KR20130108355A - Energy-ray-curable resin composition, adhesive comprising same, and cured object obtained therefrom - Google Patents

Abstract

An energy ray curable resin composition that satisfies curability, adhesiveness, and storage stability, comprising: (A) a cationically polymerizable compound, (B) a specific photocationic polymerization initiator, (C) a phenolic antioxidant, and a quinone antioxidant It is characterized by containing one or two or more of them. Moreover, the hardening body by which the said energy-beam curable resin composition hardened | cured, and the adhesive agent which consists of this energy-beam curable resin composition are also provided.

Description

Energy-beam curable resin composition, adhesive and hardening body using the same {ENERGY-RAY-CURABLE RESIN COMPOSITION, ADHESIVE COMPRISING SAME, AND CURED OBJECT OBTAINED THEREFROM}

The present invention relates to an energy ray curable resin composition, an adhesive and a cured product using the same.

In the field of electronics in recent years, devices have become high performance. In particular, optical pickup devices used for reproduction and recording of optical recording media such as Blu-ray discs and HD-DVDs corresponding to CD, DVD, blue semiconductor lasers, display components such as liquid crystals, organic electroluminescence, CCDs, In the case of bonding electronic components such as an image sensor such as a CMOS, and also an element package used for a semiconductor component or the like, if the positions of the members are shifted after the bonding, a problem occurs in the operation of these electronic components. Therefore, there is a demand for an adhesive having both high adhesion and low curing shrinkage.

Furthermore, when the positions of the members are displaced even during the bonding of optical elements used for craft glass holders, plates for fixing, lenses, prisms, cameras, binoculars, and microscopes, the aesthetics may be impaired or problems may arise as optical elements. Therefore, high adhesiveness and low curing shrinkage are required in fields other than electronics.

There is a demand for an energy ray-curable cationically polymerizable compound having high adhesion and low curing shrinkage due to the trend of such technology.

Japanese Unexamined Patent Application Publication No. Hei 1-213304 (Patent Document 1) proposes to improve adhesion and curing shrinkage property by containing an energy ray-curable cationically polymerizable organic material and an energy ray-sensitive cationic polymerization initiator in the resin composition for optical molding.

However, such an energy ray-curable resin composition has a problem that the effect on the handling and the environment is concerned because an toxic element such as arsenic (As) or antimony (Sb) is used in the anion portion of the cationic polymerization initiator. In addition, there is a problem that use is limited because fluoride ions are released by decomposing the anion site and exhibit corrosiveness to the metal (hereinafter referred to as "corrosion").

In order to solve this problem, Japanese Patent Laid-Open No. 11-501909 (Patent Document 2) uses an energy ray curable resin composition containing a photocationic polymerization initiator to improve corrosion resistance and safety without impairing fast curing properties. Has been proposed. However, when stored for a long time in a state where a cationic polymerization initiator is added to a cationic polymerizable compound, cations naturally occur from the cationic polymerization initiator even in the state where ultraviolet rays are blocked. Since the cation initiates polymerization of the cationically polymerizable compound and causes thickening and gelation, there is a problem that the storage stability is insufficient.

In order to solve this problem, Japanese Patent Application Laid-Open No. 2003-292606 (Patent Document 3) discloses storage stability without impairing the polymerizability of an oxetane compound by adding a basic compound such as an amine to a oxetane compound. It was proposed to improve the. However, the addition of basic organic compounds such as amines still has a problem that the polymerization inhibitory effect of the cationically polymerizable compound may not be sufficiently obtained, so that sufficient storage stability for practical use cannot be obtained.

In order to solve the problem of storage stability, Japanese Laid-Open Patent Publication No. 2003-155413 (Patent Document 4) discloses that by adding a phosphine oxide derivative to a compound having a cationic polymerizable group, the storage stability can be improved without lowering the polymerization performance of the cationic polymerization initiator. Has been proposed. In addition, Japanese Patent Application Laid-Open No. 2009-215329 (Patent Document 5) proposes to use a uranium-containing silica filler of 1 ppb or less as a method for solving the storage stability problem of an energy ray-curable resin composition using a photocationic polymerization initiator containing a filler. . In addition, Japanese Patent Application Laid-Open No. 2010-24364 (Patent Document 6) proposes an adhesive having both high adhesion, applicability, and low moisture permeability, which are required for bonding electronics packages. However, there is no description that can be obtained sufficient storage stability by the present invention.

