JP2007145939A - Resin composition and resin-sealed semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which gives cured articles having excellent transparency, and has good storage stability. <P>SOLUTION: This resin composition is characterized by comprising a resin component and a curing catalyst comprising a phenolic compound and an aluminum complex, wherein the resin component comprises an epoxy resin represented by the general formula (1) in an amount of 70 to 95 wt.% and a both terminal-epoxidized silicone resin in at least one part of the remainder. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an alicyclic epoxy resin composition for a light emitting diode (LED) element used for protecting a light emitting diode element.

  Conventionally, as a sealing material for a light-emitting diode element, an epoxy resin is generally used, and in particular, a liquid epoxy compound having an alicyclic skeleton having good transparency and heat resistance is frequently used.

  However, many epoxy compounds having an alicyclic skeleton have an ester bond in the molecule, and are inferior in moisture and heat resistance compared to bisphenol-type epoxy. Moreover, since it has absorption in the UV region derived from ester groups, transparency becomes a problem. Although LED light sources tend to be used at lower wavelengths, phenyl group-containing epoxy sealing materials and ester group-containing epoxy sealing materials have poor light transmission in the short wavelength region. For this reason, it is difficult to apply to an LED using a short wavelength region as a light source. In addition, epoxy resins are widely used in two-component systems in which amine compounds and carboxylic acid anhydrides are mixed as curing agents, but two-component systems using these curing agents mix components immediately before use. There must be. For this reason, the operation is complicated. In addition, there are restrictions such as being forced to be stored and transported at a low temperature and having to be used within a certain period after manufacture. Therefore, for many years, an epoxy resin composition that can be stored in a single solution at room temperature has been desired.

  In order to improve such a problem, a mold resin mainly composed of an alicyclic epoxy resin is disclosed instead of a general bisphenol type epoxy resin (see, for example, Patent Document 1). An epoxy resin composition mainly composed of an alicyclic epoxy resin and cured with an acid anhydride has a long carbon irradiation because the main skeleton contains few carbon-carbon double bonds that cause photodegradation. There is little deterioration of the resin afterwards.

However, in a surface mount type device (SMD type, SMD: Surface Mounted Device) in which a semiconductor chip is directly mounted on a substrate surface, it is necessary to form a mold resin into a thin film, so that a volatile acid anhydride that requires time for curing is required. Cannot be used as a curing agent. Moreover, the di-cured product obtained using the acid anhydride curing agent has high hygroscopicity. An epoxy resin for optical semiconductor sealing containing hydrogenated bisphenol A diglycidyl ether has also been proposed (see, for example, Patent Document 2). This resin has problems such as coloring of the cured product, weather resistance, and heat resistance.
JP 2000-196151 A Japanese Patent Laid-Open No. 9-255564

  An object of the present invention is to provide a cured resin having excellent transparency and a good storage stability, and a resin-encapsulated semiconductor device using the same.

The resin composition according to one embodiment of the present invention contains a resin component, and a curing catalyst containing a phenol compound and an aluminum complex,
The resin component includes 70 to 95% by weight of an epoxy resin represented by the following general formula (1), and a both-end epoxidized silicone resin that occupies at least a part of the balance,
The phenol compound is represented by the following general formula (2):
The aluminum complex includes at least one of the following general formulas (3a) to (3c).

(In the general formula (1), R ⁰ is an organic group selected from alcohols, phenols, carboxylic acids, amines, and thiols and having n active hydrogens, and n is 2 to 100. (It is an integer.)

(In the general formula (2), Ar is a substituted or unsubstituted aromatic group or heteroaromatic group having 2 to 14 carbon atoms. R ¹⁰ may be the same or different, and may be a hydrogen atom or a carbon number. 1 to 30 substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group or heteroaromatic group, provided that the phenol compound is a substituted or unsubstituted alkyl group having 10 or more carbon atoms, or (At least one cyclic organic structure having a substituted or unsubstituted alkyl group having 10 or more carbon atoms is included in the molecule, k is an integer of 1 to 7, and j is an integer of 1 to 7.)

