JP5964590B2 - Active energy ray-curable composition for optical material, cured product, and production method - Google Patents

Description

  The present invention relates to an active energy ray-curable composition for optical materials, a cured product, and a production method. In more detail, a vinyl polymer, a methacrylic acid ester monomer and / or an epoxy group compound having at least one (meth) acryloyl group per molecule and produced by a living radical polymerization method, a photo radical polymerization initiator Contains low viscosity, storage stability, low foamability, low temperature curing, low warpage, deep curability, heat and light resistance, rubber properties, crack resistance, moisture resistance, and design activity for optical materials The present invention relates to an energy ray curable composition, a cured product, and a production method.

  Highly transparent, heat-resistant transparency, and light-resistant transparency materials are used for optical materials including those for LEDs, solar cells, and flat panel display devices. Further, in order to protect elements and fine wiring, impact resistance, moisture permeability resistance and the like that can withstand the use environment are required. In addition, the manufacturing process is required to have low viscosity and good productivity, less shrinkage in curing, and no warping of the substrate.

  As optical materials for LEDs, hard transparent epoxy resins using acid anhydride curing agents, soft silicone resins based on methylpolysiloxane, and hard silicone resins based on phenylpolysiloxane are widely used. (Non-Patent Document 1). These resins are thermosetting resins and require a curing time of several tens of minutes to several hours at 100 ° C. or higher, and there is a problem in productivity. In addition, hard epoxy resin and silicone resin have large curing shrinkage and have restrictions on the manufacturing process. In addition to the problem of poor moisture permeation resistance, soft silicone resins have the problem of peripheral contamination due to low molecular weight siloxane.

  In addition, LED lighting includes a module manufactured by arranging LED packages on a substrate and mounting them. In addition, bullet-shaped LED packages are arranged on the road LED traffic light. As described above, the method of manufacturing the module by arranging the LED packages has a problem in productivity. As a countermeasure, a method of manufacturing a module by arranging a plurality of LED elements on a substrate and collectively sealing them with an optical material can be considered.

  The present inventors have reported a polymer having a main chain as a vinyl polymer obtained by living radical polymerization and having a (meth) acryloyl group at its terminal (Patent Documents 1 to 4). The combined cured product is excellent in rubber physical properties and heat resistance, but is light yellow and tends to be gradually colored at a high temperature of 100 ° C. or higher. Therefore, it cannot be used for optical materials that require high transparency. There were many cases.

JP 2000-72816 A JP 2002-69121 A JP 2007-77182 A JP 2006-265483 A

Advanced device sealing technology and cutting-edge materials, August 2009, CMC Publishing Co., Ltd.

  The present invention is an active energy for optical materials excellent in low viscosity, storage stability, low foamability, low temperature curing, low warpage, deep curability, heat and light resistance, rubber properties, crack resistance, moisture resistance and design. It aims at providing a linear curable composition, hardened | cured material, and a manufacturing method.

  In view of the above-mentioned present situation, the present inventors can use an active energy ray curing that cures at a low temperature within several tens of seconds if an acrylic polymer having a (meth) acryloyl group at the terminal can be used as an optical material. We thought that it would be an optical material that had never existed, because productivity improvement, improvement of cure shrinkage by polymers obtained by living radical polymerization, and improvement of moisture resistance by moisture-permeable acrylic ester monomers were possible. Further, such an optical material is considered to be optimal in a method of manufacturing a module by arranging a plurality of LED elements on a substrate and collectively sealing with the optical material.

  However, a cured product using an acrylic polymer having a (meth) acryloyl group at the terminal obtained by conventional living radical polymerization tends to be gradually colored at a high temperature of 100 ° C. or higher, and thus has high transparency. It was thought that it could not be used for the required optical material.

  If the present inventors can improve the coloring at a high temperature of 100 ° C. or higher of a cured product using an acrylic polymer having a (meth) acryloyl group at the terminal obtained by living radical polymerization, high transparency is required. As a result of diligent research, it was discovered that the cured product becomes highly transparent by using a compound having a methacrylic acid ester monomer and / or an epoxy group, and is excellent in heat resistance, light resistance and transparency. Thus, the present invention has been completed.

That is,
(A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(In the formula, Ra represents ^a hydrogen atom or an organic group having 1 to 20 carbon atoms)
An active energy ray-curable composition for optical materials, which comprises an acrylic polymer obtained by living radical polymerization having at least one (meth) acryloyl group per molecule and (B) a photoradical polymerization initiator. And
(C) General formula (2):
R ^b —OC (O) C (CH ₃ ) ═CH ₂ (2)
(In the formula, R ^b represents an organic group having an alicyclic aliphatic structure or an aliphatic branched structure having 6 to 20 carbon atoms).
A methacrylic acid ester monomer represented by: and / or (D) a compound having an epoxy group,
When the component (C) is included, the content of the component (C) is 1 to 70 parts by weight with respect to 100 parts by weight of the component (A). When the component (D) is included, the content of the component (D) It is related with the active energy ray curable composition for optical materials whose quantity is 0.1-30 weight part with respect to 100 weight part of (A) component.

(C) General formula (2):
R ^b —OC (O) C (CH ₃ ) ═CH ₂ (2)
(In the formula, R ^b represents an organic group having an alicyclic aliphatic structure or an aliphatic branched structure having 6 to 20 carbon atoms).
It is preferable to contain both the methacrylic acid ester monomer represented by these, and (D) the compound which has an epoxy group.

  The (meth) acryloyl group of the component (A) is preferably at the molecular end.

  The main chain of the vinyl polymer (A) is preferably a polymer mainly composed of a (meth) acrylic acid ester monomer.

  The main chain of the vinyl polymer (A) is preferably a polymer mainly composed of an acrylate monomer.

  The vinyl polymer as the component (A) is preferably produced by an atom transfer radical polymerization method.

  The component (A) is preferably a vinyl polymer that has been produced by a living radical polymerization method and then treated with an oxidizing agent.

  The number average molecular weight of the component (A) is preferably 3000 to 100,000.

  (A) It is preferable that the value of the ratio of the weight average molecular weight and number average molecular weight of the vinyl polymer of component (A) measured by gel permeation chromatography is less than 1.8.

(E) General formula (3):
R ^C — {OC (O) C (R ^a ) ═CH ₂ } _m (3)
(In the formula, R ^c is an organic group having 6 to 20 carbon atoms, R ^a is a hydrogen atom or an organic group having 1 to 20 carbon atoms, and m is an integer of 2 to 6)
It is preferable to contain the (meth) acrylic acid ester monomer represented by these.

  (A) It is preferable that (E) component is 1-25 weight part with respect to 100 weight part of component.

  The compound having an epoxy group as component (D) preferably has at least one (meth) acryloyl group per molecule.

  It is preferable to have at least one of hindered phenol, hindered amine, and phosphorus antioxidants (F).

  It is preferably used for an LED sealing material, a solar cell sealing material, a flat panel display sealing material, a sensor sealing material, and a lens.

  The present invention relates to a cured product for an optical material obtained from the active energy ray-curable composition for an optical material described above.

  After arrange | positioning a LED element, a solar cell element, a flat panel display element, a sensor element, and a lens on a board | substrate, it encapsulates using the active energy ray curable composition for optical materials in any one of Claims 1-15. The present invention relates to a manufacturing method of an LED module, a solar cell module, a flat panel display module, a sensor module, and a lens module that is cured after being stopped.

  For optical materials with excellent active energy ray curability, low viscosity, storage stability, low foamability, low temperature curing, low warpage, deep curability, heat and light resistance, rubber properties, crack resistance, moisture resistance, and design An active energy ray-curable composition, a cured product, and a production method are provided.

The present invention
(A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(In the formula, Ra represents ^a hydrogen atom or an organic group having 1 to 20 carbon atoms)
An active energy ray-curable composition for optical materials, which comprises an acrylic polymer obtained by living radical polymerization having at least one (meth) acryloyl group per molecule and (B) a photoradical polymerization initiator. And
(C) General formula (2):
R ^b —OC (O) C (CH ₃ ) ═CH ₂ (2)
(In the formula, R ^b represents an organic group having an alicyclic aliphatic structure or an aliphatic branched structure having 6 to 20 carbon atoms).
A methacrylic acid ester monomer represented by: and / or (D) a compound having an epoxy group,
When the component (C) is included, the content of the component (C) is 1 to 70 parts by weight with respect to 100 parts by weight of the component (A). When the component (D) is included, the content of the component (D) It is an active energy ray-curable composition for optical materials, the amount of which is 0.1 to 30 parts by weight with respect to 100 parts by weight of component (A).

In terms of heat resistance, light resistance and transparency,
(C) General formula (2):
R ^b —OC (O) C (CH ₃ ) ═CH ₂ (2)
(In the formula, R ^b represents an organic group having an alicyclic aliphatic structure or an aliphatic branched structure having 6 to 20 carbon atoms).
It is preferable to contain both the methacrylic acid ester monomer represented by these, and (D) the compound which has an epoxy group.

  Below, the curable composition of this invention is demonstrated in detail.

<< (A) component >> (A) component of this invention is
(A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(In the formula, Ra represents ^a hydrogen atom or an organic group having 1 to 20 carbon atoms)
An acrylic polymer obtained by living radical polymerization having at least one (meth) acryloyl group represented by

  Since an unreacted or side reaction may occur when the component (A) is produced, the average value of the number of (meth) acryloyl groups introduced into the acrylic polymer may deviate from the setting. In the present invention, when the average value of (meth) acryloyl groups introduced at the terminal of the acrylic polymer is 0.8 or more, this reaction product is referred to as component (A).

  The lower limit of the average value of (meth) acryloyl groups introduced into the acrylic polymer is preferably 0.8 or more, more preferably 0.9 or more, and even more preferably 1.0 or more. When the number is less than 0.8, the amount of unreacted components in the cured product increases, and thus tackiness may increase, and heat-resistant transparency, light-resistant transparency, and strength of the cured product may decrease. In addition, the upper limit of the average value of (meth) acryloyl groups introduced into the acrylic polymer is preferably 3.0 or less, more preferably 2.6 or less, and even more preferably 2.2 or less. When the number is more than 3.0, the number of cross-linking points of the cured product increases, so that the elongation of the cured product decreases, cure shrinkage increases, and cracks are likely to occur.

