JPS61159753A - Resin sealed type light-emitting device and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain a resin sealed type light-emitting device, which can scatter beams to the whole resin, by sealing a light-emitting element by a photo polymerization composition in which the component composition of an epoxy resin, an aluminum compound, an silicon compound having peroxysilyl groups, and polymethyl sesquioxan having specific mean grain size is limited. CONSTITUTION:A light-emitting element is sealed by using a photo polymerization composition consisting of a 100pts.wt. epoxy resin, a 0.001-10pts.wt. aluminum compound, a 0.1-20pts.wt. silicon compound having peroxysilyl groups and a 0.1-50pts.wt. polymethyl having 0.1-100mum mean grain size. The epoxy resin is composed of only an epoxy compound or a mixture of the epoxy compound and one kind or two kinds or more of compounds selected from a group consisting of an acid anhydride, a phenol group compound and a compound having ethylene unsaturated groups. One kind or two kinds or more of mixed system compounds may be employed as the aluminum compound, and the quantity of them added and compounded is kept within a range of, preferably, 0.1-5 pts.wt. to the 100pts.wt. epoxy resin.

Description

Detailed Description of the Invention [Technical Field of the Invention] The present invention relates to a resin-sealed light emitting device and a method for manufacturing the same, and more specifically to a photocurable epoxy resin composition that is improved so that light scattering is uniform. The present invention relates to a resin-sealed light emitting device using a resin-sealed light emitting device and a method for manufacturing the same.

[Technical Background of the Invention and its Problems] Conventionally, light emitting devices such as light emitting diodes, which have been put into practical use as various display materials, have been manufactured by resin sealing. As *m for such sealing, liquid epoxy resin compositions have conventionally been preferably used because of their excellent properties such as electrical properties, moisture resistance, and heat resistance. However, since the resins conventionally used for sealing light emitting devices are heat-curable, they require a long time to cure and have low productivity.

Photocurable epoxy resins have been reported to solve these drawbacks. In this method, the epoxy resin itself is cured using a photodecomposition type catalyst. The catalyst used at this time has the following formula: %Formula% (In the formula, A is an aryl group such as a phenyl group, X is an iodine atom, a sulfur atom, a diazo group, etc., Y is BF4, P
Represents Fs, As Fs, Sb Fs, etc. ) [Macromolecules, Vol. 10, p. 1301, 1977 (Macr.

5olecules, 1O-11307 (1977
) : Journal of Radiation Curing, Volume 5, Page 2, 1978 (Journal
of Radiation Curin (J, 5
12 (1978); Journal of Polymer Science, Polymer Chemistry Edition, 11th page, page 2817, 1919 ((Journ
al of Polymer 5cien
ce Polymer Chemistry
Edition, 17.2877 (1979))
: Id. Vol. 11, p. 1041, 1919 (Id., 1
7. 1047 (1979)): Journal of Polymer Science Polymer Letters Edition, Vol. 17, p. 759, 1979 (Jou
rnal of polymer science
nce Poly*er Letters
Edition, 171 759 (1979)
); JP-A-55-65219; U.S. Patent No. 40
69054; US Pat. No. 1,516,511 and British Patent No. 1,518,141, etc.).

Although this method improves productivity to some extent, the problem that curing takes a long time still remains.

In addition, since it is necessary to scatter light from the element to the entire resin, commercially available silica-based scattering agents are usually used for these resins, but the scattering with these commercially available silicas is insufficient, and , has the problem of precipitation of silica during storage.

[Object of the invention] The object of the present invention is to solve the above-mentioned problems and to
By using a photocurable epoxy resin composition that quickly cures with ultraviolet rays, productivity is improved, and
An object of the present invention is to provide a resin-sealed light emitting device that can scatter light throughout the resin by using polymethylsilsesquioxane as a light scattering agent, and a method for manufacturing the same.

[Summary of the Invention] As a result of extensive research, the present inventors have found that polymethyl silsesquinone is added to an epoxy resin as a light scattering agent to a photocurable epoxy resin consisting of an aluminum compound as a photocuring catalyst and a silicon compound having a peroxysilyl group. The inventors have discovered that the above object can be achieved by using oxane, and have completed the present invention.

That is, in the present invention, the light emitting element contains (A) 100 parts by weight of epoxy resin <8> 0.001 to 10 parts by weight of aluminum compound (
C) Silicon compound having peroxysilyl group 0.1~
20 parts by weight and (D) 0.1 to 50 parts by weight of polymethylsilsesquioxane with an average particle size of 0.1 to 100 μm. The light emitting device and the light emitting element contain (A) 100 parts by weight of an epoxy resin (B) 0.001 to 10 parts by weight of an aluminum compound (
C) Silicon compound having peroxysilyl group 0.1~
and (D) 0.1 to 50 parts by weight of polymethylsilsesquioxane with an average particle radius of 0.1 to 100 μm to seal the light emitting device. This is a method for manufacturing a resin-sealed light emitting device.