Patent Document 1: Japanese Patent Application Laid-Open No. 1-213304 Patent Document 2: Japanese Patent Laid-Open No. 11-501909 Patent Document 3: Japanese Patent Application Laid-Open No. 2003-292606 Patent Document 4: Japanese Patent Application Laid-Open No. 2003-155413 Patent Document 5: Japanese Patent Application Laid-Open No. 2009-215329 Patent Document 6: Japanese Patent Application Laid-Open No. 2010-24364

The present invention relates to an energy ray curable resin composition exhibiting rapid curability and having a long term storage stability and an adhesive using the same.

The present invention is directed to the following.

(1) It contains 1 type (s) or 2 or more types of the group which consists of (A) cationically polymerizable compound, (B) photocationic polymerization initiator represented by Formula (1), (C) phenolic antioxidant, and quinone antioxidant. An energy ray curable resin composition characterized by the above-mentioned.

[Formula 1]

Equation (1)

(Wherein A + is an onium cation, B is C _n X _{2n +1} , n is an integer of 1 to 10, and X represents hydrogen or a halogen atom.)

(2) The energy-ray curing resin composition which is B in formula (1) according to (1) being represented by CF _3.

(3) 100 mass parts of (A) component, 0.1-10 mass parts of (B) component, and 0.01-20 mass parts of (C) component are contained, The energy in any one of (1) or (2) characterized by the above-mentioned. Line curable resin composition.

(4) The energy-beam curable resin composition in any one of (1)-(3) characterized by containing the salt represented by (D) Formula (2).

(2)

Equation (2)

(Wherein D ⁺ represents a cation, m represents an integer of 0 to 20, and M represents an integer of 0 to 10).

(5) The energy ray curable resin composition in any one of (1)-(4) characterized by containing (E) filler.

(6) The energy-beam curable resin composition in any one of (1)-(5) characterized by containing a photosensitizer.

(7) The hardened | cured material by which the energy-beam curable resin composition in any one of said (1)-(6) is hardened | cured.

(8) Adhesive which consists of energy-beam curable resin composition in any one of said (1)-(6).

The energy ray curable resin composition which consists of the said structure can satisfy curability, adhesiveness, and storage stability, for example.

<Explanation of term>

In this specification, an energy-beam curable resin composition means the resin composition which can be hardened by irradiating an energy beam. Herein, the energy ray refers to an energy ray represented by ultraviolet rays, visible rays, or the like.

Storage stability herein means that no thickening or gelation occurs even after long term storage.

Hereinafter, embodiments of the present invention will be described in detail.

The energy-beam curable resin composition which concerns on this embodiment is 1 type from the group which consists of (A) cationically polymerizable compound, (B) photocationic polymerization initiator, (C) phenolic antioxidant, and quinone antioxidant which are described below, or It is characterized by containing 2 types.

Energy-beam curable resin composition which consists of the said structure has the outstanding safety, corrosiveness, curability, storage stability, adhesiveness.

Next, the component of the energy-beam curable resin composition which concerns on this embodiment is demonstrated.

<(A) cationically polymerizable compound>

The energy-beam curable resin composition which concerns on this embodiment makes (A) cationically polymerizable compound an essential component.

(A) As a cationically polymerizable compound, cyclic ethers, a cationically polymerizable vinyl compound, etc. are mentioned. Examples of the cyclic ethers include compounds such as epoxy and oxetane. Vinyl ether, vinylamine, styrene, etc. are mentioned as a cationically polymerizable vinyl compound. These compounds or derivatives may be used alone or in combination of two or more.

As the cationic polymerization compound, any monomer, oligomer or polymer can be used here.