  Furthermore, the position of the (meth) acryloyl group introduced into the acrylic polymer is preferably present at the molecular end. When (meth) acryloyl groups are present irregularly in the side chain of the acrylic polymer, the distance between cross-linking points cannot be controlled, so that the elongation property of the cured product is deteriorated. The position of the (meth) acryloyl group is preferably present near the molecular end, and more preferably only at the molecular end, from the viewpoint that the distance between the cross-linking points can be increased and the elongation property of the cured product is improved.

  (A) As a component, you may use individually or in mixture of 2 or more types. For example, an acrylic polymer having a (meth) acryloyl group at both ends and an acrylic polymer having a (meth) acryloyl group at one end may be used in combination.

R ^a in the (meth) acryloyl group represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. The organic group is a group shown below.

  Examples of the organic group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a nitrile group, and the like. You may have the substituent of.

  Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group.

  Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group.

  Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenylethyl group.

Preferred examples of R ^a include, for example, —H, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) _n CH ₃ (n represents an integer of 2 to 19), —C ₆ H ₅ , — CH ₂ OH, —CN and the like can be mentioned, and preferably —H, —CH ₃ .

  (A) There is no limitation in particular as an acryl-type monomer which comprises the principal chain of the acryl-type polymer of a component, A various thing can be used. For example, (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, N-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic Isodecyl acid, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth ) Dodecyl acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, (meth) acrylic 2-hydroxyethyl acid, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (Methacryloyloxypropyl) trimethoxysilane, (meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethylmethyl, (meth) acrylic acid 2-trifluoromethylethyl, (meth) acrylic acid 2-par Fluoroethylethyl, 2-methacrylic acid (meth) acrylate Oroethyl-2-perfluorobutylethyl, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethyl methyl (meth) acrylate, 2-perfluoromethyl (meth) acrylate (Meth) acrylic acid such as 2-perfluoroethylethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate Examples include ester monomers. These may be used alone or in combination. Among the above acrylic monomers, (meth) acrylic acid ester monomers are preferable. Among (meth) acrylic acid ester monomers, (meth) acrylic acid ester monomers having an aromatic group are easily oxidized and colored by light. The (meth) acrylic acid ester monomer which does not contain an aromatic group is preferable.

  Moreover, since the glass transition temperature of hardened | cured material is low and elongation property is excellent, an acrylate monomer is more preferable. Specific examples of preferred acrylate monomers are ethyl acrylate, 2-methoxyethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate because they are readily available and easy to purify.

  In view of heat resistance and moisture permeability, the vinyl monomer constituting the main chain is particularly preferably butyl acrylate or 2-ethylhexyl acrylate.

  (A) As a component, the polymer which has a (meth) acrylic acid ester monomer as a main component is preferable, and the polymer which has an acrylic acid ester monomer as a main component is more preferable. In addition, a main component means that the said monomer is contained 50weight% or more among (A) components. The monomer is preferably contained in an amount of 60% by weight or more, and more preferably 80% by weight or more.

  In the present invention, these preferable monomers may be copolymerized with the other monomers, and in this case, it is preferable that these preferable monomers are contained in an amount of 50% by weight or more. In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  The molecular weight distribution of component (A) [ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC)] is not particularly limited, but the molecular weight distribution is narrower. From the viewpoint of improving the elongation property of the cured product, it is preferably less than 1.8, more preferably 1.5 or less, and still more preferably 1.3 or less. In the GPC measurement in the present invention, usually, chloroform or tetrahydrofuran is used as a mobile phase, a polystyrene gel column is used, and the molecular weight value is obtained in terms of polystyrene.

  The number average molecular weight of the acrylic polymer (A) in the present invention is not particularly limited, but is preferably 3,000 to 100,000, more preferably 5,000 to 80,000, as measured by GPC, 8 More preferably, 50,000 to 50,000. If the molecular weight is too low, the original properties (elongation properties) of the acrylic polymer (A) tend to be difficult to be expressed. On the other hand, if the molecular weight is too high, the viscosity tends to be high and handling becomes difficult. .

  The amount of component (A) used is preferably 40% by weight or more in the curable composition, more preferably 50% by weight or more, and still more preferably 60% by weight or more. When the amount of component (A) used is less than 40% by weight, the heat generated during curing increases, resulting in a decrease in transparency of the cured product, or a decrease in the elongation of the cured product and an increase in curing shrinkage resulting in cracks. It tends to occur. On the other hand, 90 wt% or less is preferable, 80 wt% or less is more preferable, and 70 wt% or less is even more preferable. When the amount of the component (A) used is more than 90% by weight, workability is deteriorated because the viscosity of the composition is high, and heat-resistant transparency of the cured product is lowered.

  (A) A component may be individual or may use 2 or more types together.

<Synthesis Method of Acrylic Polymer (A)>
The acrylic polymer (A) used in the present invention can be obtained by a living radical polymerization method, and atom transfer radical polymerization is preferred because of availability of raw materials and ease of introduction of a functional group at the polymer terminal. The living radical polymerization method and the atom transfer radical polymerization are known polymerization methods. For each polymerization method, for example, descriptions in Japanese Patent Application Laid-Open Nos. 2005-232419 and 2006-291073 can be referred to.

  The atom transfer radical polymerization, which is one of the preferred methods for synthesizing the acrylic polymer (A) in the present invention, will be briefly described below.

  In atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl-position), or a sulfonyl halide. A compound or the like is preferably used as an initiator. Specific examples include compounds described in paragraphs [0040] to [0064] of JP-A-2005-232419.

  In order to obtain an acrylic polymer having two or more functional groups in one molecule, an organic halide having two or more starting points or a sulfonyl halide compound is preferably used as an initiator. For example,

Etc.

  There is no restriction | limiting in particular as an acryl-type monomer used in atom transfer radical polymerization, All the acryl-type monomers mentioned above can be used conveniently.

  Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses a periodic table group 7, 8, 9, 10, or 11 element as a central metal, More preferably, it is 0. A transition metal complex having valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel as a central metal, particularly preferably a copper complex. Specific examples of the monovalent copper compound used to form the copper complex include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, and oxidized oxide. Cuprous, cuprous perchlorate, and the like. In the case of using a copper compound, 2,2′-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity These polyamines are added as ligands.

The polymerization reaction can be carried out without solvent, but can also be carried out in various solvents. It does not specifically limit as a kind of solvent, The solvent of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0067] is mentioned. These may be used alone or in combination of two or more. Polymerization can also be performed in an emulsion system or a system using supercritical fluid CO ₂ as a medium.

  Although superposition | polymerization temperature is not limited, It can carry out in the range of 0-200 degreeC, Preferably, it is the range of room temperature-150 degreeC.

  When the acrylic polymer (A) obtained by the synthesis method is colored, it is preferably treated with an oxidizing agent.

  It does not specifically limit as an oxidizing agent, For example, the oxidizing agent of Unexamined-Japanese-Patent No. 2002-69121 paragraph [0074] can be used. As the oxidizing agent, hydrogen peroxide is preferable because it is easily available and decomposes into oxygen and water by heating, so that the influence on the acrylic polymer (A) is small.

  The method of treating with an oxidizing agent may be any method, but a method of adding an oxidizing agent to the acrylic polymer (A) and stirring with heating, and then removing the solvent and the like under reduced pressure is preferred. When hydrogen peroxide is used as the oxidizing agent, for example, hydrogen peroxide having a concentration of 1 to 60% by weight and an acrylic polymer (A) are mixed, and 30 to 30 ° C. in the air at 70 to 150 ° C. An example is a method of removing water under reduced pressure after stirring for 300 minutes.

<Introduction method of (meth) acryloyl group>
A known method can be used to introduce the (meth) acryloyl group. Examples thereof include the methods described in paragraphs [0080] to [0091] of JP-A No. 2004-203932. Among these methods, from the viewpoint of easier control, it is preferable that the method is produced by replacing the terminal halogen group of the acrylic polymer with a compound having a (meth) acryloyl group.

  The acrylic polymer having a terminal halogen group is a method of polymerizing a vinyl monomer using the above-described organic halide or halogenated sulfonyl compound as an initiator and a transition metal complex as a catalyst, or a halogen compound as a chain transfer agent. Is produced by a method of polymerizing a vinyl monomer, but the former is preferred.

Although it does not specifically limit as a compound which has a (meth) acryloyl group, The compound represented by following General formula (4) can be used.
M ⁺ -OC (O) C (R ^a ) ═CH ₂ (4)
(In the formula, Ra represents ^a hydrogen atom or an organic group having 1 to 20 carbon atoms)
Specific examples of R ^{a in} the general formula (4) include, for example, —H, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) _n CH ₃ (n represents an integer of 2 to 19), _{-C 6 H 5, -CH 2 OH} , -CN, etc., and is preferably -H, -CH _3.

M ⁺ in the general formula (4) is a counter cation of the oxyanion, and examples of M ⁺ include alkali metal ions, specifically lithium ions, sodium ions, potassium ions, and quaternary ammonium ions. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, and dimethylpiperidinium ion, preferably sodium ion and potassium ion.

  The usage-amount of the oxyanion of General formula (4) becomes like this. Preferably it is 1-5 equivalent with respect to a halogen group, More preferably, it is 1.0-1.2 equivalent.

  The solvent for carrying out this reaction is not particularly limited but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric Triamide, acetonitrile, etc. are used.

  Although the temperature which performs reaction is not limited, Generally it is 0-150 degreeC, In order to hold | maintain a polymeric terminal group, Preferably it carries out at room temperature-100 degreeC.

<< (B) component >>
As the photoradical initiator which is the component (B) of the present invention, acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4, 4'-dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzo Benzoin methyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxy ketal, 2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy -Cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, dibenzoyl, bis (4-diethylaminophenyl) ketone, 2,4,6-trimethylbenzophenone, 3,3′-dimethyl- 4-methoxybenzophenone, 2-benzoylbenzoic acid, 2-benzoyl Ikikosan methyl, dibenzosuberone and the like.

  Among these, as photo-radical initiators having good ultraviolet curing properties, α-hydroxy ketone compounds (for example, benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxy-cyclohexyl-phenyl-ketone, etc.), phenyl ketone derivatives (for example, Acetophenone, propiophenone, benzophenone, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, 3-methoxy Benzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4-chloro-4′-benzylbenzophenone, bis (4-dimethylamino) Phenyl) ketone, etc.) are preferable.