Moreover, in the present invention, the photopolymerizable composition may further contain a photosensitizer.

In the following, the invention will be explained in more detail.

The epoxy resin (A>) used in the present invention is an epoxy compound alone, or an epoxy compound and an acid anhydride,
It is a mixture with one or more compounds selected from the group consisting of phenolic compounds and compounds having ethylenically unsaturated groups.

The epoxy compound used in the present invention constitutes the main component of the composition of the present invention, and examples of such epoxy compounds include -functional epoxy compounds and polyfunctional epoxy compounds. -Functional epoxy compounds include, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, phenyl glycidyl ether, and butyl glycidyl ether. In addition, examples of polyfunctional epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins: phenol novolac type epoxy resins; alicyclic epoxy resins; and heterocyclic epoxy resins such as triglycidyl isocyanurate and hydantoin epoxy. : Hydrogenated bisphenol A type epoxy resin;
Aliphatic epoxy resins such as propylene glycol-diglycidyl ether and pentaerythritol-polyglycidyl ether; glycidyl ester type epoxy resins obtained by the reaction of aromatic, aliphatic or alicyclic carboxylic acids with epichlorohydrin Nispiro ring-containing epoxy Resin: Glycidyl ether type epoxy resin which is a reaction product of an 0-allyl-phenol novolac compound and epichlorohydrin: A reaction product of a diallylbisphenol compound having an allyl group at the 0-position of each hydroxyl group of bisphenol A and epichlorohydrin. Examples include certain glycidyl ether type epoxy resins, and one or more resins selected from the group consisting of these resins are used as appropriate.

Phenolic compounds used in addition to epoxy compounds include bisphenol compounds such as bisphenol A1 bisphenol F1 bisphenol S, phenol,
Examples include condensates of phenols such as cresol, catechol, and bisphenol A, and formaldehyde.

Examples of compounds having an ethylenically unsaturated group include:
Styrene and styrene derivatives, unsaturated carboxylic acids, unsaturated carboxylic acid salts, esters of unsaturated carboxylic acids with aliphatic human oxy compounds, aliphatic polyhydroxy compounds, aromatic hydroxy compounds or aromatic polyhydroxy compounds, divalent Examples include oligoesters obtained by esterification reactions with the above-mentioned polyhydric carboxylic acids, divalent or higher polyhydroxy compounds, and unsaturated carboxylic acids.

Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid.

Specific examples of aliphatic human oxy compounds include methanol, ethanol, propatool, butanol, and the like.

Examples of aliphatic polyhuman oxy compounds include ethylene glycol, triethylene glycol, tetraethylene glycol, tetramethylene glycol, neopentyl glycol, 1,10-decanediol, 1,2-butanediol, and 1.3-butanediol. , dihydric alcohols such as propylene glycol, trihydric alcohols such as nitrimethylolethane, trimethylolpropane, and their multimers; tetrahydric or higher hydric alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, and other multimers pentaerythritol alcohols; sugars such as sorbitol and d-mannitol; and dihydroxycarboxylic acids such as dihydroxymaleic acid.

Examples of aromatic hydroxy compounds and aromatic polyhydroxy compounds include phenol, hydroquinone, catechol, resorcinol, 70roglucinol, pyroganol, and the like.

Specific examples of esters of aliphatic hydroxy compounds and unsaturated carboxylic acids include acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid n-butyl ester, acrylic jlliso-propyl ester, acrylic acid n-butyl ester, and acrylic Htert. - Acrylic acid esters such as butyl ester: methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid n-propyl ester, methacrylic acid iso-propyl ester, methacrylic acid n-propyl ester, methacrylic acid n-butyl ester, methacrylic acid tert - Methacrylic acid esters such as butyl ester: itaconic acid such as methyl itaconate, ethyl itaconate, n-propyl itaconate, 1SO-propyl itaconate, n-butyl itaconate, and Htert-butyl itaconate. Esters; crotonic acid methyl ester, crotonic acid ethyl ester, crotonic acid n-propyl ester, crotonic acid l5
Examples include crotonic acid esters such as O-propyl ester, crotonic acid n-butyl ester, and croton Htert-butyl ester.