Although it does not specifically limit as an epoxy compound, For example, a bisphenol-A epoxy compound, a bisphenol F-type epoxy compound, a bisphenol S-type epoxy compound, a biphenyl type epoxy compound, a fluorene type epoxy compound, a novolak phenol type epoxy compound, a cresol furnace Divalents of alkylene glycols, such as phenolic epoxy compounds, aromatics such as modified compounds thereof, or diglycidyl ethers of ethylene glycol, diglycidyl ethers of propylene glycol, or diglycidyl ethers of 1,6-hexanediol Polyglycidyl ethers of polyhydric alcohols, such as glycidyl ethers, glycerin or diglycidyl ethers of alkylene oxide adducts thereof, polyethylene glycol or diglycidyl ethers of alkylene oxide adducts thereof, polypropylene glycols or To diglycidyl of polyalkylene glycol, such as diglycidyl ether of this alkylene oxide adduct There may be mentioned the aliphatic, such as LE. Here, as alkylene oxide, aliphatic systems, such as ethylene oxide and a propylene oxide, are mentioned.

Among the epoxy compounds, an epoxy resin having (a-1) an alicyclic epoxy compound and / or (a-2) an aromatic ring is preferable in that excellent adhesiveness, low moisture permeability, and adhesive durability can be obtained, and (a-1) It is more preferable to use together the alicyclic epoxy compound and the epoxy resin which has the (a-2) aromatic ring.

As the alicyclic epoxy compound (a-1), a compound obtained by epoxidizing a compound having a cycloalkane ring such as at least one cyclohexene or a cyclopentene ring or a pinene ring with a suitable oxidizing agent such as hydrogen peroxide or peracid, or a derivative thereof, or a bisphenol A Alicyclic epoxy compounds, such as a hydrogenated epoxy compound obtained by hydrogenating aromatic epoxy compounds, such as a type | mold epoxy compound, etc. are mentioned. These compounds may be used alone or in combination of two or more.

Among these, an alicyclic epoxy compound containing at least one epoxy group and at least one ester group in one molecule is preferable. Such an alicyclic epoxy compound is preferable because it is particularly excellent in adhesiveness and photocurability.

Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate, 3,4-epoxycyclohexylmethyl methacrylate, and the like. Of these, 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate is preferable.

(a-2) As the epoxy resin having an aromatic ring, any monomer, oligomer or polymer can be used, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol type S epoxy resin, biphenyl type epoxy resin, and naphthalene type epoxy resin can be used. , Fluorene type epoxy resins, novolac phenol type epoxy resins, cresol novolac type epoxy resins, modified substances thereof and the like. These epoxy resins may be used alone or in combination of two or more. Among these, 1 type (s) or 2 or more types from the group which consists of a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, and a biphenyl type epoxy resin are preferable at the point which is excellent in adhesiveness and low moisture permeability. In these, bisphenol F-type epoxy resin is preferable.

When considering the balance of photocurability, high accuracy coating property, adhesiveness, moisture permeability, and adhesive durability, the range of (a-2) component is 20-80 parts by mass in 100 parts by mass of the total of (a-1) and (a-2). It is preferable that it is and it is more preferable that it is the range of 40-60 mass parts.

Although it does not specifically limit as an oxetane compound, 3-ethyl-3-hydroxymethyl oxetane (trade name of OXT101 by Nippon Doa Synthetic Co., Ltd.), 1, 4-bis [(3-ethyl-3- oxetanyl) me Methoxymethyl] benzene (trade name: OXT121 manufactured by Nippon Doa Synthetic Co., Ltd.), 3-ethyl-3- (phenoxymethyl) oxetane (trade name OXT211, manufactured by Nippon Doa Synthetic Co., Ltd.), di (1-ethyl-3 -Oxetanyl) methyl ether (trade name: OXT221 manufactured by Nippon Doa Synthetic Co., Ltd.), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (trade name: OXT212 manufactured by Nippon Doa Synthetic Co., Ltd.), and the like. Can be mentioned. An oxetane compound means the compound which has one or more oxetane rings in a molecule | numerator.

Although it does not specifically limit as a vinyl ether compound, Ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol Di or trivinyl ether, such as divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexane dimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, and trimethylol propane trivinyl ether Compound, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexane dimethanol monovinyl ether, n- Propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether-o- Ropil and the like can be mentioned monovinyl ether compounds such as vinylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether.

Although it does not specifically limit as a vinylamine compound, N-vinyl dimethylamine, N-vinyl ethyl butylamine, N-vinyl diphenylamine, N-vinylformamide, an N-vinylacetamide compound, etc. are mentioned.