  Examples of the photo radical initiator capable of suppressing oxygen inhibition on the surface of the cured product include, for example, 2-hydroxy-1- [4- [4- (2-hydroxy-) having two or more photodegradable groups in the molecule. 2-Methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one (trade name IRGACURE127, manufactured by BASF), 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl -2- (4-methylphenylsulfonyl) propan-1-one (trade name ESACURE1001M, manufactured by LAMBERTI), methylbenzoylformate (trade name: SPEDCURE MBF manufactured by LAMBSON), O-ethoxyimino-1-phenylpropane- 1-one (trade name: SPEDCURE PDO LAMBSON), oligo [2-hydride Roxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone (trade name ESCURE KIP150, manufactured by LAMBERTI), and a hydrogen abstraction type photo radical initiator having three or more aromatic rings in the molecule 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (trade name IRGACURE OXE01, etc., manufactured by BASF), ethanone, 1- [9-ethyl-6 -(2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) (trade name IRGACURE OXE02, etc., manufactured by BASF), 4-benzoyl-4′methyldiphenyl sulfide, 4- Phenylbenzophenone, 4,4 ', 4 "-(hexamethyltriamino) triphenylmethane, etc. It is.

  Further, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethyl), which are characterized by improved deep curability And acylphosphine oxide photo radical initiators such as benzoyl) -2,4,4-trimethyl-pentylphosphine oxide.

  In addition, 1-hydroxy-cyclohexyl-phenyl-ketone (trade name IRGACURE 184, manufactured by BASF), 2-hydroxy-2--2-ene-2-phenyl-ketone in terms of the balance between the active energy ray curability and the storage stability of the curable composition of the present invention. Methyl-1-phenyl-propan-1-one (trade name DAROCUR1173, manufactured by BASF), bis (4-dimethylaminophenyl) ketone, 2-hydroxy-1- [4- [4- (2-hydroxy-2-) Methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one (trade name IRGACURE127, manufactured by BASF), 1- [4- (4-Benzoxylphenylsulfanyl) phenyl] -2-methyl -2- (4-Methylphenylsulfonyl) propan-1-one (trade name ESACURE1001M, LAMB ERTI), methylbenzoylformate (trade name SPEDDCURE MBF LAMBSON), O-ethoxyimino-1-phenylpropan-1-one (trade name SPEEDCURE PDO LAMBSON), oligo [2-hydroxy-2 -Methyl-1- [4- (1-methylvinyl) phenyl] propanone (trade name ESACURE KIP150 manufactured by LAMBERTI), 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyl) Oxime)] (trade name IRGACURE OXE01, etc., manufactured by BASF), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime (Product name: IRGACURE OXE02, etc., manufactured by BASF 4-benzoyl-4'methyldiphenyl sulfide, 4-phenylbenzophenone, 4,4 ', 4 "-(hexamethyltriamino) triphenylmethane, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Trade name IRGACURE 819, manufactured by BASF), bis (2,6-dimethylbenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name) Lucirin TPO, manufactured by BASF) is more preferable.

  As the near infrared light radical initiator, a near infrared light absorbing cationic dye or the like may be used. As the near-infrared light absorbing cationic dye, near-infrared light which is excited by light energy in the region of 650 to 1500 nm, for example, disclosed in JP-A-3-111402, JP-A-5-194619, etc. It is preferable to use an absorbing cationic dye-borate anion complex or the like, and it is more preferable to use a boron sensitizer together.

  These photo radical initiators may be used alone or in combination of two or more, or may be used in combination with other compounds.

  As a combination with other compounds for improving curability, specifically, a combination with an amine such as diethanolmethylamine, dimethylethanolamine, triethanolamine, and further an iodonium salt such as diphenyliodonium chloride. Examples thereof include combinations thereof, pigments such as methylene blue, and those combined with amines.

  In addition, when using the said photoradical initiator, polymerization inhibitors, such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, para tertiary butyl catechol, can also be added as needed.

  Component (B) is preferably added in an amount of 0.001 to 10 parts by weight, based on 100 parts by weight of component (A), from the viewpoints of ultraviolet curability, storage stability, and transparency of the cured product. 5 parts by weight is more preferable, 0.01 to 3 parts by weight is further preferable, and 0.02 to 1 part by weight is most preferable. When the addition amount of the component (B) is less than 0.001 part by weight, the ultraviolet curability may be deteriorated. On the other hand, when it is more than 10 parts by weight, the storage stability and the transparency of the cured product may be deteriorated.

<< (C) component >>
(C) component is
(C) General formula (2):
R ^b —OC (O) C (CH ₃ ) ═CH ₂ (2)
(In the formula, R ^b represents an organic group having an alicyclic aliphatic structure or an aliphatic branched structure having 6 to 20 carbon atoms).
A methacrylic acid ester monomer represented by R ^b has 6 or more carbon atoms, preferably 8 or more carbon atoms, and more preferably 12 or more carbon atoms. When carbon number is less than 6, (C) component becomes volatile and there exists a tendency for the weight change at the time of high temperature to become large. On the other hand, it has 20 or less carbon atoms, but preferably 18 or less carbon atoms. When the number of carbon atoms is more than 20, the component (C) tends to have a high viscosity and the effect of reducing the viscosity of the composition tends to be low.

R ^b is an organic group having an alicyclic aliphatic structure or an aliphatic branched structure, but is alicyclic in that the curability is good, the strength properties of the cured product are good, the heat resistance, light resistance, and moisture permeability are excellent. An organic group having an aliphatic structure is preferable, and an organic group having a polycyclic aliphatic structure is more preferable.

  Specific examples of the component (C) having an alicyclic aliphatic structure include cyclohexyl methacrylate, isobornyl methacrylate, 3,3,5-trimethylcyclohexane methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate. , Dicyclopentanyl methacrylate, dicyclopentanyloxyethyl methacrylate, 1-adamantyl methacrylate, tricyclopentanyl methacrylate, tricyclopentenyl methacrylate.

  Specific examples of the component (C) having a polycyclic aliphatic structure include dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanyloxyethyl methacrylate, and methacrylic acid. Examples include 1-adamantyl, tricyclopentanyl methacrylate, and tricyclopentenyl methacrylate.

  Specific examples of the component (C) having an aliphatic branched structure include isooctyl methacrylate, 2-ethylhexyl methacrylate, isononyl methacrylate, isodecyl methacrylate, and isostearyl methacrylate. Among these (C) components having an aliphatic branched structure, isostearyl methacrylate is preferable in terms of good curability, good strength physical properties of the cured product, excellent heat resistance, light resistance, and moisture permeability. Among the components (C), examples of the component (C) having excellent heat and light resistance and transparency include isostearyl methacrylate, isobornyl methacrylate, and dicyclopentanyl methacrylate.

  (C) A component may be individual or may use 2 or more types together.

  The amount of component (C) used is 1 to 70 parts by weight per 100 parts by weight of component (A). When the amount of the component (C) used in the curable composition is less than 1% by weight, the heat resistance, light resistance and low viscosity effect cannot be obtained. When the amount of the component (C) used in the curable composition is more than 70% by weight, the heat generated during curing is large, resulting in a decrease in transparency of the cured product, an increase in volatile components during curing, and the surface. May become uneven, or the substrate may be damaged by heat.

  The amount of component (C) used in the curable composition is preferably 5% by weight or more, and more preferably 10% by weight or more. Moreover, 60 weight% or less is preferable and 50 weight% or less is more preferable.

<< (D) component >>
Although it does not specifically limit as (D) the compound which has an epoxy group of this invention, If a specific example is given, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3 , 4-epoxycyclohexylmethyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, glycidol , Ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether Polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxy cyclohexenyl methyl-3 ', 4'-epoxy cyclohexene carboxylate, 1,2-epoxy-4-vinylcyclohexane 1,2,8,9 diepoxy limonene, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypro Le triethoxysilane, .gamma.-glycidoxypropyl methyl dimethoxy silane, beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, beta-(3,4-epoxycyclohexyl) ethyl triethoxy silane.

  As the epoxy group of the compound having an epoxy group as component (D), a glycidyl group is preferred in that the cured product may be less colored.

  (D) As a compound which has an epoxy group of a component, the compound which has functional groups other than an epoxy group is preferable at the point which can suppress the transfer (bleed) to the cured | curing material surface at the time of hardening and after hardening, Specifically, , Glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, γ-glycidoxypropyltrimethoxysilane, γ-glycyl Sidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane may be mentioned.

  The compound having an epoxy group as the component (D) is preferably a compound having a (meth) acryloyl group in terms of good reactivity with the components (A) and (C) of the present invention. Examples include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth) acrylate.

  As the compound having an epoxy group as the component (D), glycidyl methacrylate is preferable in that the reactivity with the components (A) and (C) of the present invention is good and the cured product may be less colored.

  (D) A component may be individual or may use 2 or more types together.

  (D) The usage-amount of a component is 0.1-30 weight part with respect to 100 weight part of (A) component. When the amount is less than 0.1 part by weight, the effect of heat resistance, light resistance and transparency cannot be obtained. On the other hand, when it is used in an amount of more than 30 parts by weight, the effect may not be obtained or the compatibility may deteriorate and the cured product may become cloudy. (D) As for the usage-amount of a component, 1 weight part or more is more preferable, and 20 weight part or less is more preferable.

<< (E) component >>
In the present invention, the following component (E) may be included.

(E) component is
General formula (3):
R ^C — {OC (O) C (R ^a ) ═CH ₂ } _m (3)
(In the formula, m represents an integer of 2 to 6, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ^c represents an organic group having 6 to 20 carbon atoms)
(Meth) acrylic acid ester monomer represented by

  The component (E) is used for improving curability and controlling mechanical properties (elongation and strength). M in the general formula (3) is preferably 3 or less, more preferably 2 in terms of excellent mechanical properties (elongation, strength) of the cured product.

R ^a may be used as well ^{R a} in formula (1) described above.

R ^a is, heat transparency, a methyl group is preferable in terms of good light transparency.

R ^c is preferably an organic group having 6 to 20 carbon atoms, more preferably an organic group having 8 to 18 carbon atoms, and even more preferably an organic group having 12 to 15 carbon atoms. When carbon number is less than 6, (E) component becomes volatile and there exists a tendency for the weight change at the time of high temperature to become large. On the other hand, when the number of carbon atoms is more than 20, the component (E) tends to have a high viscosity and the effect of reducing the viscosity of the composition tends to be low.

R ^c is preferably a chain aliphatic structure, preferably having 8 or more carbon atoms, more preferably having 12 or more carbon atoms, from the viewpoint of good mechanical properties (elongation, strength) of the cured product and excellent water absorption resistance and moisture absorption resistance. preferable.