Specific examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol triacrylate, 13-butanediol diacrylate, tetramethylene glycol diacrylate, and diacrylic acid. Polypylene glycol ester, trimethylolpropane triacrylate, trimethylol ethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, diacrylic Acid dipentaerythritol ester, triacrylic acid dipentaerythritol ester, tetraacrylic acid dipentaerythritol ester, pentaacrylic acid dipentaerythritol ester, hexaacrylic acid dipentaerythritol ester, octaacrylic acid tripentaerythritol ester, sorbitol triacrylate Acrylic acid esters such as ester, sorbitol tetraacrylate ester, sorbitol pentaacrylate ester, sorbitol hexaacrylate ester and polyester acrylate oligomer, tetramethylene glycol dimethacrylate ester, triethylene glycol dimethacrylate ester, trimethylol trimethacrylate Propane ester, trimethacrylic acid trimethylolethane ester, dimethacrylic acid pentaerythritol ester, trimethacrylic acid pentaerythritol ester, dimethacrylic acid dipentaerythritol ester, dimethacrylic acid pentaerythritol ester, tetramethacrylic acid dipentaerythritol ester, octamethacrylate Methacrylic acid esters such as acid tripentaerythritol ester, dimethacrylic acid ethylene glycol ester, dimethacrylic acid 11,3-butanediol ester, dimethacrylic acid tetramethylene glycol ester, tetramethacrylic acid sorbitol ester; diitaconic acid ethylene glycol ester, diitaconic acid Propylene glycol ester, Rytacon 111.3-butanediol ester, diitaconic acid 1,4-butanediol ester,
Itaconic acid esters such as tetramethylene glycol diitaconate, pentaerythritol diitaconate, dipentaerythritol triitaconate, dipentaerythritol pentitaconate, dipentaerythritol hexitaconate, sorbitol tetrataconate; dicrotonic acid Crotonic acid esters such as ethylene glycol ester, propylene glycol dicrotonic acid ester, tetramethylene glycol dicrotonic acid ester, pentaerythritol dicrotonic acid ester, sorbitol tetracrotonic acid ester; diisocrotonic ethylene glycol ester, pentaerythritol diisocrotonic acid ester, tetrac Ikic acid esters such as sorbitol ester of Otonate; maleic acid esters such as ethylene glycol cymaleate, triethylene glycol cymaleate, pentaerythritol cymaleate, sorbitol tetramaleate; and the above-mentioned esters A mixture of the following may be mentioned.

Specific examples of oligoesters include oligoester acrylates and oligoester methacrylates (hereinafter, both or either of them will be simply referred to as oligoester (meth)acrylates).

Oligoester (meth)acrylate is a reaction product obtained by the esterification reaction of acrylic acid, methacrylic acid, polycarboxylic acid, and polyol, and has the following general formula: % formula % (wherein R is hydrogen represents an atom or a methyl group, Q represents an ester group having at least one ester bond consisting of a polyol and a polycarboxylic acid, and p is an integer from 1 to 6. It is.

Examples of the polyol constituting the ester group represented by Q include ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, trimethylolethane, 1.2 Polyols such as 6-hexanediol, glycerin, pentaerythritol and sorbitol; and diethylene glycol, triethylene glycol, tetraethylene glycol, decaethylene glycol, polyethylene glycol, diethylene glycol,
Examples include polyether type polyols such as tripropylene glycol, tetrapropylene glycol, and polypropylene glycol.

Further, examples of the polyhydric carboxylic acid constituting the ester group represented by Q include phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid,
Aromatic polycarboxylic acids such as trimellitic acid, biomellitic acid, benzophenone dicarboxylic acid, and resorcinol diacetic acid; unsaturated aliphatic polycarboxylic acids such as maleic acid, fumaric acid, hymic acid, and itaconic acid; malonic acid, Examples include unsaturated aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, dodecanoic acid, and tetrahydrophthalic acid.

Examples of acid anhydrides used in the present invention include:
Phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, maleic anhydride, trimellitic anhydride, hexacroendomethylenetetrahydrophthalic anhydride, etc. Can be mentioned.

The aluminum compound (8) has an organic group selected from the group such as an alkyl group, a phenyl group, a haloalkyl group, an alkoxy group, a phenoxy group, an acyloxy group, a β-diketonato group, and an 0-carbonylphenorad group bonded to it. It is a compound consisting of

Among the above organic groups, examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
Examples include 5ea-butyl group, t-butyl group, and n-pentyl group; Examples of phenyl group include phenyl group, p-methoxyphenyl group, O-methoxyphenyl group, and p-ethoxyphenyl group; Examples of haloalkyl group Examples of the alkoxy group include a chloromethyl group, a chloroethyl group, and a chloropropyl group; examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a butoxy group, and a pentoxy group; examples of the phenoxy group include a phenoxy group, Examples include O-methylphenoxy group, 0-methoxyphenoxy group, 0-nidophenoxy group, and 2,6-dimethylphenoxy group; Examples of the 7-syloxy group include acetato group, probionato group, isopropionato group, and butirado group. Examples of the β-diketonato group include an acetylacetoacetato group, a probylacetoacetato group, a butylacetoacetato group, a diethylmalato group, and a divivalomethanato group; Examples include acetylacetonato group, hexafluoroacetylacetonato group, etc.;
An example is a salicylaldehydato group.