(In the above general formula, R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different and are each a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.)
The resin composition according to another aspect of the present invention contains a resin component, and a curing catalyst containing a phenol compound and an aluminum complex,
The resin component comprises at least 85% by weight of an alicyclic epoxy group-containing organopolysiloxane represented by the following general formula (A), and an epoxy resin having no remaining aromatic group or ester group,
The phenol compound is represented by the following general formula (2):
The aluminum complex includes at least one of the following general formulas (3a) to (3c).

(In the above compositional formula (A), R ⁴ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms containing an internal epoxy group, and R ⁵ is a hydrogen atom, a hydroxyl group, an alkoxy group, or a carbon number. (It is an alkyl group of 1 to 20. p and q are numerical values satisfying 0.001 ≦ p / (p + q) ≦ 0.1.)

(In the general formula (2), Ar is a substituted or unsubstituted aromatic group or heteroaromatic group having 2 to 14 carbon atoms. R ¹⁰ may be the same or different, and may be a hydrogen atom or a carbon number. 1 to 30 substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group or heteroaromatic group, provided that the phenol compound is a substituted or unsubstituted alkyl group having 10 or more carbon atoms, or (At least one cyclic organic structure having a substituted or unsubstituted alkyl group having 10 or more carbon atoms is included in the molecule, k is an integer of 1 to 7, and j is an integer of 1 to 7.)

(In the above general formula, R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different and are each a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.)
A resin-encapsulated semiconductor device according to one embodiment of the present invention includes a semiconductor element and a resin layer that encapsulates the semiconductor element, and the resin layer is obtained by curing the resin composition described above. And

  ADVANTAGE OF THE INVENTION According to this invention, the hardened | cured material excellent in transparency is obtained, and also the resin composition with favorable storage stability, and the resin sealing type semiconductor device using the same are provided.

  Embodiments of the present invention will be described below.

  As a result of intensive studies, the present inventors have found that a resin composition for encapsulating a semiconductor having good transparency after curing can be obtained by using a specific compound as a resin component.

In the resin composition concerning one Embodiment of this invention, the epoxy resin represented by following General formula (1) is contained in a resin component in a predetermined ratio.

In the general formula (1), R ⁰ is an organic group selected from alcohols, phenols, carboxylic acids, amines, and thiols and having n active hydrogens, and n is an integer of 2 to 100 It is.

Examples of organic compounds having n active hydrogens that can be introduced as R ⁰ include the following. Specifically, examples of the aliphatic alcohols include methanol, ethanol, and propanol, and examples of the aromatic alcohol include benzyl alcohol. Examples of the polyfunctional alcohol include ethylene glycol, glycerin, and pentaerythritol. Examples of phenols include phenol, catechol, pyrogallol, and phenol resin. Examples of carboxylic acids include acetic acid, maleic acid, phthalic acid, and acrylic acid. Further, a compound having both a hydroxyl group and a carboxyl group such as lactic acid can be introduced as R ⁰ . Examples of the amines include methylamine, hexamethylenediamine, and diethylenetriamine. Examples of the thiols include mercaptos such as methyl mercaptan, mercaptopropionic acid, and polyhydric alcohol esters of mercaptopropionic acid. it can. Among these organic compounds, aliphatic compounds are particularly preferable as R ⁰ because of their excellent transparency.

In order to obtain a cured product sufficient as a sealing material, R ⁰ is required to be present in the compound represented by the general formula (1). On the other hand, when R ⁰ is excessively present, the resulting composition becomes too viscous and difficult to handle. Considering these, n is defined in the range of 2 to 100. n is more preferably 2 to 10.

  Content of the epoxy resin represented by the said General formula (1) is prescribed | regulated to 70 to 95 weight% of a resin component. When the amount is less than 70% by weight, a cured product having sufficient adhesion such as a substrate cannot be obtained. On the other hand, when the content exceeds 95% by weight, the cured product becomes less flexible and cracks may occur during the cooling and heating cycle. The content of the epoxy resin represented by the general formula (1) is preferably 80 to 95 wt% of the resin component.

  Specifically, as the epoxy resin represented by the general formula (1), for example, EHPE3150 (epoxy equivalent 185, softening point 85 ° C.), EHPE 3156 (epoxy equivalent 290, softening point 59 ° C.), EHPE 3158 (epoxy equivalent 214) , Softening point 59 ° C.) (both manufactured by Daicel Chemical Industries, Ltd.).

