JP2022066273A - Photocurable adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable adhesive composition having excellent antistatic properties while having the required properties of an adhesive such as adhesiveness and transparency.

SOLUTION: A photocurable adhesive composition contains (A) a (meth) acrylate oligomer, (B) a monofunctional (meth) acrylate monomer, (C) a plasticizer, (D) a photoreaction initiator, and (E1) an ionic liquid or (E2) a metal salt.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to a photocurable adhesive composition that can be used for bonding an optical display or a touch sensor, and an optical display or a touch panel that is bonded using the same.

Materials used for optical purposes, such as display bodies such as liquid crystal panels or optical lenses such as collimator lenses, are antistatic in order to prevent the adsorption of dust due to static electricity and the damage to electrical equipment due to electric discharge. It is necessary to have sex. For this reason, an antistatic agent, which is a substance that enhances conductivity, is added, but there is a wide range of demands for members having antistatic properties (for example, Patent Document 1 for lens applications).

There are several drive systems for liquid crystal panels used in display applications. In the IPS type drive method, an electric field is applied in the plane direction (transverse electric field drive method), so if the display surface is affected by an external electric field such as charging, the orientation of the liquid crystal molecules is disturbed and display defects occur. Normally, in order to prevent this, a conductive and antistatic layer is provided on the surface of the HC layer and the adhesive layer of the polarizing plate and the CF substrate (Patent Document 2). However, in liquid crystal panel applications, the conductive and antistatic layers can be connected to the TFT only from the side surface due to their structure, so that there is a problem in their reliability.

On the other hand, in order to protect a thin glass substrate and expand applications, a protective panel or a touch panel is provided on the liquid crystal panel, and a technique of using a liquid resin for fixing them to the liquid crystal panel is known. In the technology using liquid resin, since the liquid resin is applied so as to cover the display part of the liquid crystal panel for adhesion, the area that can be connected to the TFT board is larger than other members, and the reliability in antistatic property is improved. There is expected.

However, in the technique using a liquid resin, a plurality of properties are required for the liquid resin. The glass of a liquid crystal panel is becoming thinner due to the need for thinner and lighter display devices, and the glass may be damaged or deformed due to the curing shrinkage stress when the liquid resin is cured. Since this causes display defects, it is necessary to reduce the curing shrinkage rate and elastic modulus (Patent Document 3). Further, in the technique using the liquid resin, the liquid resin is applied so as to cover the display part of the liquid crystal panel for adhesion, so that the liquid resin used is an optically transparent resin (OCR). It is required not to cause coloring, discoloration after the heat resistance test, or deterioration of strength after the moisture resistance test (Patent Document 4). Further, the liquid resin is preferably a type that is cured by light such as ultraviolet rays in order to prevent shrinkage due to thermal curing and to cure the entire resin evenly.

Japanese Unexamined Patent Publication No. 2010-007017 Japanese Unexamined Patent Publication No. 2014-199472 WO2010 / 027041 Pamphlet Japanese Unexamined Patent Publication No. 2012-046658

Since OCR has a larger area that can be connected to the TFT substrate than other members, if OCR can be made conductive and antistatic, it will be possible to manufacture highly reliable devices using OCR as an antistatic layer. Become. On the other hand, the liquid resin used as an adhesive is required to have various properties as an adhesive and an optical material.

The present inventors have found that there is a problem that the desired antistatic property cannot be exhibited only by the components of the adhesive / optical material. Therefore, an object of the present invention is to provide a photocurable adhesive composition having excellent antistatic properties while having properties required for an adhesive such as adhesiveness and transparency.

The present inventors have found that the above-mentioned problems can be achieved by adding a conductive substance such as an ionic liquid or a metal salt in a specific photocurable adhesive composition, and complete the present invention. bottom.