Specific examples of aluminum compounds include trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, triacetoxyaluminum, tri(p-methylphenoxy)aluminum, isopropoxyjethoxyaluminum, triptoxyaluminum, triacetoxyaluminum, and tristearado. Aluminum, aluminum tributyrad, aluminum tripropionate, aluminum triisoprobionate,
Tris(acetylacetonato) aluminum, tris(
tris(pentafluoroacetylacetonato)aluminum, tris(ethylacetoacetato)aluminum, ethylacetoacetatodiisoproboxyaluminum, tris(salicylaldehydato)aluminum, tris(diethylmalorad) ) aluminum, tris(propylacetoacetate)aluminum, tris(butylacetoacetate)aluminum, tris(isopropylacetoacetate)aluminum, tris(dipivaloylmethanato)
Examples include aluminum, diacetylacetonatodipivaloylmethanatoaluminum, ethylacetoacetatodiisobroboxyaluminum (hereinafter referred to as blank), and the like. Among these, tris(ethylacetoacetate)aluminum is preferred in terms of catalytic activity and reaction rate.

These aluminum compounds may be used alone or in a mixed system of two or more, and the amount added is 0.001 to 10 parts by weight, preferably 0.001 to 10 parts by weight, per 100 parts by weight of the epoxy resin (A). It ranges from 1 to 5!1 parts by weight. If the blending amount is less than 0.001% by weight, sufficient curing properties cannot be obtained, and if it exceeds 101ff1%, it will cause increased costs and deterioration of electrical properties.

The silicon compound having a peroxysilyl group (D) is
The following formula: % formula %) (In the formula, R' and R2 may be the same or different and each represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, and . represents a number from 0 to 3. ).

Substituted or unsubstituted hydrocarbon groups in the above formula include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, undecyl group, dodecyl group, hexadecyl group. , Alkyl groups such as octadecyl group: Aryl groups such as phenyl group, naphthyl group, anthranyl group, methylphenyl group, xylyl group, dodecylphenyl group: Aralkyl group such as penzyl group, phenylethyl group, α-methylstyryl group, cumyl group Groups: Cycloalkyl groups such as Schif0hexyl group and Schif0octyl group; alkenyl groups such as vinyl group, allyl group, and cyclohexenyl group; or some or all of the hydrogen atoms of these groups have been substituted with halogen atoms, etc. groups, such as chloromethyl group, β-cyanoethyl group, p-chlorophenyl group, -monochlorophenyl group, O-chlorophenyl group, E)-trifluoromethylphenyl group, -monotrifluoromethylphenyl group, 〇-trifluoro Examples include methylphenyl group, 3,3.3-trifluoropropyl group, pentafluorophenyl group, and methylphenyl group.

A specific example of a silicon compound having a peroxysilyl group is the following formula; (blank below) F3 CFx c! Examples include compounds represented by the following. Among these, [-butylperoxytriphenylsilane and cumylperoxytriphenylsilane] are preferred because of their strong ζ catalytic activity.

The amount of these silicon compounds added is in the range of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the epoxy resin (A).

If the amount is less than 0.1 part by weight, sufficient curing properties will not be obtained, and although it is possible to use more than 20 parts by weight, it will increase the cost and cause decomposition products of the catalyst component. This may become a problem.

The polymethylsilsesquioxane (D) used in the present invention scatters the light from the light emitting element so as to spread throughout the resin, and is the most characteristic feature of the present invention. This powder has a lower specific gravity in compositions than other silica-based powders with similar average particle sizes such as ground quartz and diatomaceous earth, and compared to fumed and wet silicas. There is little increase in viscosity when made into a composition.

Furthermore, in any case, the problem of sedimentation during long-term storage is significantly less compared to other powders. Therefore, a large amount can be filled. Polymethylsilsesquioxane is obtained by hydrolyzing and condensing methyltrialkoxysilane or its hydrolyzed and condensed products in an aqueous solution of ammonia or amines, and contains chlorine atoms, alkaline earth metals, and alkali metals. There are almost no impurities such as
It is also preferable because it is spherical and has excellent free-flowing properties. The average particle size of polymethylsilsesquioxane is 0.1 to 100
μ intestine, preferably 0.1 to 20 μm. 0.1μm
If it is less than 100 μm, it is difficult to manufacture, and if it exceeds 100 μm, it will not be uniformly dispersed in the resin, making it impossible to emit uniform light. The blending amount is 0.1 to 50 parts by weight per 100 parts by weight of the epoxy resin (A). If it is less than 0.1 part by weight, uniform light emission cannot be obtained, and if it exceeds 50 parts by weight, the light transmittance will be poor.