Among the cationic polymerizable compounds (A), epoxy compounds are preferred in that excellent adhesion, low moisture permeability, and adhesion durability can be obtained.

<(B) photocationic polymerization initiator>

The photocationic polymerization initiator is a compound described below in which cationic species generate | occur | produce by irradiating an energy ray.

As a cationic species of a photocationic polymerization initiator, an onium cation is preferable. As an onium cation, an arylsulfonium salt derivative, an aryl iodonium salt derivative, etc. are mentioned. As the anionic species of the photocationic polymerization initiator, a compound represented by the formula (1) is used in terms of safety, corrosiveness, curability, adhesion, and storage stability such as carcinogenesis.

(3)

Equation (1)

(Wherein A + is an onium cation, B is C _n X _{2n +1} , n is an integer of 1 to 10, and X represents hydrogen or a halogen atom.)

Of these, it is preferable that B in the formula (1) is CF _3. Formula (1) B is CF ₃ the photo cationic polymerization initiator as but not limited to those manufactured by Chiba Japan bis - (4-t- butyl-phenyl) iodonium-tris (trifluoromethane sulfonyl) methoxy Tide (CGI * BBI C1), triphenylsulfonium-tris (trifluoromethanesulfonyl) methide (CGI * TPS C1), tris-'4-acetyl-sulfanyl'-phenyl'-sulfonium-tris ( Trifluoromethanesulfonyl) methide (GSID26-1) and the like. Among these are bis- (4-t-butyl-phenyl) -iodonium-tris (trifluoromethanesulfonyl) methide, triphenylsulfonium-tris (trifluoromethanesulfonyl) methide and tris-sulfone 1 type, or 2 or more types are preferable from the group which consists of 4-acetyl- sulfanyl-phenyl- sulfonium- tris (trifluoromethanesulfonyl) metide, and bis- (4-t-butyl-phenyl)- More preferred is iodonium-tris (trifluoromethanesulfonyl) methide.

(B) As a photocationic polymerization initiator, for example, an arylsulfonium salt derivative (for example, CGI * TPS C1 by Chiba Japan, GSID26-1, etc.), an arylyodonium salt derivative (for example, CGI * BBI by Chiba Japan Co., Ltd.) C1) etc. can be mentioned. You may use 1 type (s) or 2 or more types of photocationic polymerization initiators in arbitrary ratios.

It is preferable to contain (B) photocationic polymerization initiator in the ratio of 0.1-10 mass parts with respect to 100 mass parts of (A) photocationic polymerization compounds. If it exists in this range, hardenability will not worsen and storage stability will not fall, either. From the point of curability and storage stability, the amount of the photocationic polymerization initiator to be used is more preferably 0.5 to 5 parts by mass, and most preferably 1 to 3 parts by mass.

<(C) Phenolic antioxidant and quinone antioxidant>

It is essential for the energy-beam curable resin composition which concerns on this embodiment to contain 1 type or 2 types of the group which consists of a phenolic antioxidant and a quinone antioxidant as antioxidant.

Phenothiazine, 2,2-methylene-bis (4-methyl-6-tert-butylphenol), catechol, tert-butylcatechol, 2-butyl-4-hydroxyanisole, 2 as a phenolic antioxidant , 6-di-tert-butyl-p-cresol, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenylacrylate, 4,4'-butylidenebis (6-tert-butyl-3 -Methylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5- Methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, pentaerythritol tetrakis [3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy-C7-C9 branched alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ＇, 3", 5,5 ＇, 5" -hexa-tert-butyl-a, a ', a "-(mesitylene-2,4,6-tolyl) tri-p-cresol, calcium diethylbis [ [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate , 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione , 1,3,5-tris ((4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, N-phenylbenzene Reaction product of amine with 2,4,6-trimethylpentene, 2,6-di-tert-butyl-4- (4, 6-bis (octylthio) -1,3,5-triazin-2-yl Amino) phenol, picric acid, citric acid, etc. are mentioned.

As the quinone antioxidant, β-naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, 2,5-di -tert- butylhydroquinone, p-benzoquinone, 2, 5- diphenyl- p- benzoquinone, 2, 5- di-tert- butyl- p- benzoquinone, etc. are mentioned.