Specific examples of the component (E) having a chain aliphatic structure include triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and 3-methyl-1,5-pentanediol di (meth) acrylate. 1,6-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 2-methyl-1,8-octanediol di ( And (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, and the like. Moreover, the compound shown by the following Formula etc. are mentioned.
_{CH 2 = CHC (O) O-} (CH 2) n -OC (O) CH = CH 2
(N is an integer from 6 to 20)
_{CH 2 = C (CH 3)} C (O) O- (CH 2) n -OC (O) C (CH 3) = CH 2
(N is an integer from 6 to 20)
_{CH 2 = CHC (O) O-} (CH 2 CH 2 O) n -OC (O) CH = CH 2
(N is an integer of 3 to 10)
_{CH 2 = C (CH 3)} C (O) O- (CH 2 CH 2 O) n -OC (O) C (CH 3) = CH 2
(N is an integer of 3 to 10)
As the component (E) having a chain aliphatic structure, a vinyl monomer having no ether structure is preferable from the viewpoint of good heat resistance and insulation. Examples of vinyl monomers having no ether structure include 3-methyl-1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,7-heptanediol di (Meth) acrylate, 1,8-octanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decane Examples thereof include diol di (meth) acrylate.

R ^c is preferably a cyclic structure, more preferably an alicyclic aliphatic structure, and even more preferably a polycyclic aliphatic structure in that the cured product has excellent water absorption resistance and moisture absorption resistance.

  Specific examples of the component (E) having an alicyclic aliphatic structure include cyclohexanedimethanol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, 1,3-adamantanedimethanol di (meth) ) Acrylate and the like. (E) component with particularly good balance of water absorption resistance, moisture absorption resistance, low volatility and low viscosity effect includes 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate And dimethylol-tricyclodecane di (meth) acrylate.

  Although it does not specifically limit as a vinyl-type monomer which has 3-6 (meth) acryloyl type groups, A trimethylol propane tri (meth) acrylate and a pentaerythritol are the points with low viscosity, high reactivity, and good availability. Tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are preferred.

  As the component (E), two or more kinds may be used in combination.

  (E) The usage-amount of a component is 1 weight part or more with respect to 100 weight part of (A) component, and 5 weight part or more is more preferable. When the amount is less than 1 part by weight, the effect of improving curability may not be obtained. On the other hand, it is preferably 25 parts by weight or less, and more preferably 20 parts by weight or less. If it exceeds 25 parts by weight, the cured product becomes hard and warpage and cracking tend to occur.

<< (F) component >>
In the present invention, the following component (F) may be included.

  (F) A component is at least 1 sort (s) among a hindered phenol type, a hindered amine type, and a phosphorus antioxidant, and is used for the heat resistant coloring and light resistant coloring of hardened | cured material. Antioxidants containing sulfur are not preferred because they tend to cause coloration in the light resistance test.

  It does not specifically limit as a hindered phenolic antioxidant, A conventionally well-known thing can be used widely. Specific examples include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono (or di or tri) (α methylbenzyl) phenol, 2 2,2'-methylenebis (4ethyl-6-tert-butylphenol), 2,2'-methylenebis (4methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, triethyleneglycol-bis- [3- (3-t-butyl-5-methyl-4hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl Propionate], pentaerythrityl-tetrakis [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-tert-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate Diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-t-butyl-4- Ethyl hydroxybenzylphosphonate) calcium, tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, N, N′-bis [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris (2,4-di-t-butylphenyl) phosphite, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2 -[2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl)- Benzotriazole, condensate with methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol (molecular weight about 300), hydroxyphenylbenzotriazole Derivatives, bis (1,2,2,6,6-pentamethyl-4-piperidyl) 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 2,4 -Di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate and the like.

  In terms of trade names, Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack NS-7, Nocrack DAH (all of which are Ouchi Shinsei Chemical Industries Co., Ltd.), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330 (all of which are ADEKA) IRGANOX-245, IRGANOX-259, IRGANOX-1010, IRGANOX-1024, IRGANOX-1076, IRGANOX-1098, IRGANOX-1330, IRGANOX-1425WL Manufactured by Ciba Inc.), SumilizerGM, manufactured by Sumitomo Chemical Co., Ltd. Any SumilizerGA-80 (or higher) do not can be exemplified as being limited thereto and the like. These hindered phenolic antioxidants may be used alone or in combination of two or more.

  A hindered phenol-based antioxidant having a hindered phenol structure on one side is preferable to a hindered phenol structure on both sides, from the viewpoint of good coloration suppression effects on heat and light.

  Further, tetrakis- [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl), in which the hindered phenolic antioxidant has a molecular weight of 600 or more in that the volatilization loss with respect to heat may be small. Propionate] methane, tris- [N- (3,5-di-t-butyl-4-hydroxybenzyl)] isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di -T-butyl-4-hydroxybenzyl) benzene, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane is more preferred. The molecular weight can be measured using GC-MS or LC-MS.

  The amount of hindered phenolic antioxidant used is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 3 parts by weight, based on 100 parts by weight of component (A). Most preferably, it is 0.03 to 1 part by weight. If the amount is less than 0.01 part by weight, the effect of suppressing coloring is small, and if it exceeds 5 parts by weight, it may cause coloring.

  It does not specifically limit as a hindered amine type antioxidant, A conventionally well-known thing can be used widely.

  The hindered amine antioxidant is at least one of the following general formula (5) in one molecule.

(In the formula, X is represented by —H, —R, —OR ′, —R ″, and R, R ′, R ″ represents a monovalent or divalent substituent containing carbon, hydrogen, or oxygen. Typical examples include a methyl group, an ethyl group, an alkyl group containing an alicyclic structure having 3 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms such as an acetyl group and a propionyl group, and 1 carbon atom. Examples include, but are not limited to, an alkylene group having ˜20, a polyester unit from succinic acid / ethylene glycol, etc. In addition, an alkylene group having 1 to 20 carbon atoms, and a divalent compound such as a polyester unit from succinic acid / ethylene glycol. In the case of the substituent, the other end is bonded to another hindered piperidine group.)).

  Specific examples, CHIMASSORB119, CHIMASSORB2020, CHIMASSORB944, TINUVIN622, TINUVIN B75, TINUVIN783, TINUVIN111, TINUVIN791, TINUVIN C353, TINUVIN494, TINUVIN492, TINUVIN123, TINUVIN144, TINUVIN152, TINUVIN292, TINUVIN5100, TINUVIN765, TINUVIN770, TINUVIN XT850, TINUVIN XT855, TINUVIN440 TINUVIN NOR371 (manufactured by Ciba Japan), ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67 , ADK STAB LA-63, ADK STAB LA-63P, ADK STAB LA-68LD, ADK STAB LA-82, ADK STAB LA-87, ADK STAB LA-501, ADK STAB LA-502XP, ADK STAB LA-503, ADK STAB LA-77, ADK STAB LX-335 , Adecanol UC-605 (manufactured by ADEKA), SANOL LS770, SANOL LS765, SANOL LS292, SANOL LS440, SANOL LS744, SANOL LS2626, SANOL LS944 (manufactured by Sankyo Lifetech), Hostavin (HOSTAVIN) N20, Hostabin N24, Hostabin N30, Hostabin N321, Hostabin PR31, Hostabin 3050, Hostabin 3051, Hostabin 305 Hostabin 3053, Hostabin 3055, Hostabin 3058, Hostabin 3063, Hostabin 3212, Hostabin TB01, Hostabin TB02, Nyrostab (Nylostab) S-EED (manufactured by Clariant Japan), Tomissorb 77 (manufactured by Yoshitomi Fine Chemicals), Siasorb (CYASB) ) UV3346, Siasorb UV3529, Siasorb UV3853 (manufactured by Sun Chemical) SUMISORB TM61 (manufactured by Sumitomo Chemical), Goodlight UV3159, Goodlight UV3034, Goodlight UV3150, Goodlight 3110 × 128 (above BF Goodrich) ), Ubinur 4049, Ubinur 4050, Ubinur 5050 Above but BASF Corp.) and the like can be exemplified, without limitation. These may be used alone or in combination of two or more.

  Among these hindered amine antioxidants, Adekastab LA-63, Adekastab LA-63P, TINUVIN152, TINUVIN123, Sanol LS765, Hostabin N24 from the viewpoint of excellent storage stability of the curable composition and weatherability of the resulting cured product. Hostabin N30 is preferred.

  The amount of hindered amine antioxidant used is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 3 parts by weight, based on 100 parts by weight of component (A). Most preferred is 03 to 1 part by weight. If it is less than 0.01 part by weight, the effect of suppressing coloration is not exhibited, and if it exceeds 5 parts by weight, it may cause coloration.

  The phosphorus antioxidant is not particularly limited and any one can be used. However, since phosphoric acid and phosphoric acid ester containing active hydrogen affect the storage stability of the composition and the heat resistance of the cured product, Alkyl phosphites, aryl phosphites, alkylaryl phosphite compounds and the like that do not contain phosphoric acid and phosphate ester in the molecule are preferred.

  Specific examples of phosphorus antioxidants include tris (nonylphenyl) phosphite, tris (mono, dinonylphenyl) phosphite, diphenyl, mono (2-ethylhexyl) phosphite, diphenyl, mono (tridecyl) phosphite, Diphenyl, mono (isodecyl) phosphite, diphenyl, mono (isooctyl) phosphite, diphenyl, mono (nonylphenyl) phosphite, triphenyl phosphite, tris (tridecyl) phosphite, triisodecyl phosphite, tris (2- Ethylhexyl) phosphite, trilauryl phosphite, trioleyl phosphite, tristearyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetraphenyldipropylene glycol-diphosphite Tetraphenyltetra (tridecyl) pentaerythritol-tetraphosphite, 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-tert-butylphenyl) butane, 4,4′-butylidenebis (3 -Methyl-6-t-butyl-di-tridecyl phosphite), 2,2'-methylenebis (4,6-di-t-butylphenol) octyl phosphite, 4,4'-isopropylidene-diphenol alkyl ( C12-C15) phosphite, cyclic neopentanetetrayl bis (2,4-di-t-butylphenyl phosphite), cyclic neopentanetetrayl bis (2,6-di-t-butyl-4-methylphenylphos) Phyto), cyclic neopentanetetraylbis (nonylphenyl phosphite), bis (nonylpheny) ) Pentaerythritol diphosphite, distearyl pentaerythritol, diphosphite, bis [2,4-bis (1,1'-dimethylethyl) -6-methylphenyl] ethyl ester phosphite, and the like.