In the present invention, it may be preferable to use a photosensitizer if necessary in order to improve curability. The photosensitizer used here includes the above-mentioned compounds. The photosensitizer used here may be any substance as long as it is capable of photosensitizing the compound, and is appropriately selected depending on the epoxy resin, light source, etc.

Examples of such photosensitizers include aromatic hydrocarbons, benzophenone and its derivatives, 0-benzoylbenzoic acid ester, acetophenone and its derivatives, benzoin and benzoin ether and its derivatives, xanthone and its derivatives, thioxanthone and its derivatives. derivative,
Examples include disulfide compounds, quinone compounds, halogenated hydrocarbons, and amines.

Specific examples of aromatic hydrocarbons include benzene, benzene-d6, toluene, p-xylene, fluorobenzene,
Chlorobenzene, bromobenzene, iodobenzene, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 1-fluoronaphthalene, 1-chloronaphthalene,
2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, 1-iodonaphthalene, 2-iodonaphthalene, 1-naphthol, 2-naphthol, biphinyl, fluorene, p-terphenyl, 7-cenaphthene, p
-quaterphenyl, trinoenylene, phenanthrene, azulene, fluoranthene, chrysene, pyrene, 1,
2-benzpyrene, anthracene, 1,2-benzanthracene, 9.10-benzanthracene, 9,10
-dibromoanthracene, 9.10-diphenylanthracene, perylene, tetracene, pentacene and benzyl.

Examples of benzophenone and its derivatives include benzophenone, 2,4-dimethylbenzophenone, 2,4
-dichlorobenzophenone and 4°4'-bis(dimethylamino)benzophenone.

As the 0-benzoylbenzoate ester, for example, 0
-Benzoylbenzoic acid methyl ester, O-benzoylbenzoic acid ethyl ester, O-benzoylbenzoic acid phenyl ester, and the like.

Examples of acetophenone and its derivatives include acetophenone, 4-methylacetophenone, 3-methylacetophenone, and 3-methoxyacetophenone.

Examples of benzoin, benzoin ether, and derivatives thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin 1so-propyl ether, benzoin lobutyl ether, benzoin triphenylsilyl ether, C2H5, and the like.

Examples of xanthone and its derivatives include quinanthone, 2,4-dimethylxanthone, and 2°4-dichloroxanthone.

Examples of thioxanthone and its derivatives include thioxanthone, 2,4-dimethylthioxanthone and 2,4
-dimethylthioxanthone and the like.

Examples of the disulfide compound include the following.

Examples of the quinone compound include benzoquinone, naphthoquinone, acitraquinone, 5,12-naphetacenedione, and 2,7-pyrenedione.

Examples of the halogenated hydrocarbons include carbon tetrachloride, hexachloroethane, tetrachlorinated carbon, and CH.

Examples of the amine term include diphenylamine, carbazole, triphenylamine, and the like.

(Left below) Examples of things in the pond include propiophenone, anthrone, benzaldehyde, butyrophenone, 2-naphthylphenyl ketone, 2-naphthaldehyde, 2-acetonaphthone, 1-naphthylphenyl ketone, 1-acetonaphthone, 1-naphthaldehyde. , fluorenone, 1-phenyl-1,2-butanedione, benzonitrile, acetone, piacetyl, acridine orange, acridine, O
-Damine 8, eosin, fluorescein, etc., but from the viewpoint of photopolymerizability, benzophenone, 1-(4-
isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-phenyl-2-human 0x-
Preferably, it is one or more photosensitizers selected from 2-methylpropan-1-one and jetoxyacetophenone.

These photosensitizers can be used alone or in combination of two or more, and the amount thereof is preferably 20 parts by weight or less per 100 parts by weight of the epoxy resin (A), More preferably, it is 0°1 to 10°.

In addition to the above-mentioned components, the photocurable epoxy resin composition according to the present invention may contain a colorant, an inorganic filler, or other additives, if necessary.

The method for manufacturing a resin-sealed light-emitting device of the present invention includes sealing a light-emitting element using the above-mentioned photocurable epoxy resin composition by a known method such as botting, casting, dipping, or dropping. , especially those that are cured by UV light. The wavelength of the light irradiated during photocuring varies depending on the type of resin composition and the sealing method, but is usually 180 to 700 rv, preferably 250 rv.
~500n-. The light irradiation time varies depending on the type of resin composition, the sealing method, and the type of light source, but is usually 10 seconds to 180 minutes, preferably 30 seconds to 30 minutes. As a light source for light irradiation, for example, a low pressure mercury lamp, a high pressure mercury lamp, a carbon arc lamp, a xenon lamp, an argon glow discharge tube, a metal halide lamp, etc. can be used.