In these, pentaerythryl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-t-butyl- One or two or more of the group consisting of 4-hydroxyphenyl) propionate and 2,5-di-tert-butyl-hydroquinone are preferable, and pentaerythritol tetrakis [3- (3,5-di -t-butyl-4-hydroxyphenyl) propionate] is more preferable.

(C) It is preferable to contain 1 type or 2 types from the group which consists of a phenolic antioxidant and a quinone type antioxidant in the ratio of 0.01-20 mass parts with respect to 100 mass parts of (A) photocationic polymerization compounds. If it is 0.01 mass part or more, storage stability will improve, and if it is 20 mass parts or less, it will not reduce curability. From the point of curability and storage stability, the amount of one or two of the group consisting of phenolic antioxidants and quinone antioxidants is more preferably 0.05 to 10 parts by mass, and most preferably 0.1 to 5 parts by mass.

<Salt represented by (D) Formula (2)>

The energy-beam curable resin composition which concerns on this embodiment may use the phosphine oxide derivative represented by (D) Formula (2) from a storage stability point. (D) The salt represented by Formula (2) can be used by arbitrary ratios selecting only 1 type or 2 or more types.

[Formula 4]

Equation (2)

(Wherein D ⁺ represents a cation, m represents an integer of 0 to 20, and M represents an integer of 0 to 10).

Examples of the compound represented by the formula (2) include, but are not limited to, sodium tripolyphosphate, sodium tetrapolyphosphate, ammonium phosphate, tricalcium phosphate, and silver phosphate. Of these, sodium tripolyphosphate is preferred.

It is preferable to contain a phosphine oxide derivative in the ratio of 0.01-10 mass parts with respect to 100 mass parts of (A) photocationic polymerization compounds. If it is 0.01 mass part or more, storage stability will improve and if it is 10 mass parts or less, it will not reduce curability. In terms of curability and storage stability, the amount of the phosphine oxide derivative used is more preferably 0.05 to 5 parts by mass, and most preferably 0.1 to 3 parts by mass.

<(E) filler>

The energy ray curable resin composition which concerns on this embodiment may further contain a filler (inorganic filler).

As the filler, oxides such as silica particles, glass fillers, spherical alumina, crushed alumina, magnesium oxide, beryllium oxide and titanium oxide, nitrides such as boron nitride, silicon nitride and aluminum nitride, carbides such as silicon carbide, aluminum hydroxide and hydroxide Hydroxides such as magnesium, metals such as copper, silver, iron, aluminum, nickel and titanium, alloys, carbon-based fillers such as diamond and carbon, and silica particles. The 50% particle diameter of the filler is preferably in the range of 0.1 µm or more and 15 µm or less, and it is preferable that the 90% particle diameter is in the range of 3 µm or more and 20 µm or less. Due to such a range, the particle diameter is too small to easily aggregate, and the particle diameter is too large to easily settle. Among these, silica particles are preferable.

The 50% particle diameter and the 90% particle diameter referred to here refer to the particle diameter at 50% and 90% of the cumulative volume.

Although it does not specifically limit as a measuring method of particle diameter, For example, a laser diffraction particle size distribution meter, a laser Doppler particle size distribution meter, a dynamic light scattering particle size distribution meter, an ultrasonic particle size distribution meter, etc. are mentioned.

Silica particles are silica particles having a purity of 99% or more represented by SiO _x (1 ≦ _X ≦ 2) as a chemical composition and refer to zhouranium silica particles having a uranium content of 1 ppb or less.

The method for synthesizing the silica particles is not particularly limited, but neutralizing alkali gels, drying and pulverizing the flame, and then flame melting the alkoxysilane, vapor phase hydrolysis of volatile silicon compounds such as silicon tetrachloride, and uranium crystal The method of grind | pulverizing and melting it, etc. are mentioned. This method is preferred because it is easy to obtain stable zuranium silica particles.

It is preferable to contain (E) filler in the ratio of 50-300 mass parts with respect to 100 mass parts of (A) photocationic polymerization compounds. If it is 50 mass parts or more, low moisture permeability can be obtained, and if it is 300 mass parts or less, a filler will not aggregate and it can maintain a dispersed state. Since the effect is large, the usage-amount of a filler is more preferable 100-200 mass parts, and 120-180 mass parts is the most preferable.