  The epoxy resin represented by the general formula (1) can be synthesized, for example, by the following method. First, a polyether compound as a precursor is synthesized by reacting a compound containing one or more active hydrogens with 4-vinyl-1-cyclohexene. An epoxy resin represented by the general formula (1) is obtained by oxidizing and epoxidizing a vinyl group contained in the polyether compound. Although it is desirable to oxidize all vinyl groups, it may remain in the target compound as long as it is 10% or less based on the epoxy group. If the residual ratio of the vinyl group exceeds 10%, the light transmittance of the cured product may be lowered.

  Examples of the epoxidizing agent include peracids and hydroperoxides. Specifically, as the peracids, formic acid, peracetic acid, perbenzoic acid and the like can be used. As hydroperoxides, hydrogen peroxide, cumene peroxides, and the like can be used.

At least a part of the remaining part of the resin component is composed of a both-end epoxidized silicone resin, and specifically, a compound represented by the following general formula (4) can be used.

In the general formula (4), R ¹ is a disubstituted or unsubstituted divalent alkylene group having 1 to 10 carbon atoms. Specifically, as R ¹ , a compound having a branched or linear substituent such as methylene, dimethylene, trimethylene, hexamethylene, octamethylene, and decylmethylene and a steroid skeleton such as cholesterol can be used. These may be the same or different. Considering ease of synthesis, a methyl group or an ethyl group is preferable as R ¹ .

R ² is an alkyl group having 1 to 10 carbon atoms. Specifically, examples of R ² include methyl, ethyl, propyl, butyl, hexyl, and decyl.

  m is an integer of 0 or more and 20 or less. Since a low viscosity silicone resin has an excellent dilution effect, the case where m is 0 is also included. In general, a long chain epoxidized silicone oil having a molecular weight of more than 2,000 has a very poor compatibility with an epoxy resin and tends to have a low reactivity. It is prescribed. m is preferably 10 or less.

  Examples of the compound represented by the general formula (4) include 1,3-bis (3-glycidoxypropyl) tetramethyldisiloxane (molecular weight 362, epoxy equivalent 181, GE Toshiba Silicones, TSL9906), 1 , 5-bis (3-glycidoxypropyl) -1,1,3,3,5,5-hexamethyltrisiloxane, and epoxypropoxypropyl-terminated polydimethylsiloxane (molecular weight 1,000-1,400, GELEST) , DMS-E11) and the like.

  In the embodiment of the present invention, in addition to the epoxy resin represented by the general formula (1), another epoxy resin can be used in combination. In this case, from the viewpoint of transparency of the sealing resin, hydrogenated one is preferable. Any hydrogenated compound having two or more epoxy groups in one molecule can be used.

  For example, bisphenol A type, bisphenol AD type, bisphenol D type, phenol novolak type, cresol novolak type, naphthol novolak type, bisphenol A novolak type, trifunctional hydrogenated epoxy resin, alicyclic epoxy resin, and An aliphatic epoxy resin etc. can be mentioned. However, the blending amount of such an epoxy resin is preferably 20% by weight or less in the total epoxy resin. If it exceeds 20% by weight, the light transmittance of the resulting cured product may be lowered.

The resin composition according to the embodiment of the present invention contains a curing catalyst containing a specific phenol compound and an aluminum complex.
The phenol compound is a compound represented by the following general formula (2).

  In the general formula (2), Ar is a substituted or unsubstituted aromatic group or heteroaromatic group having 2 to 14 carbon atoms. Specifically, examples of Ar include the following. That is, phenyl group, benzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, chlorobenzyl group, dichlorobenzyl group, trichlorobenzyl group, nitrobenzyl group, dinitrobenzyl group, trinitrobenzyl group, naphthylmethyl group; naphthyl Condensed aromatic ring groups formed by condensation of 2 to 3 benzene rings such as anthracenyl and phenanthrenyl groups; furanyl, thiophenyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazolyl , Pyrazolidinyl, triazolyl, furazanyl, tetrazolyl, pyranyl, thiinyl, pyridinyl, piperidinyl, oxazinyl, morpholinyl, thiazinyl, pyri Monocyclic heteroaromatic groups such as dinyl, pyrimidinyl, pyrazinyl, piperazinyl and triazinyl groups; benzofuranyl, isobenzofuranyl, benzothiophenyl, indolyl, indolinyl, isoindolyl, benzoxazolyl, benzothiazolyl, indazolyl, imidazolyl, chromenyl , Chromanyl, isochromanyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, dibenzofuranyl, carbazolyl, xanthenyl, acridinyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenoxazinyl, thianthridyl, indolidinyl, quinolizinyl , Condensed heteroaromatic groups such as purinyl and pteridinyl groups. In the aforementioned aromatic group or heteroaromatic group, at least one hydrogen atom may be substituted. Examples of the substituent that can be introduced include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, and hexadecane. When two or more substituents are present, they may be the same or different.