[Effects of the Invention] The curable composition of the present invention uses an aluminum compound and a silicon compound having a peroxysilane group as catalyst components, and uses polymethylsilsesquioxane as a light scattering agent, so that it can be easily cured by light irradiation. curing time can be significantly shortened, and light can be scattered throughout the resin. Therefore, the effect on improving the productivity and quality of light emitting devices such as light emitting diodes is extremely large.

[Embodiments of the invention] Next, the present invention will be explained with reference to Examples and Reference Examples.

Reference Example 1 (Production of polymethylsilsesquioxane) 500 parts of water and 50 parts of an ammonia aqueous solution at a temperature of 28% were charged into a four-bottle flask equipped with a thermometer, a reflux device, and a stirrer. Methyltrimethoxysilane shown in Table 1 was gradually added dropwise over 60 to 120 minutes while stirring. The reaction temperature started at 10℃,
At the end of the dropwise addition, the temperature reached 30°C. Next, the mixture was heated with a mantle heater to reflux at 84°C, and stirring was continued at this temperature for about 1 hour. After cooling, the product precipitated in the flask is collected, washed with water, dried, and then pulverized to produce powdered polymethylsilsesquioxane (with excellent free-flowing properties) shown in Table 1.
F-1 to F-3) were obtained.

Table 1 Reference Example 2 (Production of Botmethylsilsesquioxane) Methyltriethoxysilane 178 containing 1% by weight of chlorine atoms
9 parts of water was added to the mixture and heated at 180°C for about 2 hours to obtain a partially hydrolyzed condensate. This is ethylenediamine 3
When added dropwise to 500 parts of a wt% aqueous solution and hydrolyzed and condensed under the same conditions as in Reference Example 1, the average particle size was 8 μm.
A powdered polymethylsilsesquioxane (F-4) was obtained.

Example 1 (Preparation of resin) ERL-4221 (trade name, manufactured by UCC Co., Ltd.)
I-cyclic epoxy resin, epoxy equivalent = 145) 160 parts, Epicoat 1004 (trade name, manufactured by Shell Chemical ■, bisphenol A type epoxy resin, epoxy equivalent: 900~
1000, molecule 1: approx. 1400) 40 parts, Tris (n-
butylacetoacetonato)aluminum 0.4 parts, diphenyldi(tert-butylperoxy)silane 4 parts,
The epoxy resin composition of the above formulation was heated and stirred at 80° C. for 10 minutes to obtain a uniform sealing resin comparison composition A.

100 parts of this composition was transferred to a universal kneader, 12 parts of polymethylsilsesquioxane of F-1 was blended, and 2 hours lil.
A uniform sealing resin composition B was obtained by mixing and stirring.

(Sealing of Light-Emitting Elements) After immersing the light-emitting elements in the thus obtained resin composition B and comparative composition A, the light-emitting elements were taken out and irradiated with light for 2 minutes. Two high-pressure mercury lamps with an output of 2 KW were used as light sources, and irradiation was performed at a distance of 1 cm from the light sources to obtain a resin-sealed light emitting device.

Regarding the resin type light emitting device obtained in this way, the second
Each characteristic was investigated under the conditions shown in the table. The results are shown in Table 3.

(Hereafter the margin) (Hereafter the margin) Example 2 (Preparation of resin) ・Epicote 828 (trade name, manufactured by Shell Chemical ■, bisphenol A type epoxy resin, epoxy equivalent: 190-2
10, Molecular weight: 330) 100 parts, ERL-4221, 100 parts, trissalicylaldehydatoaluminum 0.2 parts, triphinyl (tert-butylperoxy) silane 6 parts The epoxy resin composition of the above formulation was heated at 50°C for 10 minutes. The mixture was stirred to obtain a uniform sealing resin composition.

Transfer 100 parts of this composition to a universal mixer, mix with 2.5 parts of F-2 polymethylsilsesquioxane, and mix at 2 tmm.
A homogeneous composition C was obtained by stirring.

As a comparative composition, a uniform comparative composition was obtained in the same manner except that 2.5 parts of Nip Seal VN3 (trade name, manufactured by Nippon Silica ■, wet silica) was mixed instead of 5 parts of F-22. Ta.