<Other ingredients>

(Sensitizer)

The energy ray curable resin composition which concerns on this embodiment may use various photosensitizers together. A photosensitizer means the compound which absorbs an energy ray and generate | occur | produces a cation efficiently from a photocationic polymerization initiator.

Although it does not specifically limit as a photosensitizer, A benzophenone derivative, a phenothiazine derivative, a phenyl ketone derivative, a naphthalene derivative, an anthracene derivative, a phenanthrene derivative, a naphthacene derivative, a chrysene derivative, a perylene derivative, a pentacene derivative, an acridine Derivatives, benzothiazole derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, xanthone derivatives, thioxanthene derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, Cyanine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives, azulene derivatives, triallyl methane derivatives, phthalocyanine derivatives, spiropyrane derivatives, spiroxazine derivatives, thiospyropyran derivatives, organoruthenium complexes and the like Can be. It is not limited to these, A well-known photosensitizer can be applied. Among these, phenyl ketone derivatives such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one are preferred, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one is more preferred. desirable.

It is preferable to contain a photosensitizer in the ratio of 0.1-10 mass parts with respect to 100 mass parts of (A) photocationic polymerization compounds. If it exists in this range, hardenability will not worsen and storage stability will not fall, either. From the point of curability and storage stability, the amount of the photosensitizer used is more preferably 0.5 to 5 parts by mass, and most preferably 1 to 3 parts by mass.

(additive)

Graft copolymers, such as various elastomers, such as an acrylic rubber and a urethane rubber, a methyl methacrylate butadiene-styrene graft copolymer, an acrylonitrile butadiene-styrene graft copolymer, in the range which does not impair the objective of this embodiment, Additives such as solvents, extenders, reinforcing agents, plasticizers, thickeners, dyes, pigments, flame retardants and surfactants may be contained.

Moreover, a well-known silane coupling agent can be contained in arbitrary ratios.

The energy ray curable resin composition which consists of the said structure may be hardened | cured by irradiation of an energy ray, and may be set as a hardened | cured material.

You may use the energy-beam curable resin composition which consists of the said structure as an adhesive agent. This adhesive is used for optical pickup devices used for the reproduction and recording of optical recording media such as Blu-ray discs and HD-DVDs for CD, DVD, blue semiconductor lasers, display components such as liquid crystals, organic electroluminescence, CCDs, CMOS, etc. It can be used very suitably for adhesion | attachment in the electronics field, such as an electronic component, such as an image sensor, and also an element package used for semiconductor components. Furthermore, it becomes a suitable adhesive agent for the bonding of the optical element used for the base of a craft glass, the fixation of a plate, two or more lenses, a prism, a camera, binoculars, and a microscope.

[Manufacturing method]

There is no restriction | limiting in particular about the manufacturing method of the energy-beam curable resin composition which concerns on this embodiment as long as said material can be fully mixed. Although it does not specifically limit as a mixing method of a material, The stirring method using the stirring force according to the rotation of a propeller, the method of using normal dispersers, such as a planetary stirrer by rotating revolution, etc. are mentioned. Such a mixing method is preferable because stable mixing can be performed at low cost.

After performing the said mixing, you may harden an energy-beam curable resin composition by irradiation of an energy beam using the following light sources.

(Light source)

Although it does not specifically limit as a light source used for hardening and bonding of an energy-beam curable resin composition in this embodiment, A halogen lamp, a metal halide lamp, a high power metal halide lamp (containing indium etc.), a low pressure mercury lamp, a high pressure mercury lamp, And ultrahigh pressure mercury lamps, xenon lamps, xenon excimer lamps, xenon flash lamps, light emitting diodes (hereinafter referred to as LEDs), and the like. These light sources are preferable at the point which can irradiate an energy beam corresponding to the reaction wavelength of each photoinitiator efficiently.

The light source differs in emission wavelength and energy distribution, respectively. Therefore, the said light source is suitably selected by the reaction wavelength of a photoinitiator, etc. In addition, natural light (sunlight) can also be a reaction start light source.

The light source may be condensed irradiation by direct irradiation, light condensing by a reflector, or the like. A low wavelength cut filter, a hot wire cut filter, a cold mirror, etc. can also be used.