The present invention is specified by the following matters.
That is, the first invention is the (A) (meth) acrylate oligomer,
(B) Monofunctional (meth) acrylate monomer,
(C) Plasticizer,
It is a photocurable adhesive composition containing (D) a photoreaction initiator and (E1) an ionic liquid.
The second invention is (A) (meth) acrylate oligomer,
(B) Monofunctional (meth) acrylate monomer,
(C) Plasticizer,
It is a photocurable adhesive composition containing (D) a photoreaction initiator and (E2) a metal salt.
In the third aspect of the invention, the component (A) is one or more selected from the group consisting of a polyurethane (meth) acrylate oligomer and a (meth) acrylic copolymer having a (meth) acryloyl group. Alternatively, it is the photocurable adhesive composition according to the second invention.
The fourth invention is the photocurable adhesive composition according to any one of the first to third inventions, wherein the acrylic equivalent of the component (A) is 200 g / mol or more.
A fifth invention is the photocurable adhesive composition according to any one of the first to fourth inventions, which is used for bonding an optical display or a touch sensor.
The sixth invention is a laminated body bonded with the photocurable adhesive composition according to any one of the first to fifth inventions.
The seventh invention is the laminated body according to the sixth invention, which is an optical display or a touch sensor.

According to the present invention, there is provided a photocurable adhesive composition having excellent antistatic properties while having properties required for an adhesive such as adhesiveness and transparency.

Hereinafter, the photocurable adhesive composition of the present invention will be described in detail. In the first aspect, the present invention comprises (A) (meth) acrylate oligomers, (B) monofunctional (meth) acrylate monomers, (C) plasticizers, (D) photoinitiators, and (E1) ions. A photocurable adhesive composition comprising a liquid. Hereinafter, each of these components will be described.

[(A) (meth) acrylate oligomer]
The photocurable adhesive composition of the present invention contains a (meth) acrylate oligomer. Preferably, one or more selected from the group consisting of a polyisoprene (meth) acrylate oligomer, a polybutadiene (meth) acrylate oligomer, a polyurethane (meth) acrylate oligomer, and a (meth) acrylic copolymer having a (meth) acryloyl group. Contains (meth) acrylate oligomers. More preferably, it contains one or more selected from the group consisting of polyurethane (meth) acrylate oligomers and (meth) acrylic copolymers having (meth) acryloyl groups. The acrylic equivalent of the (meth) acrylate oligomer is preferably 200 g / mol or more from the viewpoint that the curing shrinkage rate of the adhesive composition can be further reduced.

The polyisoprene (meth) acrylate oligomer is also called (meth) acrylic modified polyisoprene and has a molecular weight of preferably 1000 to 100,000, more preferably 1000 to 50,000. Moreover, these hydrogenated bodies can also be used. As a commercially available product, for example, there is "UC-1" (molecular weight 25000) manufactured by Kuraray Co., Ltd.

The polybutadiene (meth) acrylate oligomer is also called (meth) acrylic modified polybutadiene and has a molecular weight of preferably 500 to 100,000, more preferably 1000 to 30,000. Moreover, these hydrogenated bodies can also be used. As a commercially available product, for example, there is "TE2000" (molecular weight 2000) manufactured by Nippon Petroleum Co., Ltd.

Polyurethane (meth) acrylate oligomers, also referred to as (meth) acrylic modified polyurethanes, preferably have a molecular weight of 1000-100,000, more preferably 1000-50,000. The structure of polyurethane is not particularly limited as long as it is modified with a (meth) acrylic group, and for example, a polyurethane (meth) acrylate oligomer can be obtained from a polyurethane having a skeleton such as polyether or polycarbonate as a raw material. As a commercially available product, for example, there is "UA-1" manufactured by Light Chemical Co., Ltd.

The (meth) acrylic copolymer having a (meth) acryloyl group is a copolymer containing a monomer having a (meth) acryloyl group, and has a molecular weight of preferably 5,000 to 300,000, more preferably 10,000 to 100,000.

[(B) Monofunctional (meth) acrylate monomer]
The photocurable adhesive composition of the present invention further contains a (meth) acrylate monomer. The photocurable adhesive composition of the present invention can impart elongation to the cured product by containing the (meth) acrylate monomer.