(Sealing of light emitting element) The resin composition obtained in this way is poured into a transparent container,
The light emitting element was buried to a specified position, and then light was irradiated for 3 minutes. Two metal halide lamps with an output of 2 kW were used as light sources, and irradiation was performed at a distance of 10 cm from the light source. The characteristics of the resin-sealed light emitting device thus obtained were investigated. The results are shown in Table 4.

(Margins below) In addition, when we left both sets of acid compounds in C1D and observed their appearance, C had uniformity over the course of 3 months and no change was observed, but D had no filler after 1 month. Sedimentation was observed.

Example 3 (Preparation of resin) - 100 parts of ERL-4221 - 90 parts of anhydrous 4-methylhexahydrophthal M - 0.5 part of trisethylacetoacetonatoaluminum - 4 parts of triphenyl (α, α-benzylperoxy)silane The epoxy resin composition of the above formulation was heated and stirred at 50° C. for 10 minutes to obtain a uniform sealing resin composition.

100 parts of this composition was transferred to a universal kneader, mixed with 1.5 parts of polymethylsilsesquioxane F-3, and stirred for 2 hours to obtain a uniform composition E.

In addition, as a comparative composition, a uniform comparative composition F was prepared in the same manner except that 2.5 parts of Aerosil 200 (trade name, Nippon Silica @ Jl, fumed silica) was mixed instead of 1.5 parts of F-3. Obtained.

(Sealing of Light Emitting Device) The resin composition thus obtained was poured into a transparent container, the light emitting device was placed therein, and light was irradiated for 2 minutes. Two high-pressure mercury lamps with an output of 2 kW were used as light sources, and irradiation was performed at a distance of 10 cm from the light sources. The characteristics of the resin-sealed light emitting device thus obtained were investigated. The results are shown in Table 5.

(Margins below) In addition, when we left both sets of acid products E and F and observed their appearance, E was uniform even after 3 months, and no change was observed, but D was found to be uniform after 2 weeks. Filler sedimentation was observed.

Example 4 (made by resin lI) - ERL-4221210 parts - Epicote 1004 90 parts - Hexahydrophthalic anhydride 100 parts - Tris (n-
1 part of (butylacetoacetonato)aluminum, 10 parts of diphenyldi(tert-butylperoxy)silane, and 1 part of diphenyldi(tert-butylperoxy)silane. The epoxy resin composition having the above composition was heated and stirred at 80°C for 10 minutes to obtain a uniform resin composition for sealing.

This composition was placed in a universal mixer, and 10 g of polymethylsilsesquioxane F-2 was blended therein to obtain a uniform sealing resin composition.

(Sealing of Light-emitting Element) After immersing the light-emitting element in the resin composition obtained in this manner, it was pulled up and irradiated with light for 2 minutes.

Two metal halide lamps with an output of 2 kW were used as light sources, and irradiation was performed at a distance of 10 G- from the light sources. The characteristics of the resin-sealed light emitting device thus obtained were investigated. The results are shown in Table 6.

Table 6 Examples 5 to 18 Twelve types of photocurable epoxy resin compositions having the compositions shown in Table 8 were prepared.

In addition, the epoxy resins include ERL-4221, alicyclic epoxy resin of the formula), Chissonox 234 (trade name, manufactured by Chisso ■, alicyclic epoxy resin of the formula, epoxy weight: approx. 140),
Epicoat 828, Epicoat 1001 (trade name, Epoxy ffl: 450-525, molecular weight: 900) and Epikot 1004 were used.

As phenolic compounds, (1) bisphenol A and (2) phenol were used.

As the ethylenic compound, (3) diacrylic acid ethylene glycol ester and (4) dimethacrylic acid 1.3-
Dibutanediol ester was used.

I! As anhydride (5) hexahydrophthalic anhydride, (
8) Methylhexahydrophthalic anhydride and (7) Methyltetrahydrophthalic anhydride were used.

In addition, as aluminum compounds, (a) tris(isoprogolacetoacetate)aluminum, (O) tris(n
-butylacetylacetato)aluminum, (iii) trisacetylacetonadoaluminum, (d)tris(ethylacetoacetato)aluminum, and (v) trissalicylaldehydatoaluminum.

Furthermore, as a silicon compound, (a) triphenyl (ter
t-butylperoxy)silane, (b) triphenyl(
α,α′-dimethylbenzylperoxy)silane, (C
) vinyldiphenyl(tert-butylperoxy)silane and (d) diphenyl(α,α'-dimethylbenzylperoxy)silane were used.

As a sensitizer (A) naphthacene, (B) benzophenone, (C) benzoin-1so-propyl ether and (
D) 2,4-dimethylthioxanthone was used.

F-2, F-3 as polymethylsilsesquioxane,
F-4 was used.