In the general formula (2), R ¹⁰ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic group, or a heteroaromatic group. is there. Examples of the alkyl group introduced as R ¹⁰ include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, and nonadecane. A compound having a branched or linear substituent such as icosane, henicosane, docosane, tricosane, tetracosane, pentacosane, hexacosane, heotacosane, octacosane, nonacosane, triacosane, or a steroid skeleton such as cholesterol can be used.

  The alkyl group described above may contain a heteroatom such as F, Si, O, N, or S.

  However, the compound represented by the general formula (2) is a molecule having a cyclic organic structure having a substituted or unsubstituted alkyl group having 10 or more carbon atoms, or a substituted or unsubstituted alkyl group having 10 or more carbon atoms. Have one or more inside. This is to facilitate the phase separation of the compound represented by the general formula (2) in the epoxy resin. This is because the storage stability of the epoxy resin can be improved by phase separation.

  In addition, k is prescribed | regulated to 1-7 from the ease of a synthesis | combination. Moreover, j is prescribed | regulated to 1-7 from a viewpoint of catalyst activity. k is preferably 1 to 4, and j is preferably 1 to 4.

  Specifically, the phenol compound represented by the general formula (2) includes bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone monooctadecyl ether, bis (4-hydroxy-3-octadecyloxyphenyl). ) Sulfone, bis (4-hydroxyphenyl) sulfide monooctadecyl ether, (4-hydroxyphenyl) octadecyl sulfone, 4.4′-dihydroxydiphenyl ether monooctadecyl ether, and bis (2- (6-hydroxyphenyl)) sulfone monooctadecyl Examples include ether.

  These phenol compounds can be used alone or in combination of two or more. The content of the phenol compound in the composition is usually 0.01 to 20% by weight with respect to the epoxy resin. If it is less than 0.01% by weight, curing may be insufficient. On the other hand, if the content exceeds 20% by weight, the electrical characteristics may be adversely affected. Specifically, inconvenience such as a decrease in volume resistivity occurs. In addition, the cost increases. The addition amount of the phenol compound is preferably 0.5 to 10% by weight with respect to the epoxy resin.

On the other hand, the aluminum complex which is another component of the curing catalyst is selected from the following general formulas (3a), (3b) and (3c).

In the above general formula, R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different, and are each a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. Specifically, examples of the alkyl group that can be introduced into R ²¹ , R ²² , R ²³ and R ²⁴ include methyl, ethyl, propyl, butyl, hexyl, hexadecyl and octadecyl. In consideration of ease of synthesis, methyl and ethyl are preferable.

However, in any compound, it is preferable that at least one compound in which R ²¹ , R ²² , R ²³ and R ²⁴ have 10 or more carbon atoms is contained in one ligand. This is for facilitating phase separation of the aluminum complex in the epoxy resin.

  Examples of compounds that satisfy these conditions include tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, tris (salicylaldehyde) aluminum, tris (octadecylacetoacetate) aluminum, tris (hexadecylacetoacetate). Examples include aluminum, tris (tetradecylacetoacetate) aluminum, tris (dodecylacetoacetate) aluminum, and tris (octylsalicylaldehyde) aluminum, and tris (behenyloxyacetoacetate) aluminum. In particular, tris (octadecyl acetoacetate) aluminum and tris (behenyloxy acetoacetate) aluminum are preferably used.