As mentioned above, although embodiment of this invention was described, these are various illustrations other than the above in the range which does not impair the objective of this invention as an illustration of this invention.

<Examples>

Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in more detail, this invention is not limited to these.

In the Examples and Comparative Examples, the following compounds were used.

The following were used as a cationically polymerizable compound of (A) component.

(A-1) 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate ("cell oxide 2021P" by Daicel Chemical Corporation)

(A-2) Bisphenol F type epoxy resin (`` YL-938U '' made in Japan epoxy resin company)

(A-3) Novolak phenol type epoxy resin (`` EP-152 '' made in Japan epoxy resin company)

(A-4) Polypren glycol epoxy resin (SR-PTMG, manufactured by Sakamoto Pharmaceutical Co., Ltd.)

(A-5) Di (1-ethyl-3-oxetanyl) methyl ether (Doa synthetic company "OXT221")

The following were used as a photocationic polymerization initiator of (B) component.

(B-1) Bis- (4-t-butyl-phenyl)-iodonium-tris (trifluoromethanesulfonyl) meted ("CGI * BBI C1" by Chiba Japan)

(B-2) triphenylsulfonium-tris (trifluoromethanesulfonyl) methide (CGI * TPS C1 manufactured by Chiba Japan)

(B-3) Tris- {4-acetyl-sulfanyl-phenyl} sulfonium-tris (trifluoromethanesulfonyl) methide ("GSID26-1" by the Chiba Japan company)

The following photo cationic initiators (B-4 and B-5) were used for the comparison.

(B-4) iodonium # 4- (2-methylpropyl) phenyl｝ (hexafluorophosphate) (containing 75% by mass in propylene carbonate solvent) (`` Irgacure-250 '' made by Chiba Japan)

(B-5) Aromatic sulfonium PF ₆ salt (adeca optomer SP-150)

(C) The following were used as a phenolic antioxidant or quinone antioxidant.

(C-1) pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] ("Irganox-1010" made by Chiba Japan)

(C-2) Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ("Irganox-1076" made by Chiba Japan)

(C-3) 2,5-di-tert-butyl-hydroquinone ("DBHQ" made by Kawaguchi Chemical Co., Ltd.)

(C-4) 4,4'-thiobis (6-tetra-butyl 1-3-methylphenol)

(SUMILIZER WX-R made by Sumitomo Chemical Co., Ltd.)

2-hydroxy-2-methyl-1-phenyl-propan-1-one ("Tarocure 1173" by Chiba Japan Corporation) was used as a photosensitizer.

(D) The following were used as the phosphine oxide derivative represented by Formula (2).

(D-1) Sodium polyphosphate (manufactured by Kanto Chemical Co., Ltd.)

Diethyl phosphite (D-2), a phosphorus compound, was used for comparison.

(D-2) Diethyl Phosphate (manufactured by Wako Pure Chemical Industries, Ltd.)

As the filler (E), denka fused silica FB-3SDX (manufactured by Electrochemical Industry Co., Ltd., 50% particle diameter 2.8 μm, 90% particle diameter 6.2 μm) was used.

(Examples 1 to 9)

The raw materials of the kind shown in Table 1 were mixed by the composition ratio shown in Table 1, and the resin composition of Examples 1-9 was prepared. The evaluation mentioned later about photocurability, tensile shear adhesive strength, and storage storage stability was performed, and the result was shown in Table 1.

[Table 1]

(Comparative Examples 1 to 3)

The raw materials of the kind shown in Table 2 were mixed by the composition ratio shown in Table 2, and the resin composition of Comparative Examples 1-3 was prepared. The evaluation results are shown in Table 2.

[Table 2]

(Examples 10 to 13)

The raw materials of the kind shown in Table 3 were mixed by the composition ratio shown in Table 3, and the resin composition of Examples 10-13 was prepared. Table 3 shows the results of the evaluation.