  In terms of product names, ADK STAB 1178, ADK STAB 329K, ADK STAB 135A, ADK STAB C, ADK STAB TPP, ADK STAB 3010, ADK STAB 2112, ADK STAB 522A, ADK STAB 260, ADK STAB HP-10, ADK STAB 1500, ADK STAB PEP-24PEP, ADK STAB PEP-24PE -36, ADK STAB PEP-4C, ADEKASTA PEP-8 (all manufactured by ADEKA), JPM-308, JPM-313, JPM-333E, JPP-100, JPP-613M, JPP-31, JP-351, JP -308E, JP-310, JP-312L, JP-333E, JP-318O, JP-318E (all manufactured by Johoku Chemical Co., Ltd.), CHELEX-M, (manufactured by Sakai Chemical Co., Ltd.), IRGAFOS 8 but (BASF Corp.) or the like can be exemplified but is not limited thereto.

  The phosphorus-based antioxidant preferably has a hydrocarbon group having 8 or more carbon atoms in all of the substituents of the phosphorus atom from the viewpoint of being stable with respect to hydrolyzability and having good heat resistance. Specifically, tris (nonylphenyl) phosphite, tris (mono, dinonylphenyl) phosphite, tris (tridecyl) phosphite, triisodecyl phosphite, tris (2-ethylhexyl) phosphite, trilauryl phosphite , Trioleyl phosphite and tristearyl phosphite are preferable.

  Phosphorous antioxidants may be used alone or in combination of two or more.

  The amount of the phosphorus antioxidant used is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 3 parts by weight, based on 100 parts by weight of component (A). Most preferred is 03 to 1 part by weight. If it is less than 0.01 part by weight, the effect of suppressing coloration is not exhibited, and if it exceeds 5 parts by weight, it may cause coloration.

  Phosphorous antioxidants exhibit excellent coloration suppression effects against heat and light when used in combination with the hindered phenol antioxidants and / or hindered amine antioxidants. The use ratio of the hindered phenol-based antioxidant and / or hindered amine-based antioxidant and the phosphorus-based antioxidant is not particularly limited, but from the viewpoint of more effectively improving the coloring suppression effect against heat and light. The ratio of (total amount of hindered phenol-based antioxidant and hindered amine-based antioxidant) / (phosphorus-based antioxidant amount) is preferably in the range of 0.1 to 10, preferably 0.3 to 3. It is particularly preferred.

  (F) The preferred combination of components is not particularly limited, but for example, a combination of IRGANOX 1010 and ADK STAB 1178 or JP-308E, a combination of Sumilizer GA-80 and ADK STAB 1178 or JP-308E, ADK STAB LA-63P and ADK STAB 1178 or The combination of JP-308E and the combination of Sumilizer GA-80 and Adeka Stub LA-63P and Adeka Stub 1178 or JP-308E are mentioned.

  The total amount of component (F) used is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 3 parts by weight, relative to 100 parts by weight of component (A). Most preferably, it is 0.03 to 1 part by weight. If it is less than 0.01 part by weight, the effect of suppressing coloration is not exhibited, and if it exceeds 5 parts by weight, it may cause coloration.

<< Curable composition >>
The active energy ray-curable composition of the present invention contains the components (A) to (B), the component (C) and / or the component (D), and if necessary, the component (E) and / or (F). In order to adjust the physical properties, various additives such as polymerizable monomers and / or oligomers, photocurable resins, air oxidation curable substances, initiators, and adhesion imparting agents are included. , Coupling agent, cure modifier, metal soap, filler, fine hollow particles, plasticizer, solvent, flame retardant, UV absorber, light stabilizer, antioxidant, heat stabilizer, physical property modifier, radical inhibitor , Metal deactivator, ozone degradation inhibitor, phosphorus peroxide decomposer, lubricant, pigment, foaming agent, surfactant, storage stability improver, inorganic filler, thickener, thixotropic agent, conductivity Giving agents, antistatic agents, radiation blocking agents, nucleating agents, etc. It may be appropriately blended according to necessity. These various additives may be used alone or in combination of two or more.

  Specific examples of such additives are described in, for example, the specifications of JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, and JP-A-64-22904. Yes.

<Polymerizable monomer and / or oligomer>
In the curable composition of the present invention, a monomer and / or an oligomer other than the component (A), the component (C), the component (D), and the component (E) may be added as long as the effects of the present invention are not impaired. it can. A monomer and / or oligomer having a radical polymerizable group is preferred from the viewpoint of curability.

  Examples of the radical polymerizable group include (meth) acryloyl groups such as (meth) acrylic groups, styrene groups, acrylonitrile groups, vinyl ester groups, N-vinylpyrrolidone groups, acrylamide groups, conjugated diene groups, vinyl ketone groups, and vinyl chloride. Groups and the like. Among these, those having a (meth) acryloyl group similar to the vinyl polymer used in the present invention are preferable in terms of good copolymerizability and few unreacted components.

Specific examples of the monomer include (meth) acrylate monomers, cyclic acrylates, styrene monomers, acrylonitrile, vinyl ester monomers, N-vinyl pyrrolidone, acrylamide monomers, conjugated diene monomers, vinyl ketone monomers, vinyl halides. -Halogenated vinylidene monomers and the like. (Meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2- (meth) acrylic acid 2- Hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 2-aminoethyl (meth) acrylate, N- (meth) acryloylmorpholine, tetrahydrofuranyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ( Ethylene oxide adduct of (meth) acrylic acid, (meth) Propylene oxide adduct of crylic acid, trifluoromethyl methyl (meth) acrylate, 2-trifluoromethyl ethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2-par (meth) acrylic acid Fluoroethyl-2-perfluorobutylethyl, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoro (meth) acrylate Methyl-2-perfluoroethylethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate, n-hexyl ( (Meth) acrylate, n-heptyl (meth) acrylate , N-octyl (meth) acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, isononyl acrylate, n-decyl (meth) acrylate, isodecyl acrylate, n-dodecyl (meth) acrylate, tridecyl (meth) ) Acrylate, stearyl (meth) acrylate, isostearyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 3,3,5-trimethylcyclohexane acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, di Cyclopentanyloxyethyl acrylate, 1-adamantyl acrylate, tricyclopentanyl acrylate, tricyclopentenyl acrylate Relate, N- (meth) acryloyl-ε-caprolactam, 3-ethyl-3-oxetanyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, Nonylphenoxypolyethylene glycol (meth) acrylate, O-phenylphenol (meth) acrylate, etc. are mentioned. Moreover, the compound shown by the following Formula etc. are mentioned.
_{CH 2 = CHC (O) O-} (CH 2) n -CH 3
(N is an integer from 5 to 19)
_{CH 2 = C (CH 3)} C (O) O- (CH 2) n -CH 3
(N is an integer from 5 to 19)
_{CH 2 = CHC (O) O-} (CH 2 CH 2 O) n -CH 3
(N is an integer from 3 to 9)
_{CH 2 = C (CH 3)} C (O) O- (CH 2 CH 2 O) n -CH 3
(N is an integer from 3 to 9)
_{CH 2 = CHC (O) O-} (CH 2 CH 2 O) n -CH 2 CH 3
(N is an integer from 2 to 9)
_{CH 2 = C (CH 3)} C (O) O- (CH 2 CH 2 O) n -CH 2 CH 3
(N is an integer from 2 to 9)

  Examples of the styrenic monomer include styrene and α-methylstyrene.

  Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, and vinyl butyrate.

  Examples of the acrylamide monomer include acrylamide and N, N-dimethylacrylamide.

  Examples of the conjugated diene monomer include butadiene and isoprene.

  Examples of the vinyl ketone monomer include methyl vinyl ketone.

  Examples of the vinyl halide / vinylidene halide monomer include vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, and vinylidene bromide. Examples of the polyfunctional monomer include neopentyl glycol polypropoxydi (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, trimethylolpropane polyethoxy (meth) triacrylate, and the like.

  Examples of the oligomer include epoxy acrylate resins such as bisphenol A type epoxy acrylate resin, phenol novolak type epoxy acrylate resin, cresol novolak type epoxy acrylate resin, and COOH group-modified epoxy acrylate type resin; polyol (polytetramethylene glycol, ethylene glycol Adipic acid polyester diol, ε-caprolactone-modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc.) and organic isocyanate (tolylene diisocyanate, isophorone diisocyanate, Diphenylmethane diisocyanate, hexamethylene dii A urethane resin obtained from cyanate, xylylene diisocyanate, etc.) with a hydroxyl group-containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, etc.} Urethane acrylate resin obtained by reaction; resin in which a (meth) acryl group is introduced into the polyol via an ester bond; polyester acrylate resin, poly (meth) acryl acrylate resin (having a polymerizable reactive group) Poly (meth) acrylic ester resin) and the like.

  Moreover, radical reactive oligomers having a hydrophobic main chain can be added to improve insulation. For example, di (meth) acrylate having a butadiene skeleton (trade name; BAC-45, manufactured by Osaka Organic Chemical Industry), urethane acrylate having a bis A skeleton, epoxy acrylate having a bis A skeleton, polyester acrylate having a bis A skeleton, Each hydrogenated product etc. are mentioned.

  Of the above, monomers and / or oligomers having a (meth) acryloyl group are preferred. The number average molecular weight of the monomer and / or oligomer having a (meth) acryloyl group is preferably 5000 or less. Furthermore, in the case of using a monomer for improving the surface curability and reducing the viscosity for improving workability, it is more preferable that the molecular weight is 1000 or less because of good compatibility.

  The amount of the polymerizable monomer and / or oligomer used is preferably 1 to 200 parts with respect to 100 parts by weight of the component (A), from the viewpoint of improving surface curability, imparting toughness, and workability due to viscosity reduction. 5 to 100 parts is more preferable.

  In addition, radical curing by ultraviolet rays tends to inhibit surface curing by oxygen. In order to reduce surface hardening inhibition, it is preferable to use a monomer and / or oligomer having an ether group, a hydroxyl group or an amino group. The preferred amount is 1 to 10 parts per 100 parts by weight of component (A). If it is less than 1 part, the effect cannot be obtained. On the other hand, if it exceeds 10 parts, the physical properties may be adversely affected.

  The curable composition of the present invention may be used in combination with a curing reaction other than the curing reaction by polymerization of the (meth) acryloyl group of the (A) component, (C) component, (D) component, and (E) component. it can. As an advantage of using the curing reaction in combination, for example, when the active energy ray-curable composition of the present invention is UV-cured, a shadow portion that is not exposed to UV light becomes poorly cured. In such a case, the shadow can be cured by using a curing reaction in combination.