  In addition to the components described above, various additives can be blended in the resin composition according to the embodiment of the present invention as long as the transparency does not adversely affect the viscosity. Examples of such additives include silicone-based and fluorine-based antifoaming agents, silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, fused silica, crystalline silica, calcium silicate, calcium carbonate, Fillers such as barium sulfate, alumina, magnesia, aluminum nitride, silicon nitride, boron nitride, beryllium oxide, magnesium oxide, mica, magnesium titanate, and barium titanate, aluminum hydroxide as a halogen-free flame retardant imparting agent And metal hydrates such as magnesium hydroxide, flame retardants such as boric acid compounds and phosphorus compounds, and colorants such as carbon black and titanium oxide.

  Since the resin composition concerning embodiment of this invention is excellent in storage stability and high transparency, it can be used suitably for sealing of a semiconductor element. As a semiconductor element, a light emitting element etc. are mentioned, for example. In particular, when used in an optical semiconductor element such as a white LED, the effect of the resin composition according to the embodiment of the present invention is sufficiently exhibited.

  The resin composition concerning other embodiment of this invention is obtained by changing the resin component using the curing catalyst which consists of a specific phenol compound and aluminum complex as mentioned above.

In the resin composition according to another embodiment of the present invention, an alicyclic epoxy group-containing organopolysiloxane represented by the following general formula (A) is contained as a resin component.

In the composition formula (A), R ⁴ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms including an internal epoxy group, and R ⁵ is a hydrogen atom, a hydroxyl group, an alkoxy group or 1 to 1 carbon atoms. 20 alkyl groups. Specific examples of the alkyl group that can be introduced into R ⁴ and R ⁵ include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane. , Heptadecane, octadecane, nonadecane, icosane, heicossan, docosane, tricosane, tetracosane, pentacosane, hexacosane, heotacosane, octacosane, nonacosane, triacosane and the like, and compounds having a steroid skeleton such as cholesterol It is done. Two or more R ⁴ may be the same or different, and two or more R ⁵ may also be the same or different. In view of ease of synthesis, the alkyl group is preferably a methyl group or an ethyl group.

Preferred R ⁴ can be represented by the following general formula.

In the above general formula, R ^x may be the same or different and is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. Furthermore, a residue from which at least one hydrogen atom has been removed is introduced as R ^x .

  Examples of the hydrocarbon group include methyl, ethyl, propyl, butyl, hexyl, hexadecyl and octadecyl. Methyl, ethyl, propyl and butyl are preferred because they are easy to synthesize.

  s is 1-10. If it exceeds 10, the reaction may be slow. Moreover, the above-described hydrocarbon group may contain a hetero atom such as a halogen atom, Si, O, N, or S. Specifically, it may have a substituent such as a chloromethyl group, a thiomethylmethyl group, a nitro group, a methoxy group, and a dimethylamino group.

Such an alicyclic epoxy group-containing silicone resin may have a linear, cyclic, branched, ladder-like or cage-like structure. In any structure, the number of moles of the alicyclic epoxy group-containing substituent in the resin is desirably 0.01 to 50 mol% with respect to one (—Si—O—) bond.
When the number of moles of the alicyclic epoxy group-containing substituent is 0.01 mol% or less, the properties of the silicone resin become remarkable, which may cause poor adhesion and make it difficult to dissolve the catalyst. On the other hand, when the number of moles of the alicyclic epoxy group-containing substituent exceeds 50 mol%, sufficient storage stability cannot be obtained. The number of moles of the alicyclic epoxy group-containing substituent is more preferably from 0.1 to 10.

  Furthermore, the viscosity at 25 ° C. is preferably 10,000 mPa · sec or less, and more preferably 5000 mPa · sec or less. When the viscosity at 25 ° C. is 10,000 mPa / sec or less, the viscosity suitable for the sealing material is maintained.