[Table 3]

[Photocurability Evaluation]

Rheometer ("MCR-301" made by Anton Paar) can measure the stiffness under UV irradiation. The measurement was carried out at 25 ° C. (± 0.5 ° C.) and frequency 10 Hz while sandwiching the prepared resin composition between both surfaces of a circular plate having a diameter of 8 mm and irradiating the resin composition with UV (365 nm roughness: 150 mW / cm ² ). It was judged good that the storage stiffness (G ') increased to 1.00E + 4 (1.00 * 10 <^4> ) or more until 200 second after the start of UV irradiation, and the symbol "(circle)" was attached. On the other hand, it was judged that the storage stiffness (G ') was less than 1.00E + 4 until 200 second after the start of UV irradiation, and the symbol "x" was added.

[Evaluation of Tensile Shear Adhesion Strength]

Tensile shear bond strength: Measured according to JIS K 6850. Specifically, two pieces of heat-resistant glass were made of the resin composition produced by using a heat-resistant glass (trade name "Heat-resistant Pyrex (registered glass), 25 mm x 5 mm x 2.0 mm) made of an adherend in a circular shape of 8 mm in diameter. Tensile strength test piece using a UV irradiator and cured under the conditions of accumulated light quantity 52000mJ / cm ² (365 nm illuminance: 400mW / cm ² , USP's `` SP-7 (UV curing device with mercury xenon lamp) ''). Made. The produced test piece measured tensile shear adhesive strength using the universal testing machine in the environment of 23 degreeC and 50% of humidity.

[Evaluation of Preservation Storage Stability]

After measuring the initial viscosity (V ₀ ) of the composition, it was placed in a container and covered with a lid (sealing system) under a high temperature environment at 40 ° C., and the viscosity (V ₄ ) of the composition after 4 weeks was measured. And the formula: The viscosity was determined according to the rate of change V ₄ / V _0. A viscosity change rate of 4 or less was judged to be good storage stability.

[Measurement of viscosity]

The viscosity of the composition was measured under conditions of a temperature of 25 ° C. and a rotation speed of 10 rpm using an E-type clay meter.

According to the present invention as described above, it contains one or two kinds of the group consisting of (A) cationic polymerizable compound, (B) photocationic polymerization initiator, (C) phenolic antioxidant and quinone antioxidant. An energy ray curable resin composition is provided. The energy-beam curable resin composition which consists of the said structure not only has high adhesiveness and low hardening shrinkage property, but can satisfy | fill corrosiveness, safety, curability, and storage stability. The use of (D) phosphine oxide derivatives further improves storage stability.

An energy ray curable resin composition can be used as an adhesive agent. This adhesive is used for optical pickup devices used for the reproduction and recording of optical recording media such as Blu-ray discs and HD-DVDs corresponding to CD, DVD, blue semiconductor lasers, display components such as liquid crystals, organic electroluminescence, CCD, CMOS, etc. Electronic components such as image sensors, and also electronics fields such as device packages used for semiconductor components, and furthermore, when bonding optical elements used for fixing glass plates, fixing plates, lenses, prisms, cameras, binoculars, and microscopes, etc. It is a very suitable adhesive capable of satisfying safety, corrosiveness, curability, adhesiveness and storage stability.

Claims (8)

(A) a cationically polymerizable compound, (B) a photocationic polymerization initiator represented by formula (1), (C) a phenol-based antioxidant and a quinone-based antioxidant. An energy ray curable resin composition.
[Formula 1]
Equation (1)

(Wherein A + is an onium cation, B is C _n X _{2n +1} , n is an integer of 1 to 10, and X represents hydrogen or a halogen atom.) The method according to claim 1, formula (1) B is an energy ray curable resin composition, characterized in that represented by CF ₃ at. The energy-beam curable resin composition of Claim 1 or 2 containing 100 mass parts of (A) components, 0.1-10 mass parts of (B) components, and 0.01-20 mass parts of (C) component. (D) The salt represented by Formula (2) is contained, The energy-beam curable resin composition of any one of Claims 1-3 characterized by the above-mentioned.
(2)
Equation (2)

(Wherein D ⁺ represents a cation, m represents an integer of 0 to 20, and M represents an integer of 0 to 10). The energy ray curable resin composition of any one of Claims 1-4 containing (E) filler. The energy ray curable resin composition of any one of Claims 1-5 containing a photosensitizer. Hardened | cured material formed by hardening | curing the energy-beam curable resin composition of any one of Claims 1-6. The adhesive agent which consists of energy-beam curable resin composition of any one of Claims 1-6.