<Other vinyl polymers>
When the above curing reaction is used in combination, another vinyl polymer can be added and cured. As the other vinyl polymer, a vinyl polymer in which the (meth) acryloyl group, which is a functional group, is changed to an alkenyl group or a hydrolyzable silyl group in the component (A) can be used. The method for introducing these functional groups is shown below.

[Alkenyl group]
As a method for introducing an alkenyl group capable of hydrosilylation reaction into the obtained vinyl polymer, a known method can be used. For example, the method of Paragraph [0042]-[0086] of Unexamined-Japanese-Patent No. 2004-059783 is mentioned. Further preferred examples are also described in the same paragraph.

[Hydrolyzable silyl group]
As a method for introducing the hydrolyzable silyl group into the obtained vinyl polymer, a known method can be used. Examples thereof include the methods described in paragraphs [0076] to [0138] of JP-A-2000-191912. Further preferred examples are also described in the same paragraph.

  The following can be used as a polymerization initiator or a polymerization catalyst when using a vinyl polymer whose terminal functional group is an epoxy group, an alkenyl group, or a hydrolyzable silyl group.

  In the case of a vinyl polymer in which the terminal functional group is an alkenyl group, it is preferable to further use a hydrosilyl group-containing compound, for example, those described in JP-A-2004-059783 [0087] to [0091]. . In order to promote the hydrosilylation reaction, it is preferable to use a hydrosilylation catalyst in combination, and examples include those described in the publication [0092].

  In the case of a vinyl polymer in which the terminal functional group is a hydrolyzable silyl group, a curing catalyst is suitable, and examples include those described in paragraphs [0147] to [0150] of JP-A-2000-191912. Moreover, you may use together hardening reaction other than the above, and cyanate resin, a phenol resin, a polyimide resin, a urethane resin, a silicone resin etc. are mentioned.

<Initiator>
As an initiator other than the photoradical initiator of component (B), a thermal radical initiator or a redox initiator can be used. These initiators may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular as a thermal radical initiator, An azo initiator, a peroxide initiator, a persulfate initiator, etc. are mentioned. The azo initiator is not limited, but 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (VAZO33), 2,2′-azobis (2-amidinopropane) Dihydrochloride (VAZO50), 2,2'-azobis (2,4-dimethylvaleronitrile) (VAZO52), 2,2'-azobis (isobutyronitrile) (VAZO64), 2,2'-azobis-2 -Methylbutyronitrile (VAZO67), 1,1-azobis (1-cyclohexanecarbonitrile) (VAZO88) (all available from DuPont Chemical), 2,2'-azobis (2-cyclopropylpropionitrile), and 2,2'-azobis (methylisobutyrate) (V-601) (available from Wako Pure Chemical Industries)

  Peroxide initiators include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t-butylcyclohexyl) peroxy. Dicarbonate (Perkadox 16S) (available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11) (available from Elf Atochem), t-butyl peroxy-2- Examples include ethyl hexanoate (Trigonox 21-C50) (available from Akzo Nobel) and dicumyl peroxide.

  Persulfate initiators include, but are not limited to, potassium persulfate, sodium persulfate, ammonium persulfate, and the like.

  A preferable thermal radical initiator is selected from the group consisting of an azo initiator and a peroxide initiator. More preferred are 2,2'-azobis (methylisobutylate), t-butyl peroxypivalate, di (4-t-butylcyclohexyl) peroxydicarbonate, and mixtures thereof.

  A thermal radical initiator may be used independently or may use 2 or more types together.

  The amount of the thermal radical initiator used is preferably 0.01 to 5 parts by weight and more preferably 0.05 to 2 parts by weight with respect to 100 parts by weight as the total of the active energy ray-curable composition.

  Redox (redox) initiators can be used in a wide temperature range. In particular, the following initiator species can be advantageously used at room temperature.

  Suitable redox initiators include, but are not limited to, combinations of the above persulfate initiators and reducing agents (sodium metabisulfite, sodium bisulfite, etc.); organic peroxides and tertiary amines. Combinations such as a combination of benzoyl peroxide and dimethylaniline, a combination of cumene hydroperoxide and anilines; a combination of organic peroxide and transition metal, such as a combination of cumene hydroperoxide and cobalt naphthate, and the like.

  Preferred redox initiators are a combination of organic peroxide and tertiary amine, a combination of organic peroxide and transition metal, and more preferably a combination of cumene hydroperoxide and anilines, cumene hydroperoxide. And cobalt naphthate. A redox initiator may be used independently or may use 2 or more types together.

  The amount of the redox initiator used is preferably 0.01 to 5 parts by weight and more preferably 0.05 to 2 parts by weight with respect to 100 parts by weight as the total of the active energy ray-curable composition.

<Adhesive agent>
A silane coupling agent or an adhesion-imparting agent other than the silane coupling agent can be added to the active energy ray-curable composition of the present invention. When the adhesion imparting agent is added, the risk that the cured product of the present invention is peeled off from the adherend can be further reduced. In some cases, simplification of primer treatment used for improving adhesiveness is expected.

  Specific examples of the silane coupling agent include amino groups, mercapto groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, halogen and other functional groups such as halogens. , Γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and other isocyanate group-containing silanes; γ-aminopropyltrimethoxysilane, γ -Aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropylto Methoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ- (2 -Aminoethyl) aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ- Amino group-containing silanes such as aminopropyltriethoxysilane; mercaptors such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane Group-containing silanes; carboxysilanes such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane Vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-acryloyloxypropylmethyltriethoxysilane; γ-chloropropyltrimethoxysilane, etc. And halogen-containing silanes; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate; In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, blocked isocyanate silanes, silylated polyesters, etc., which are derivatives of these, are also used as silane coupling agents. Can be used.

  0.1-20 weight part is preferable with respect to 100 weight part of active energy ray-curable compositions, and, as for the silane coupling agent used for this invention, 0.5-10 weight part is more preferable.

  Although it does not specifically limit as a specific example other than a silane coupling agent, For example, a phenol resin, sulfur, alkyl titanates, aromatic polyisocyanate etc. are mentioned.

  The adhesiveness-imparting agent may be used alone or in combination of two or more.

<Solvent>
Although the composition of the present invention can be directly formed into a thin film such as a film, the composition can be dissolved in an organic solvent to form a varnish. Solvents that can be used are not particularly limited, and specific examples include hydrocarbon solvents such as benzene, toluene, hexane, and heptane, ether solvents such as tetrahydrofuran, 1,4-dioxane, and diethyl ether, and acetone. A ketone solvent such as methyl ethyl ketone, an ester solvent such as propylene glycol monomethyl ether acetate or ethylene glycol monomethyl ether acetate, or a halogen solvent such as chloroform, methylene chloride or 1,2-dichloroethane can be preferably used. The solvent can also be used as a mixed solvent of two or more types. As the solvent, toluene, tetrahydrofuran, and propylene glycol monomethyl ether acetate are preferable.

  It is preferable to use the solvent in an amount of 0.1 to 10 mL with respect to 1 g of the active energy ray-curable composition. If the amount used is small, it is difficult to obtain effects such as viscosity reduction. On the other hand, if the amount used is large, the solvent may remain in the cured product, resulting in problems such as peeling and coloring.

<Inorganic filler>
You may add an inorganic filler to the composition of this invention as needed. Addition of an inorganic filler is effective in preventing fluidity of the composition and increasing the strength of the material. As the inorganic filler, fine particles that do not deteriorate the optical properties are preferable, and examples thereof include alumina, aluminum hydroxide, fused silica, crystalline silica, ultrafine amorphous silica, hydrophobic ultrafine silica, talc, and barium sulfate. it can.

  Various additives for improving LED characteristics may be added to the composition of the present invention. Examples of additives include phosphors such as yttrium, aluminum, and garnet phosphors that absorb light from light emitting elements to emit longer wavelength fluorescence, and colorants such as bluing agents that absorb specific wavelengths. Various inorganic or organic diffusing materials such as titanium oxide, aluminum oxide, silica, silica glass, etc. for diffusing light, talc, calcium carbonate, melamine resin, CTU guanamine resin, benzoguanamine resin, glass, aluminosilicate And the like, and metal oxides such as aluminum nitride, boron nitride and other metal nitrides. The additive for improving the characteristics of the light emitting diode may be contained uniformly, or the content may be added with a gradient. The optical material of the present invention refers to general materials used for the purpose of allowing light such as ultraviolet rays, visible rays, infrared rays, X-rays, and lasers to pass through the materials.

<< Method for Preparing Curable Composition >>
The method for preparing the active energy ray-curable composition of the present invention is not particularly limited, but all the blending components may be prepared as a one-component type, and the blending components are taken into account in view of the storage stability of the composition. May be prepared separately and adjusted as a two-component type to be mixed before use.

  In the case of the one-component type, there is no need for mixing and kneading at the time of construction, and at the same time, there is no weighing error (incorrect mixing ratio), and thus errors such as poor curing can be prevented.

  In the case of the two-component type, each compounding component can be arbitrarily divided into two liquids and adjusted as a two-component type in which the compounding components are mixed before use. The method for dividing the liquid A and the liquid B can be variously combined in consideration of the mixing ratio of the curable composition, the storage stability, the mixing method, the pot life, and the like.

  Moreover, if necessary, it is possible to prepare a three-component curable composition by preparing a third component in addition to the liquid A and the liquid B, and further division can be adjusted as necessary. is there.

  The mixing method of the composition of the present invention is not particularly limited. For example, the above-described components are blended, and if necessary, light-shielded, mixed with a hand mixer or a static mixer, a planetary mixer, a disper, a roll, Examples of the conventional method include kneading using a kneader or the like at room temperature or under heating, and using a small amount of a suitable solvent to dissolve and mix the components.

  The viscosity at 23 ° C. of the active energy ray-curable composition is preferably 100 Pa · s or less, more preferably 30 Pa · s or less, even more preferably 10 Pa · s or less, and most preferably 5 Pa · s or less. When the viscosity is higher than 100 Pa · s, productivity may be deteriorated. On the other hand, 0.05 Pa · s or more is preferable, 0.1 Pa · s or more is more preferable, and 0.2 Pa · s or more is even more preferable. When the viscosity is lower than 0.05 Pa · s, there may be a problem that the resin flows out from the needle tip during dispensing. The viscosity here can be measured with an E-type viscometer in accordance with JIS K 7117-2 conical-flat plate system.