Examples of the (meth) acrylate monomer include 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, and alkyl (meth) acrylate. ) Acrylate, methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, benzyl (meth) Acrylate, phenyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, hydroxyethyl (meth) acrylate, 1,3-butylene glycol di (meth) acrylate , 1,4-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) ) Acrylate, norbonene (meth) acrylate, phenoxyethyl (meth) acrylate (PO), phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, cyclohexyl (meth) acrylate (CH), nonylphenol It is selected from EO adduct (meth) acrylates, methoxytriethylene glycol (meth) acrylates and tetrahydrofurfuryl (meth) acrylates. One kind or two or more kinds of these (meth) acrylate monomers can be used.

The (meth) acrylate monomer is contained in an amount of preferably 5 to 80 parts by mass, more preferably 5 to 70 parts by mass, and most preferably 5 to 60 parts by mass with respect to the entire composition.

[(C) Plasticizer]
The photocurable adhesive composition of the present invention further contains a plasticizer. The photocurable adhesive composition of the present invention can control the elastic modulus and the shrinkage rate by containing a plasticizer.
Examples of the plasticizer include polymers compatible with (meth) acrylate oligomers, oligomers, phthalates, castor oil, xylene resin, terpene resin, rosin and the like. Examples of the oligomer or polymer include polyisoprene-based, polybutadiene-based or xylene-based oligomers or polymers. These softening ingredients are commercially available from Kuraray as the LIR series, Degussa as the polyoil series, and Fudo as the Nicanor series. One kind or two or more kinds of these softening components can be used.

The plasticizer is contained in an amount of preferably 5 to 90 parts by weight, more preferably 10 to 80 parts by mass, still more preferably 20 to 70 parts by mass or less with respect to the entire composition.

[(D) Photochemical initiator]
The photocurable adhesive composition of the present invention further comprises a photoinitiator. As the photoinitiator, a general initiator can be used, for example, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 1-Hydroxycyclohexyl-phenyl-ketone, benzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide, 2,4,6-trimethylbenzoylphenyl Ethoxyphosphine 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, benzoinmethyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 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, isopropylthioxanthone, methyl o-benzoylbenzoate, [4- (methylphenylthio) phenyl] phenylmethane, 2,4-diethylthioxanthone, 2-chlorothioxanthone, benzophenone, ethylanthraquinone, benzophenoneammonium Salt, thioxanthone ammonium salt, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphinoxide, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4'-bisdiethylaminobenzophenone, 1,4dibenzoylbenzene, 10-butyl-2-chloroacrydone, 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, acrylic Benzophenone, bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, o-methylbenzoylbenzoate, p. -Dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamylethyl ester, active tertiary amine, carbazole-phenone-based photopolymerization initiator, aclydin-based photopolymerization initiator, triazine-based photopolymerization initiator, benzoyl-based photopolymerization An initiator and the like can be exemplified. One or more of these photoinitiators can be used.

The amount of the photoinitiator is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 0.5 to 15 parts by mass with respect to the entire composition.

In the present invention, preferred photoinitiators include 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide and 1-hydroxy-cyclohexyl-phenyl-ketone, which may be used alone or in combination. good.

[(E1) Ionic liquid]
The photocurable adhesive composition of the present invention in the first aspect contains an ionic liquid. The ionic liquid is a salt that exists in a liquid state, and in the present invention, the photocurable adhesive composition exhibits good conductivity by containing the ionic liquid. The type of ionic liquid is not particularly limited as long as it has a melting point of 150 ° C. or lower, preferably a melting point of 100 ° C. or lower, and particularly preferably a liquid at room temperature (25 ° C., 1 atm).