  The silicone resin having an alicyclic epoxy group represented by the general formula (A) can be easily obtained by allowing an alicyclic epoxy compound having a vinyl group to act on polyhydrosiloxane. A platinum catalyst is mentioned as a curing catalyst used in this case. The platinum catalyst can be selected from platinum metal, platinum compounds and platinum complexes on a support. Examples of platinum compounds and platinum complexes include chloroplatinic acid, chloroplatinic acid hexahydrate, Karstedt's catalyst, dichlorobis (triphenylphosphine) platinum (II), cis-dichlorobis (acetonitrile) platinum ( II), dicarbonyldichloroplatinum (II), platinum chloride, platinum oxide and the like. In epoxidation, it is not always necessary to replace all hydrogen atoms in the hydrosiloxane with alicyclic epoxy groups. If it is 10 mol% or less of the total hydrosiloxane, hydrogen atoms may remain. If the hydrogen atom is present in excess of 10 mol% in the silicone resin, the durability of the resin composition may be reduced.

Specific examples of the compound represented by the general formula (A) include compounds represented by the following chemical formula.

  In the above formula, m, n, and p represent positive integers.

  In another embodiment of the present invention, an epoxy resin can be used in combination with the siloxane represented by the general formula (A) to constitute a resin component. In order to obtain a sealing material with excellent transparency, hydrogenated ones are preferred. Any hydrogenated type having two or more epoxy groups in one molecule may be used. For example, bisphenol A type, bisphenol AD type, bisphenol D type, phenol novolak type, cresol novolak type, naphthol novolak type, bisphenol A novolak type, trifunctional hydrogenated epoxy resin, alicyclic epoxy resin, aliphatic An epoxy resin etc. can be mentioned. However, it is preferable that the compounding quantity of such an epoxy resin shall be 50 weight% or less in all the resin components. If it exceeds 50% by weight, the storage stability may be lowered.

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

Example I
First, the following compounds were prepared as resin components.
・ EHPE-3150
(Daicel Chemical Industries, alicyclic epoxy resin, epoxy equivalent 168)
・ TLS 9906
(Toshiba Silicone, epoxy group-containing silicone resin, epoxy equivalent 181)
Epoxypropoxypropyl terminated polydimethylsiloxane (molecular weight 1,000-1,400, GELEST, DMS-E11)
・ Bisphenol A (manufactured by Yuka Shell, epoxy equivalent 170)
These structures are shown in the chemical formula below.

  As is clear from the above chemical formula, EHPE-3150 corresponds to the epoxy resin represented by the general formula (1). TSL9906 and DMS-E11 correspond to the both-end epoxidized silicone resin represented by the general formula (4).

As the phenol compound, bisphenol S (4,4-dihydroxyphenylsulfone) represented by the following chemical formula was prepared.

  The following three types of aluminum complexes were prepared.

・ Al (heaa) ₃ (Aluminum tris (hexadecyl acetoacetate))
(Long chain alkyl group has 16 carbon atoms)
・ Al (staa) ₃ (Aluminum tris (octadecyl acetoacetate))
(Long chain alkyl group has 18 carbon atoms)
・ Al (beaa) ₃ (Aluminum tris (behenyl acetoacetate))
(Long chain alkyl group has 22 carbon atoms)
The structures of these aluminum complexes are represented by the following chemical formula. As apparent from the chemical formula, Al (heaa) ₃ , Al (staa) ₃ , and Al (beaa) ₃ have 16, 18 and 22 carbon atoms in the long-chain alkyl group, respectively.

The components described above were blended according to the formulation (parts by weight) shown in Table 1 below and mixed uniformly to prepare the resin compositions of Examples I-1 to I-6.

  Moreover, the resin composition of the comparative example was prepared using the following compounds.

・ Celoxide 3000 (manufactured by Daicel Chemical Industries, limonene diepoxide, epoxy equivalent 94)
・ QH200 (manufactured by Nippon Zeon Co., Ltd., acid anhydride, equivalent 170)
・ 2MZ (manufactured by Shikoku Kasei Co., Ltd., 2-methylimidazole)
・ Al (etaa) ₃ (Aluminum tris (ethyl acetoacetate))
The aluminum complex used here is represented by the following chemical formula.

The components described above were blended in the formulation (parts by weight) shown in Table 1 below and mixed uniformly to prepare resin compositions of Comparative Examples I-1 to I-8.

  Each composition obtained was examined for storage stability. Specifically, each composition was accommodated in a 200 ml glass sample bottle, and the bottle was allowed to stand in a constant temperature water bath at 25 ° C. The viscosity of the composition was measured with a B-type viscometer, and the storage stability was evaluated by the time (days) until the initial viscosity was doubled. Storage stability is required to be 15 hours or longer.