<< cured product >>
The cured product of the present invention is obtained by curing the above active energy ray-curable composition. Although it does not specifically limit as a hardening method, It can be hardened by irradiating light or an electron beam with an active energy ray source. Although there is no limitation in particular as an active energy ray source, According to the property of the photoradical initiator to be used, a high pressure mercury lamp, a low pressure mercury lamp, an electron beam irradiation apparatus, a halogen lamp, a light emitting diode, a semiconductor laser, a metal halide etc. are mentioned, for example.

As the illuminance, preferably 50~1500mW / cm ^2, more preferably 100~1000mW / cm ^2, even more preferably 200~800mW / cm ^2. When it is less than 50 mW / cm ² , since the amount of light is small, it takes time to cure and the productivity is deteriorated. On the other hand, when it exceeds 1500 mW / cm ² , it may not be cured beautifully or the substrate may be damaged.

The amount of light, preferably 100~10000mJ / cm ^2, more preferably 300~6000mJ / cm ^2, even more preferably 500-3000 mW / cm ^2. When it is less than 100 mJ / cm ² , uncured components increase and adversely affect physical properties. On the other hand, when it exceeds 10,000 mJ / cm ² , energy cost is increased and productivity is deteriorated.

  The above illuminance and light quantity can be measured with an ultraviolet light quantity meter. For example, Ushio Electric, UIT-150, a light receiving sensor having a peak wavelength of 365 nm can be used.

  The curing temperature is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and even more preferably 50 ° C. or lower. When it hardens | cures at 100 degreeC or more, distortion becomes large because of the linear expansion difference between hardened | cured material and a base material.

<< Molding method >>
The molding method when the curable composition of the present invention is used as a molded body is not particularly limited, and various commonly used molding methods can be used. For example, cast molding, compression molding, transfer molding, injection molding, extrusion molding, rotational molding, hollow molding, thermoforming, and the like can be given. In particular, roll molding, calender molding, extrusion molding, liquid injection molding, and injection molding are preferred because they can be automated and continuous, and are excellent in productivity.

<< Usage >>
The active energy ray-curable composition for optical materials and the cured product of the present invention are suitable for applications that allow light such as ultraviolet rays, visible rays, infrared rays, X-rays, and lasers to pass through the materials.

  Specifically, the following uses are mentioned. Flat panel display and sealing material thereof; light guide plate, prism sheet, deflector plate, retardation plate, viewing angle correction film, front glass protective film, polarizer protective film, adhesive, panel or film in the liquid crystal display field Adhesives, fillers between panels or films, liquid crystal display peripheral materials such as liquid crystal films; color PDP (plasma display) sealing materials, antireflection films, optical correction films, front glass protective films, adhesives, Adhesives between panels or films, fillers between panels or films; molding materials for light emitting elements used in light emitting diode display devices, sealing materials for light emitting diodes (LEDs), protective films for front glass, adhesives, panels Or adhesive between films, filler between panels or films; Light guide plate, prism sheet, deflector plate, retardation plate viewing angle correction film, polarizer protective film, adhesive, adhesive between panel or film, filler between panel or film in organic liquid crystal (PALC) display; organic EL (Electroluminescence) Protective film on front glass in display, adhesive, adhesive between panel or film, filler between panel or film; between protective film, adhesive, panel or film in organic TFT (organic thin film transistor) display Adhesives, fillers between panels or films; various film substrates in field emission displays (FED), protective films for front glass, adhesives, adhesives between panels or films, fillers between panels or films; Protective films, adhesives in panels, adhesives between panels or films, fillers between panels or films; protective films for touch panels, mobile phone displays, car navigation displays, adhesives, adhesives between panels or films, panels Or the filler between films; It is a peripheral material of said display apparatus.

  In the optical recording field, VD (video disc), CD, CD-ROM, CD-R, CD-RW, DVD, DVD-ROM, DVD-R, DVD-RW, BD, BD-ROM, BD-R, BD -RE, MO, MD, PD (phase change disk), hologram, disk substrate material for optical card, pickup lens, protective film, sealing material, adhesive, and the like.

In the optical equipment field, they are still camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor sections. It is also a photographic lens and viewfinder for video cameras. Projection lenses for projection televisions, protective films, sealing materials, adhesives, and the like. These include lens materials, sealing materials, adhesives, and films for optical sensing devices.

  In the field of optical components, they are fiber materials, lenses, waveguides, element sealing materials, adhesives and the like around optical switches in optical communication systems. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. In optical passive components and optical circuit components, they are lenses, waveguides, sealing materials for light emitting elements, adhesives, and the like. These are substrate materials around an optoelectronic integrated circuit (OEIC), sealing materials for fiber material elements, adhesives, and the like.

  In the field of optical fiber, it is an optical fiber for lighting, light guides for decorative displays, sensors for industrial use, displays / signs, etc., and for communication infrastructure and home digital equipment connection.

  As the semiconductor integrated circuit peripheral material, it is a resist material for microlithography for LSI and VLSI material.

  In the LED peripheral field, it is an LED sealing material, a die bonding material, a reflector, and a substrate sealing material in which LEDs are arranged on a substrate having heat dissipation performance.

  In the solar cell peripheral field, it is a sealing material for an element, a protective film for a front glass, and an adhesive.

  The active energy ray-curable composition for optical materials and the cured product of the present invention can be used for applications other than those described above. For example, elastic sealants for buildings, sealants for siding boards, sealants for double-glazed glass, sealants for vehicles such as sealants for vehicles, electrical / electronic component materials such as solar cell backside sealants, electric wires・ Electrical insulation materials such as insulation coating materials for cables, adhesives, adhesives, elastic adhesives, contact adhesives, adhesives for tiles, reactive hot melt adhesives, paints, powder paints, coating materials, foams, Seals for can lids, heat dissipation sheets, electrical and electronic potting agents, films, gaskets, marine deck caulking, casting materials, various molding materials, artificial marble, and meshed glass and laminated glass end faces (cutting parts) Rust / waterproof sealing materials, vibration-proof / vibration-proof / sound-proof / isolation materials used in automobiles, ships, home appliances, automobile parts, electrical parts, various machine parts Liquid sealing agent used in etc., it is available in a variety of applications such as waterproofing agents.

<< Module manufacturing method >>
An LED module, a solar cell module, or a flat panel display module can be manufactured by collective sealing using the active energy ray-curable composition of the present invention. For example, an LED module can be obtained by arranging LED elements on a substrate, sealing them together with a curable composition, and then curing them.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

  In the following Examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column filled with polystyrene cross-linked gel (shodex GPC K-804 and K-802.5; manufactured by Showa Denko KK) and chloroform as a GPC solvent were used.

In the following Examples, “number of (meth) acryloyl groups introduced per polymer molecule” was calculated from the number average molecular weight determined by ¹ H-NMR analysis and GPC. (However, ¹ H-NMR was measured at 23 ° C. using Bruker ASX-400 and deuterated chloroform as a solvent.)

(viscosity)
The viscosity of the obtained polymer and the blending part was measured at a measurement temperature of 23 ° C. using an E-type viscometer manufactured by Toki Sangyo, in accordance with JIS K 7117-2 conical plate system.

(Production of cured product)
Made of Matsunami glass, white slide glass (model number: S1111, 1 mm thickness), a 1 mm thick silicone sheet with a 15 x 55 (mm) cut inside is attached, and active energy ray curable on the inside The composition was poured, the excess composition was removed with a spatula, and a cured product having a thickness of 1 mm was obtained by ultraviolet irradiation. Using the obtained cured product, the appearance of the cured product, evaluation of tack, and measurement of light transmittance were carried out.

(UV curing)
Fusion UV Systems Japan Co., Ltd. make, model LH6, H bulb was used, and ultraviolet curing conditions were 500 mW / cm ² and 3000 mJ / cm ² under nitrogen. The ultraviolet light meter used was Ushio Electric, UIT-150, and a light receiving sensor with a peak wavelength of 365 nm. For UV curing under nitrogen, a sample was placed in a sealable box equipped with a quartz glass lid and UV cured at an oxygen concentration of 5000 ppm or less. The oxygen concentration was confirmed by placing a commercially available oxygen concentration meter in a box and measuring it in advance.

(Appearance of cured product)
The cured product obtained was warped and no shrinkage was evaluated as ◯, and the warped and contracted material was rated as x.

(tack)
When the obtained cured product was touched with a finger, the case where there was no tack was indicated as ◯, the case where there was a tack as Δ, and the case where there was a deposit on the finger as ×.

(Light transmittance)
The light transmittance of the test piece was measured using a UV-visible spectrophotometer V-560 manufactured by JASCO Corporation under the condition of a scan speed of 200 nm / min. Each table shows the measurement result at 450 nm. Matsunami glass white slide glass (model number: S1111, 1 mm thickness) was used as a standard sample.

(Light resistance test)
Using a metering weather meter type M6T manufactured by Suga Test Instruments Co., Ltd., a test piece for measuring light transmittance was measured at an on-site temperature of 120 ° C. for 26 hours, an irradiance of 0.53 kW / m ² , and an integrated irradiance. After 50 MJ / m ² irradiation, the light transmittance was measured.

(Heat resistance test)
A specimen for measuring light transmittance was stored in an oven at 150 ° C. for 500 hours, and then light transmittance was measured.

(Synthesis Example 1)
<Synthesis example of poly (n-butyl acrylate) having acryloyl groups at both ends>
Using cuprous bromide as a catalyst, pentamethyldiethylenetriamine as a ligand, diethyl-2,5-dibromoadipate as an initiator, n-butyl acrylate as a monomer, (n-butyl acrylate) / (diethyl-2, Polymerization was carried out at a 5-dibromoadipate) molar ratio of 80 to obtain a terminal bromine group poly (n-butyl acrylate).

  This polymer was dissolved in N, N-dimethylacetamide, potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. in a nitrogen atmosphere. N, N-dimethylacetamide in this mixed solution was distilled off under reduced pressure, butyl acetate was added to the residue, and insoluble matter was removed by filtration. The filtrate was distilled off butyl acetate under reduced pressure to obtain poly (n-butyl acrylate) having both ends of acryloyl group.

  To 800 g of the obtained polymer, 4 g of 50% hydrogen peroxide water was added and stirred for about 10 minutes under air. The mixture was further stirred at 100 ° C. for 1 hour under air, then devolatilized at 120 ° C. for 1.5 hours, and water was distilled off under reduced pressure to obtain a polymer [P1].