Using the above materials, epoxy resin compositions were prepared according to the formulations listed in Table 7.

(Sealing of light emitting device) The photocurable epoxy resin composite acid obtained in this way was
Each was poured into a transparent mold, a light emitting element was placed therein, and light was irradiated for 1 minute.

Next, it was taken out from the mold to obtain a resin-sealed light emitting device. As a light source, two high-pressure mercury lamps with an output of 2 kW were used.
Using this method, irradiation was performed at a position where the distance from the light source was iQcm.

The appearance of the resin-sealed light emitting device thus obtained is as follows:
In both cases, the entire resin emitted light uniformly and was in a favorable state. In addition, a continuous current test was conducted. The results are shown in Table 7. In addition, the continuous current test was conducted at 1f40 intestine A, 25°C.
Under these conditions, the rate of change in the optical output PO after 110 hours, that is, the optical output PO deterioration was measured.

(Margin below)

Claims (18)

[Claims] (1) The light emitting element contains (A) 100 parts by weight of epoxy resin (B) 0.001 to 10 parts by weight of aluminum compound (C
) silicon compound having peroxysilyl group 0.1-2
and (D) 0.1 to 50 parts by weight of polymethylsilsesquioxane with an average particle diameter of 0.1 to 100 μm. Light emitting device. (2) The epoxy resin is an epoxy compound or a mixture of an epoxy compound and one or more selected from the group consisting of acid anhydrides, phenolic compounds, compounds having ethylenically unsaturated groups, and imide compounds. A resin-sealed light emitting device according to claim 1. (3) The resin-sealed light emitting device according to claim 1, wherein the aluminum compound (B) is trisethylacetoacetatoaluminum. (4) The blending amount of the aluminum compound in (B) is 0.1~
5 parts by weight of the resin-sealed light emitting device according to any one of claims 1 to 3. (5) The resin-sealed light emitting device according to claim 1, wherein the silicon compound (C) is i-butylperoxytriphenylsilane or cumylperoxytriphenylsilane. (6) The resin-sealed light emitting device according to any one of claims 1 to 5, wherein the amount of the silicon compound (C) is 0.5 to 10 parts by weight. (7) Claim 1, wherein (D) is polymethylsilsesquioxane obtained by hydrolyzing and condensing methyltrialkoxysilane or its hydrolyzed and condensed product in an aqueous solution of ammonia or amines. The resin-sealed light-emitting device described in 2. (8) The resin-sealed light emitting device according to any one of claims 1 to 7, wherein (D) has an average particle diameter of 0.1 to 20 μm. (9) The resin-sealed light emitting device according to claim 1 or 2, wherein the photopolymerizable composition contains a photosensitizer. (10) The light-emitting element includes (A) 100 parts by weight of an epoxy resin (B) 0.001 to 10 parts by weight of an aluminum compound (C) 0.1 parts by weight of a silicon compound having a peroxysilyl group
~20 parts by weight and (D) 0.1 to 50 parts by weight of polymethylsilsesquioxane with an average particle diameter of 0.1 to 100 μm is used to seal the light emitting element. A method for manufacturing a resin-sealed light emitting device. (11) The epoxy resin is an epoxy compound or a mixture of an epoxy compound and one or more selected from the group consisting of acid anhydrides, phenolic compounds, compounds having ethylenically unsaturated groups, and imide compounds. A method for manufacturing a resin-sealed light emitting device according to claim 10. (12) Claim 1, wherein the aluminum compound (C) is trisethylacetoacetatoaluminum.
A method for manufacturing a resin-sealed light emitting device according to item 0. (13) The amount of aluminum compound in (C) is 0.1
~5 parts by weight Claims 10 to 12
A method for manufacturing a resin-sealed light emitting device according to any one of paragraphs. (14) The method for manufacturing a resin-sealed light emitting device according to claim 10, wherein the silicon compound (D) is t-butylperoxytriphenylsilane or cumylperoxytriphenylsilane. (15) The amount of silicon compound (D) is 0.5 to 10
The method for manufacturing a resin-sealed light emitting device according to any one of claims 10 to 14, wherein the amount is parts by weight. (16) Claim 10, wherein (D) is polymethylsilsesquioxane obtained by hydrolyzing and condensing methyltrialkoxysilane or its hydrolyzed and condensed product in an aqueous solution of ammonia or amines. A method for manufacturing a resin-sealed light emitting device as described in 1. (17) The apparatus for manufacturing a resin-sealed light emitting device according to any one of claims 10 to 16, wherein the average particle diameter of (D) is 0.1 to 20 μm. (18) The method for manufacturing a resin-sealed light emitting device according to claim 10 or 11, wherein the photopolymerizable composition contains a photosensitizer.