（式中、Ｒ、Ｒ’、Ｒ”及びＲ’’’は、各々独立して、水素、ハロゲン特にフッ素により置換されていてもよい、アルキル基、芳香族基又は複素環基であり、
Ｘ^－は、各構造のカチオン部分のカウンターアニオンであり、好ましくは、ＢＦ_４ ^－、ＰＦ_６ ^－、ＳＯ_４Ｒ^－、Ｎ（ＳＯ_２Ｒ）_２ ^－、Ｃｌ^－、Ｂｒ^－（ここで、Ｒは、上記定義のとおりである）からなる群より選択され、より好ましくは、ＢＦ_４ ^－、ＰＦ_６ ^－、Ｎ（ＳＯ_２ＣＦ_３）_２ ^－、Ｃｌ^－、Ｂｒ^－からなる群より選択される）
で示されるような化合物のうち、イオン液体としての性質を示すものが挙げられる。 As an example of a preferred ionic liquid, the following structural formula:

(In the formula, R, R', R "and R''' are alkyl groups, aromatic groups or heterocyclic groups which may be independently substituted with hydrogen, halogen, particularly fluorine, respectively.
X ^- is a counter anion of the cation moiety of each structure, preferably BF _4- ^, PF _6- ^, SO ₄ R- ^, N (SO ₂ R) _2- , ^{Cl- ,} Br- ⁽ where R). Is selected from the group consisting of (as defined above), and more preferably selected from the group consisting of BF _4- ^, PF _6- ^, N (SO ₂ CF ₃ ) _2- ^{, Cl- ,} Br-. )
Among the compounds shown in the above, those showing the properties as an ionic liquid can be mentioned.

Examples of ionic liquids include imidazoliums such as 1,3-dimethylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium bis (pentafluoroethylsulfonyl) imide, and 1-ethyl-3-methylimidazolium bromide. Salt derivative; Pyridinium salt derivative such as 3-methyl-1-propylpyridimiumbis (trifluoromethylsulfonyl) imide, 1-butyl-3-methylpyridiniumbis (trifluoromethylsulfonyl) imide; tetrabutylammonium heptadecafluoro Alkylammonium derivatives such as octansulfonate and tetraphenylammonium methanesulfonate; phosphonium salt derivatives such as tetrabutylphosphonium methanesulfonate; composite conductivity of polyalkylene glycol and lithium perchlorate composites, etc. It is possible to indicate an imparting agent or the like.

The amount of the ionic liquid is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass with respect to the entire composition. Within this range, better conductivity can be provided without impairing the function as an adhesive.

In a second aspect of the invention, the invention comprises (A) (meth) acrylate oligomers, (B) monofunctional (meth) acrylate monomers, (C) plasticizers, (D) photoreactive initiators, and (D) photoreactive initiators. E2) A photocurable adhesive composition containing a metal salt. As for the components (A) to (D), the examples and preferred embodiments as described above are similarly applied.

[(E2) Metal salt]
The photocurable adhesive composition of the present invention in the second aspect contains a metal salt. The type of the metal salt is not particularly limited as long as it is uniformly dispersed in the components (A) to (D) and does not impair the transparency of the entire composition. As examples of metal species, a wide range of metal elements are used, such as group 1 elements (alkali metals) such as lithium and sodium, group 2 elements such as calcium and strontium, and transition metals such as titanium, nickel, palladium and osmium. be able to. As an example of the counter ion of the metal species, an organic anion species such as halogen, sulfonamide, and acetate ion can be used. Preferred examples of counter anions are RCOO- ^, BF _4- ^, PF _6- ^, SO ₄ R- ^, NO _3- ^, N (SO ₂ R) _2- ^, C (SO ₂ R) _3- ^, N (SO ₂ R). ) (COR) ^- , ^- O ₃ S (R) ₃ SO _3- , ^{Cl- ,} ClO _4- ^, Br- ^, I- ^, AlCl _4- ^, Al ₂ Cl _7- ^, AsF _6- ^, SbF _6- ^, NbF It is selected from the group consisting of _6- ^, TaF _6- ^, (CN) ₂ N- ⁽ where R is the same as defined in the section on ionic liquids), more preferably BF _4- ^, PF _6- . ^- , N (SO ₂ CF ₃ ) _2- ^, N (SO ₂ C ₂ F ₅ ) _2- , ^{Cl- , Br- Selected} from the group)

Examples of metal salts include sodium acetate, sodium alginate, sodium lignin sulfonate, sodium toluene sulfonate, LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, Li (C ₂ F ₅ SO ₂ ) ₂ N, Li (C ₄ F ₉ SO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) ₃ C, KO ₃ S (CF ₂ ) ₃ SO ₃ K, LiO ₃ S (CF ₂ ) ₃ SO ₃ K can be shown. However, if it is a combination of the above metal and counter ion, it is not limited to a profit.