  The number average molecular weight of the polymer [P1] was 12,000, the molecular weight distribution was 1.2, and the average number of terminal acryloyl groups was 1.8.

(Synthesis Example 2)
<Synthesis example of poly (n-butyl acrylate) having acryloyl group at one end>
Using cuprous bromide as catalyst, pentamethyldiethylenetriamine as ligand, α-ethyl bromobutyrate as initiator, and n-butyl acrylate as monomer, (n-butyl acrylate) / (ethyl α-bromobutyrate) mol Polymerization was performed at a ratio of 40 to obtain n-butyl terminal bromine group polyacrylate.

  This polymer was dissolved in N, N-dimethylacetamide, potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. in a nitrogen atmosphere. N, N-dimethylacetamide in this mixed solution was distilled off under reduced pressure, butyl acetate was added to the residue, and insoluble matter was removed by filtration. The butyl acetate in the filtrate was distilled off under reduced pressure to obtain acryloyl group single-ended poly (n-butyl acrylate).

  To 800 g of the obtained polymer, 4 g of 50% hydrogen peroxide water was added and stirred for about 10 minutes under air. Furthermore, after stirring at 100 ° C. for 1 hour under air, devolatilizing and stirring at 120 ° C. for 1.5 hours and distilling off water under reduced pressure, acryloyl group-terminated poly (n-butyl acrylate), polymer [P2] Got. The number average molecular weight of the polymer [P2] was 6,500, the molecular weight distribution was 1.2, and the average number of terminal acryloyl groups was 0.9.

(Synthesis Example 3)
<Synthesis example of poly (acrylic acid 2-ethylhexyl acrylate / n-butyl acrylate) having acryloyl groups at both ends>
Cuprous bromide as catalyst, pentamethyldiethylenetriamine as ligand, diethyl-2,5-dibromoadipate as initiator, 2-ethylhexyl acrylate and n-butyl acrylate as monomer, monomer ratio (molar ratio) as acrylic 2-ethylhexyl acid (98) and n-butyl acrylate (2) were polymerized with a molar ratio of (2-ethylhexyl acrylate, n-butyl acrylate) / (diethyl-2,5-dibromoadipate) being 80. Terminal bromine group poly (2-ethylhexyl acrylate / n-butyl acrylate) was obtained.

  This polymer was dissolved in N, N-dimethylacetamide, potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. in a nitrogen atmosphere. N, N-dimethylacetamide in this mixed solution was distilled off under reduced pressure, butyl acetate was added to the residue, and insoluble matter was removed by filtration. The filtrate was distilled off butyl acetate under reduced pressure to obtain poly (acryloyl group-terminated poly (2-ethylhexyl acrylate / n-butyl acrylate)).

  To 200 g of the obtained polymer, 1 g of hydrogen peroxide solution having a concentration of 50% was added and stirred under air for about 10 minutes. The mixture was further stirred at 100 ° C. for 1 hour under air, then devolatilized at 120 ° C. for 1.5 hours, and water was distilled off under reduced pressure to obtain a polymer [P3].

  The number average molecular weight of the polymer [P3] was 13,500, the molecular weight distribution was 1.3, and the average number of terminal acryloyl groups was 1.5.

(Examples 1-19, Comparative Examples 1-7)
A blending method will be described. Add the antioxidant (F) component to the polymer (A) component ([P1] to [P3]) or other component urethane acrylate (E8402), and heat mix at 120 ° C. for 2 hours. And dissolved. After cooling to 50 ° C. or lower, the (C) component methacrylate ester monomer, the (D) component epoxy group compound, the (E) component polyfunctional (meth) acrylate monomer, (B ) Component radical photopolymerization initiator was added, and the mixture was homogenized with a stirring deaerator (ARE-250, manufactured by Shinkey Co., Ltd.). In addition, IRGACURE819 of (B) component used what was previously melt | dissolved in DAROCUR1173. The blending amount (“parts by weight”) is shown in Tables 1 to 4. In the table, component (B) DAROCUR1173 is 2-hydroxy-2-methyl-1-phenyl-propan-1-one, IRGACURE819 is bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, (F ) Component Sumilizer GA80 is 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8, 10-tetraoxaspiro [5,5] undecane, Adekastab 1178 is tris (nonylphenyl) phosphite, and the other component urethane acrylate is a product name E8402, bifunctional, molecular weight 1000, manufactured by Daicel Cytec.

(Comparative Example 8)
The epoxy resin is a two-pack type thermosetting resin mainly made of Pernox, trade name ME562 / HV562, hydrogenated epoxy compound and acid anhydride. After the same amount was uniformly mixed and defoamed, a sample having a thickness of 1 mm similar to that for ultraviolet curing was prepared under curing conditions of 110 ° C. for 3 hours and 130 ° C. for 3 hours.

From Table 1, it can be seen that light transparency and heat-resistant transparency are improved by using a methacrylic acid ester monomer as the component (C) and / or a compound having an epoxy group as the component (D). In particular, by using a compound having an epoxy group as component (D), light resistance and heat resistance transparency were improved. In addition, when the (C) component methacrylic acid ester monomer and the (D) component epoxy group-containing compound were used in combination, the initial light transmittance maintenance rate after the light resistance test and the heat resistance test was good, and there was little coloring even in visual evaluation. .

  From Table 2, methacrylic acid ester having an alicyclic aliphatic structure or an aliphatic branched structure organic group, whereas lauryl methacrylate having an aliphatic linear structure organic group of Comparative Example 3 was uncured. It can be seen that a cured product is obtained with the monomer, and the light resistance and heat transparency are improved. Further, when a methacrylic acid ester monomer was used as the component (E), the initial light transmittance was maintained well after the light resistance test and heat resistance test, and coloring was small even in visual evaluation.

From Table 3, light resistance transparency and heat-resistant transparency were good by using the compound which has the epoxy group of (D) component. It can also be seen that when the component (D) exceeds 30 parts by weight , the initial light transmittance is significantly reduced. As the component (D), the compound having a (meth) acryloyl group had good light resistance and heat transparency, and the light resistance and heat transparency of the glycidyl methacrylate having a methacryloyl group were better.

  When the component (C) and the component (D) were not used as compared with Comparative Example 5, the viscosity of the curable composition was high and the heat-resistant transparency was low. From Comparative Example 6, when urethane acrylate was used instead of the component (A), the light resistance and heat resistance transparency were remarkably low. From Comparative Example 7, when the component (A) was not used, a transparent cured product could not be obtained due to warpage and shrinkage of the cured product. From Comparative Example 8, the heat resistant transparency was remarkably low with the epoxy resin alone.

  The active energy ray-curable composition and cured product of the present invention have low viscosity, storage stability, low foamability, low temperature curing, low warpage, deep curability, heat and light resistance, rubber properties, crack resistance and moisture permeability. Since it is excellent in design properties and the like, it is suitable for optical material applications requiring these physical properties.

Claims (16)

(A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(In the formula, Ra represents ^a hydrogen atom or a methyl group)
An active energy ray-curable composition for optical materials, which comprises an acrylic polymer obtained by living radical polymerization having at least one (meth) acryloyl group per molecule and (B) a photoradical polymerization initiator. And
(D) containing a compound having an epoxy group (excluding a compound having a benzene ring ),
The active energy ray-curable composition for optical materials, wherein the content of the component (D) is 0.1 to 30 parts by weight with respect to 100 parts by weight of the component (A). Furthermore, (C) general formula (2):
R ^b —OC (O) C (CH ₃ ) ═CH ₂ (2)
(In the formula, R ^b represents an organic group having an alicyclic aliphatic structure or an aliphatic branched structure having 6 to 20 carbon atoms).
The active energy ray curability for an optical material according to claim 1, wherein the content of the component (C) is 1 to 70 parts by weight with respect to 100 parts by weight of the component (A). Composition. The active energy ray-curable composition for optical materials according to claim 1 or 2, wherein the (A) component (meth) acryloyl group is at the molecular end. The active energy ray-curable composition for an optical material according to any one of claims 1 to 3, wherein the main chain of the vinyl polymer of the component (A) is a polymer mainly composed of a (meth) acrylic acid ester monomer. object. The active energy ray-curable composition for an optical material according to claim 4, wherein the main chain of the vinyl polymer (A) is a polymer mainly composed of an acrylate monomer. The active energy ray-curable composition for an optical material according to any one of claims 1 to 5, wherein the vinyl polymer as the component (A) is produced by an atom transfer radical polymerization method. The active energy ray-curable composition for an optical material according to any one of claims 1 to 6, wherein the component (A) is a vinyl polymer that is produced by a living radical polymerization method and then treated with an oxidizing agent. The number average molecular weight of (A) component is 3,000-100,000, The active energy ray curable composition for optical materials in any one of Claims 1-7. The optical material according to any one of claims 1 to 8, wherein the vinyl polymer (A) has a ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography of less than 1.8. Active energy ray-curable composition for use. (E) General formula (3):
^{R C - {OC (O)} C (R a) = CH 2} m (3)
(Wherein R ^c is an organic group having 6 to 20 carbon atoms, R ^a is a hydrogen atom or a methyl group, and m is an integer of 2 to 6)
The active energy ray curable composition for optical materials in any one of Claims 1-9 containing the (meth) acrylic acid ester monomer represented by these. The active energy ray-curable composition for an optical material according to claim 10, wherein the component (E) is 1 to 25 parts by weight with respect to 100 parts by weight of the component (A). The active energy ray-curable composition for optical materials according to any one of claims 1 to 11, wherein the compound having an epoxy group as component (D) has at least one (meth) acryloyl group per molecule. The active energy ray-curable composition for an optical material according to any one of claims 1 to 12, comprising at least one of a hindered phenol-based, hindered amine-based, and phosphorus-based antioxidant (F). The active energy ray curable composition for optical materials according to any one of claims 1 to 13, which is used for an LED sealing material, a solar cell sealing material, a flat panel display sealing material, a sensor sealing material, and a lens. The hardened | cured material for optical materials obtained from the active energy ray curable composition for optical materials in any one of Claims 1-14. After arrange | positioning an LED element, a solar cell element, a flat panel display element, a sensor element, and a lens on a board | substrate, it encapsulates using the active energy ray curable composition for optical materials in any one of Claims 1-14. A method for manufacturing an LED module, a solar cell module, a flat panel display module, a sensor module, and a lens module, which is cured after being stopped.