  Moreover, each resin composition was hardened and the light transmittance of the obtained hardened | cured material was investigated. Specifically, each composition was applied onto a quartz substrate with a bar coder to form a coating film. This coating film was cured by heat treatment using a hot plate at 120 ° C. for 1 hour and further at 150 ° C. for 5 hours to form a cured product consisting of a thin film having a thickness of 0.03 mm. The light transmittance at a wavelength of 400 nm of the obtained cured product was measured using a spectrophotometer. In order to obtain a sealing resin excellent in light transmittance, the light transmittance is required to be 85% or more at 400 nm.

  Further, a resin-sealed LED as shown in FIG. 1 was prepared using each resin composition, and a thermal cycle test was performed. In FIG. 1, 11 is a light emitting element (gallium arsenide diode), 12 is a transparent resin layer, 13 is a glass epoxy substrate, 14 is a lead wire, and 15 is an electrode. Using each resin composition, a resin was injected into a spherical frame, and a transparent resin layer 12 was formed by disposing an element therein and curing the resin, thereby producing a resin-sealed LED.

  In the cooling / heating cycle test, each resin-sealed LED was absorbed at 85 ° C./85% for 2 hours and then subjected to a heat treatment at 260 ° C./10 seconds. At this time, peeling of the permeable resin layer 12 was observed. This was repeated 5 times, and (number of defects / number of test samples) was examined.

The results obtained are summarized in Tables 3 and 4 below.

From the comparison between Tables 3 and 4, the compositions of Examples I-1 to I-7, in which 70% by weight or more and 95% by weight or less of the resin component are EHPE-3150, are all excellent in storage stability. I understand that. This is presumably due to the fact that the aluminum complex having a long-chain alkyl group blended as a curing catalyst is phase-separated in the resin. Examples I-2 to I-5, in which a complex having a long-chain alkyl group having 22 carbon atoms (Al (beaa) ₃ ) was blended, were particularly excellent in storage stability.

  On the other hand, in Comparative Examples I-1 to I-6 in which the content of EHPE-3150 was less than 70% by weight or more than 95% by weight, the storage stability was poor. When the content of EHPE-3150 is less than 70% by weight, it becomes difficult for the aluminum complex as a curing catalyst to maintain a good phase separation state in the resin. On the other hand, if it exceeds 95% by weight, the viscosity of the resin becomes too high, and the phase separation state of the aluminum complex is similarly deteriorated. For this reason, in any case, the storage stability is insufficient.

  Since the predetermined epoxy compound is contained in a predetermined ratio, the resin compositions of Examples I-1 to I-6 all have high light transmittance. Moreover, the resin-sealed LED produced using the resin composition of the example had a defect rate of 0 as a result of the thermal cycle test. This is because the specific both-end epoxidized silicone resin is contained as at least a part of the remainder of the resin component.

  On the other hand, in Comparative Examples I-3 and I-7 having a high content of silicone resin (TSL9906), defects occurred. It can be seen that a cured product obtained by curing a resin composition containing a large amount of silicone resin has a poor adhesion and adversely affects the results of the thermal cycle test.

  FIG. 2 is a schematic diagram showing a configuration of a semiconductor device according to an embodiment of the present invention. The illustrated semiconductor device is an LED light emitting device, and includes a substrate 24 having a recess, a diode chip 26 disposed in the recess, and a transparent resin layer 22 covering the diode chip. An internal electrode 25 a and an external electrode 25 b are provided on the substrate 24, and a connection terminal (not shown) of the diode chip 6 is connected to the internal electrode 25 a by the conductive wire 3.

  Since light emitted from the diode passes through the transparent resin layer, in the LED light emitting device 21 as shown in the figure, the transparent resin layer 22 covering the diode chip 26 is required to have high transparency. Since the resin composition concerning embodiment of this invention has the outstanding transparency as mentioned above, it is used suitably for formation of the transparent resin layer 22. FIG.