The amount of the metal salt is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass with respect to the entire composition. Within this range, better conductivity can be provided without impairing the function as an adhesive.

The photocurable adhesive composition of the present invention can contain additives known to those skilled in the art in both the first aspect and the second aspect.

The photocurable adhesive composition of the present invention can further contain an adhesive-imparting agent. As the adhesion imparting agent, a silane coupling agent such as vinyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldi Ethoxysilane, 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-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) Propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyl, methyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis ( Examples thereof include triethoxysilylpropyl) tetrasulfide and 3-isopropylpropyltriethoxysilane. One or more of these adhesives can be used. The amount of the adhesive-imparting agent is preferably 10 parts by mass or less, more preferably 1 part by mass or less, based on the entire composition.

The photocurable adhesive composition of the present invention may further contain an antioxidant. Antioxidants include BHT, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl. Tetrakiss [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-hexanediol-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-hydrocinnamamide), 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-) Examples thereof include butyl-4-hydroxyphenyl) propionate and dibutylhydroxytoluene. One type or two or more types of these antioxidants can be used. The amount of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 3 parts by mass with respect to the entire composition.

In the photocurable adhesive composition of the present invention, when a part of the adhesive composition applied to the adhesive surface is not exposed to light due to the structure of the material to be adhered, the part exposed to the light is cured by light, and the light is applied. It is also possible to make an adhesive composition of a combined type of photo-curing and heat-curing, in which an organic peroxide is added and the adhesive is cured by heat. Examples of organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates. As these organic oxides, one kind or two or more kinds can be used. One kind or two or more kinds of these organic oxides can be used, and the amount thereof is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 3 parts by mass with respect to the entire composition. .. As the curing accelerator for the above organic peroxide, a naphthenic acid metal complex, dimethylaniline, a quaternary ammonium salt, and phosphoric acid esters can be used.

The photocurable adhesive composition of the present invention can exhibit high antistatic properties by having a low resistance value. The photocurable adhesive composition of the present invention preferably has a volume resistance value of 1.0 × 10 ¹¹ Ω · cm or less, and more preferably a volume resistance value of 1.0 × 10 ¹⁰ Ω · cm or less. Has.

The photocurable adhesive composition of the present invention can be used as an adhesive in an optical display or a touch sensor. For example, the optical display panel and the touch panel are bonded, the optical display panel and the protective panel are bonded, the touch panel and the protective panel are bonded, the optical display panel and the optical display panel are bonded, and the optical display panel and the parallax barrier are bonded. It can be used for bonding with. The bonding can be performed by a usual method.

The present invention also relates to an optical display or a touch sensor bonded with the above-mentioned photocurable adhesive composition. These laminated bodies can be incorporated into electronic devices such as televisions, digital cameras, mobile phones, personal computers, monitors, and televisions.

ＫＥ－３１１：水添ロジンエステル
ＩＬ－Ｐ１４：ピリジニウムカチオン系イオン液体
ＩＬ－Ａ１２：アンモニウムカチオン系イオン液体
ＩＬ－ＡＰ３：ホスホニウムカチオン系イオン液体
ＩＬ－ＩＭ１：イミダゾリニウムカチオン系イオン液体
ＩＬ－ＭＡ２：アクリル変性アンモニウムカチオン系イオン液体
ＩＬ－ＭＡ３：アクリル変性アンモニウムカチオン系イオン液体
ＥＦ－Ｎ１１５：リチウムビス（トリフルオロメチルスルホニル）イミド（三菱マテリアル電子化成（株）製） The present invention will be described with reference to the following examples, but the present invention is not limited to these examples. The reagents used in Examples and Comparative Examples are as follows.
UA10000B: Polyether Urethane Acrylate LA: Lauryl Acrylate FA513AS: Dicyclopentanyl Acrylate 4HBA: 4-Hydroxybutyl Acrylate I-TPO: Lucillin TPO (2,4,6-trimethylbenzoylphenylethoxyphosphine oxide)
I-184: Irgacure 184 (1-hydroxy-cyclohexyl-phenyl-ketone)
DINCH: Diisononylcyclohexane-1,2-dicarboxylate Nicanor H: Compound represented by the following structural formula

