30 × 40 mm) were bonded to a cured thickness of 100 μm using a photocurable resin composition to prepare a test piece (glass / glass test piece). . The test piece was subjected to 500 cycles at -40 ° C to 85 ° C for 30 minutes each, and then visually confirmed the presence of peeling, bubbles and breakage after the test.

In the heat resistance test, the same test piece as used in the heat shock test was kept in an oven at 85 ° C. for 500 hours, and after the test, it was visually checked for the presence of peeling, bubbles and breakage.

In the moisture resistance test, the same test piece as used in the heat shock test was kept for 500 hours in a constant temperature and humidity of 60 ° C./90%, and after the test, it was visually checked for the presence of peeling, bubbles and breakage.

In addition, the adhesive property for touch panel adhesion can be measured in the test by glass / glass test piece, and the adhesive property of a display body and an optical function material can be measured in the test by glass / acrylic test piece.

(Example 2)

The components shown in Table 6 below were blended in the amounts shown in Table 6 to obtain photocurable resin compositions of Examples A2 to H2.

UC-1: polyisoprene methacrylate oligomer (molecular weight 25000)

HOB: 2-hydroxybutyl methacrylate

QM657: dicyclopentenyloxyethyl methacrylate

BZ: benzyl methacrylate

Karenz PE-1: pentaerythritol tetrakis (3-mercaptobutyrate)

TMMP: trimethylolpropane tris (3-mercaptopropionate)

Lucirin TPO: 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide

Irgacure 184: 1-hydroxy-cyclohexyl-phenyl-ketone

Polyyl 110: liquid polybutadiene

L-LIR: Liquid Polyisoprene

Irganox 1520L: 4,6-bis (octylthiomethyl) -o-cresol

(Test Example 2)

Using the photocurable resin compositions of Examples A2 to H2 prepared in Example 2, various tests were performed to analyze characteristic values.

The analysis results are shown in Table 7 below. In neither of Examples A2 to H2, bubbles were present in the heat shock test, the heat test and the moisture test.

According to the first aspect of the present invention, when bonding a decorative plate or an icon sheet on a touch panel, or when bonding a transparent substrate and a transparent plate on which a transparent electrode is formed in a capacitive touch panel, a sufficient adhesiveness is imparted to bubbles. It is possible to provide a photocurable adhesive composition for bonding without including.

According to 2nd or 3rd this invention, the display panel which bonded the photocurable resin composition and the display body and optical functional material for bonding a display body and an optical functional material to which an adhesive surface is not peeled off or glass of a display body is not broken is carried out. Can be provided.

Claims

The photocurable adhesive composition for touch panel bonding containing (A) (meth) acrylate oligomer which has polyisoprene, polybutadiene, or polyurethane in frame | skeleton, and (B) softening component.

The method of claim 1, further comprising (C) phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, cyclohexyl (meth (Meth) acrylate monomer (C1) or thiol compound selected from acrylate, nonylphenol EO adduct (meth) acrylate, methoxytriethyleneglycol (meth) acrylate and tetrahydrofurfuryl (meth) acrylate Photocurable adhesive composition containing C2).

The photocurable adhesive composition according to claim 1 or 2, wherein in the capacitive touch panel, a photocurable adhesive composition for bonding a transparent substrate and a transparent plate on which a transparent electrode is formed or for bonding a sheet or a plate on the touch panel. .

The bonded body of the transparent substrate and transparent plate in which the transparent electrode in the capacitive touch panel bonded with the photocurable adhesive composition of Claim 2, or 3, or the bonded body of a touch panel, a sheet, or a board.

(A) (meth) acrylate oligomers having polyisoprene, polybutadiene or polyurethane in the skeleton, (B) softening component and (C1) phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, nonylphenol EO adduct (meth) acrylate, methoxytriethylene glycol (meth) acrylate and tetrahydrofurfuryl A photocurable resin composition for bonding a display member and an optically functional material containing a (meth) acrylate monomer selected from (meth) acrylates, the cured product having an elastic modulus of less than 12 kPa and an elongation at break of the cured product of 300% The photocurable resin composition characterized by the above.

The initial transmittance of 400-800 nm light in hardened | cured material is 95% or more, The transmittance | permeability is 70% or more after leaving for 500 hours at 60 degreeC and 90% of humidity, After leaving for 500 hours at 85 degreeC The photocurable resin composition whose transmittance | permeability is 90% or more.

The photocurable resin composition of Claim 5 or 6 whose refractive index of hardened | cured material is 1.45-1.55.

The (meth) acrylate oligomer of (A) is 100 mass parts, the softening component of (B) is 10-400 mass parts, and the (meth) acryl of (C1) in any one of Claims 5-7. The photocurable resin composition containing 1-100 mass parts of rate monomers.

The photocurable resin composition of Claim 8 whose quantity of the (meth) acrylate monomer of (C1) is 5-50 mass parts.

The photocurable resin composition of any one of Claims 5-9 whose (meth) acrylate oligomer of (A) is the (meth) acrylate oligomer which has polyisoprene in frame | skeleton.

The photocurable resin composition according to any one of claims 5 to 10, wherein the (meth) acrylate monomer of (C1) is cyclohexyl methacrylate and / or phenoxyethyl methacrylate.

The display panel containing the display body and optical functional material bonded by the photocurable resin composition of any one of Claims 5-12.

Photocurable resin for bonding a display body and an optical functional material containing (A) (meth) acrylate oligomer which has polyisoprene, polybutadiene, or polyurethane in frame | skeleton, (B) softening component, and (C2) thiol compound As a composition, the elasticity modulus of hardened | cured material is less than 10 kPa, and elongation at break of hardened | cured material is 300% or more, The photocurable resin composition characterized by the above-mentioned.

The method according to claim 13, wherein the initial transmittance of 400 to 800 nm light in the cured product is 95% or more, after 500 hours at 60 ° C. and 90% humidity, the transmittance is 70% or more, and after 500 hours at 85 ° C. The photocurable resin composition whose transmittance | permeability is 90% or more.

The photocurable resin composition of Claim 13 or 14 whose refractive index of hardened | cured material is 1.45-1.55.

The method according to any one of claims 13 to 15, wherein the (meth) acrylate oligomer of (A) is 100 parts by mass, the softening component of (B) is 10 to 300 parts by mass and the thiol compound of (C2) is 0.05. Photocurable resin composition containing 100 mass parts.

The photocurable resin composition of Claim 16 whose quantity of the thiol compound of (C2) is 0.1-10 mass parts.

The photocurable resin composition according to any one of claims 13 to 17, wherein the (meth) acrylate oligomer of (A) is a (meth) acrylate oligomer having polyisoprene in a skeleton.

The photocurable resin composition according to any one of claims 13 to 18, wherein the thiol compound of (C2) is selected from 3-mercaptobutyrate derivatives.

The photocurable resin composition according to claim 19, wherein the 3-mercaptobutyrate derivative is pentaerythritol tetrakis (3-mercaptobutyrate).

The photocurable resin composition according to any one of claims 13 to 20, further comprising a (meth) acrylate monomer.

The display panel containing the display body and optical functional material bonded by the photocurable resin composition of any one of Claims 13-21.