KE-311: Hydrogenated rosin ester IL-P14: Pyridinium cation-based ionic liquid IL-A12: Ammonium cation-based ionic liquid IL-AP3: Phosphonium-cationic ionic liquid IL-IM1: Imidazolinium cation-based ionic liquid IL-MA2: Acrylic-modified ammonium cationic ionic liquid IL-MA3: Acrylic-modified ammonium cationic ionic liquid EF-N115: Lithium bis (trifluoromethylsulfonyl) imide (manufactured by Mitsubishi Materials Electronics Co., Ltd.)

(Examples 1 to 10 and Comparative Examples 1 to 3)
The components shown in Table 1 were blended in an amount (mass basis) shown in Table 1 to obtain photocurable adhesive compositions of Examples 1 to 10 and Comparative Examples 1 to 3. A cured product was obtained by irradiating the obtained composition with ultraviolet rays. For the ultraviolet irradiation, Eye Grantage manufactured by Eye Graphics Co., Ltd. was used, and irradiation of 3000 mJ / cm ² was performed with an illuminance of 400 mW / cm ² . The cured product was attached to the testing machine and the resistance value was measured. The measurement was carried out at 100 V using a super insulation meter SM-8220 manufactured by Hioki Sangyo Co., Ltd. From the obtained resistance value, the following formula:
ρv = (R × A) / L
(In the formula, ρv is the resistivity, R is the resistance value, A is the cross section, and L is the length.)
The volume resistivity was calculated according to the above. The composition of each component and the measurement results of the volume resistivity in Examples and Comparative Examples are shown in Table 1 below.

(Curing shrinkage rate)
The specific densities of the liquids and cured products of the compositions of Examples 1 to 10 and Comparative Examples 1 to 3 were measured by a specific gravity cup, and the curing shrinkage rate was calculated from the ratios.

The compositions of Examples 1 to 10 and Comparative Examples 1 to 3 were used as dumbbell-shaped cured product test pieces having a measuring section length of 30 mm, a width of 5 mm, and a thickness of 1 mm. A tensile test was performed at a speed of 10 mm / min using 2 kN to obtain an elastic modulus.

The photocurable adhesive composition of the present invention contains a compound having a low curing shrinkage and elasticity, maintaining excellent physical properties as an adhesive, and ionizing to form an ionic species such as an ionic liquid or a metal salt. It was clarified that the volume resistance value was significantly reduced as compared with the conventional composition (comparative example). Therefore, it has been shown that the photocurable adhesive composition of the present invention is a useful material for bonding liquid crystal panels and the like as an adhesive having excellent antistatic properties.

Claims (7)

(A) (meth) acrylate oligomer,
(B) Monofunctional (meth) acrylate monomer,
(C) Plasticizer,
A photocurable adhesive composition comprising (D) a photoreaction initiator and (E1) an ionic liquid. (A) (meth) acrylate oligomer,
(B) Monofunctional (meth) acrylate monomer,
(C) Plasticizer,
A photocurable adhesive composition comprising (D) a photoreaction initiator and (E2) a metal salt. The photocuring according to claim 1 or 2, wherein the component (A) is at least one selected from the group consisting of a polyurethane (meth) acrylate oligomer and a (meth) acrylic copolymer having a (meth) acryloyl group. Mold adhesive composition. The photocurable adhesive composition according to any one of claims 1 to 3, wherein the acrylic equivalent of the component (A) is 200 g / mol or more. The photocurable adhesive composition according to any one of claims 1 to 4, for bonding an optical display or a touch sensor. A laminated body bonded with the photocurable adhesive composition according to any one of claims 1 to 5. The laminate according to claim 6, which is an optical display or a touch sensor.