Example II
First, the following compounds were prepared as resin components.
・ Silicon compound 1
3,4-epoxycyclohexylethylmethylsiloxane dimethylsiloxane copolymer (viscosity: 800 mPa · sec, alicyclic epoxy group-containing substituent 3 mol%)
・ Silicon compound 2
3,4-epoxycyclohexylethylmethylsiloxane hexylmethylsiloxane copolymer (viscosity: 1000 mPa · sec, alicyclic epoxy group-containing substituent 3 mol%)
・ Silicon compound 3
3,4-epoxycyclohexylethylmethylsiloxane diethylsiloxane copolymer (viscosity: 900 mPa · sec, alicyclic epoxy group-containing substituent 3 mol%)
・ Silicon compound 4
3,4-epoxycyclohexylethylmethylsiloxane methylhydrogensiloxane copolymer (viscosity: 800 mPa · sec, alicyclic epoxy group-containing substituent 3 mol%)
・ Silicon compound 5
3,4-epoxycyclohexylethylmethylsiloxane methylphenylsiloxane copolymer (viscosity: 2000 mPa · sec, alicyclic epoxy group-containing substituent 3 mol%)
・ Silicon compound 6
3,4-epoxycyclohexylethylmethylsiloxane dimethylsiloxane copolymer (viscosity: 4,000 mPa · sec, alicyclic epoxy group-containing substituent 15 mol%)
These structures are shown in the chemical formula below.

  As shown in the above chemical formula, the silicon compounds 1 to 4 are compounds represented by the general formula (A). The silicon compound 5 includes a phenyl group, and the silicon compound 6 includes 15 mol% of an epoxy group. Therefore, these silicon compounds are not compounds represented by the general formula (A).

The components described above were blended according to the formulation (parts by weight) shown in Table 5 below, and mixed uniformly to prepare resin compositions of Examples II-I-1 to II-7.

Furthermore, each component was mix | blended with the prescription shown in following Table 6, and it mixed uniformly, and prepared the resin composition of Comparative Example II-I-1-II-7.

  About each obtained composition, the storage stability was investigated by the method similar to the above, and it evaluated similarly. Moreover, the resin composition was lowered | hung by the method similar to the above, the hardened | cured material was formed, and the light transmittance was investigated.

  Further, a resin-sealed LED as shown in FIG. 1 was prepared using each resin composition, and a cooling / heating cycle test was performed. Using each resin composition, the transparent resin layer 12 was formed by the same method as described above, and a resin-sealed LED was produced. In the cooling / heating cycle test, the same treatment as described above was performed to determine the number of defects / the number of test samples.

The results obtained are summarized in Tables 7 and 8 below.

From comparison of Tables 7 and 8 above, Examples II-1 to II-7, in which 85% by weight or more of the resin components are alicyclic epoxy group-containing organopolysiloxanes represented by the general formula (A), It can be seen that the storage stability is excellent. This is presumably due to the fact that the aluminum complex having a long-chain alkyl group blended as a curing catalyst is phase-separated in the resin. Examples II- ₃ to II-6 containing an aluminum complex (Al (beaa) ₃ ) having a long-chain alkyl group having 22 carbon atoms were particularly excellent in storage stability.

And the hardened | cured material formed by hardening | curing the composition of these Examples is excellent in light transmittance, and all are as favorable as 93%.
Further, in Examples II-1 to II-7, no defect occurs at all even when the cooling cycle test is performed. From this, it can be seen that the cured products of the examples have high adhesion.

  Thus, the composition of an Example is equipped with all the characteristics of storage stability, light transmittance, and adhesiveness. This is due to the use of an epoxy group-containing silicone resin that does not contain any UV-absorbing phenyl group or ester group and a phase-separated aluminum complex.

  The comparative example shows that when the content of the polysiloxane represented by the general formula (A) in the resin component is less than 85% by weight, a resin composition having all these characteristics cannot be obtained. .

  The compositions of the comparative examples are all inferior in light transmittance due to the low content of the predetermined polysiloxane. In addition, Comparative Examples II-2, II-3, and II-4 have poor adhesion. In Comparative Example II-4, the storage stability is remarkably inferior. This is because a compatible aluminum complex is used.

  By using the resin composition according to the embodiment of the present invention, a resin-sealed LED using a light source in a short wavelength region is realized.

1 is a schematic diagram showing a semiconductor device according to an embodiment of the present invention. 1 is a schematic diagram illustrating a semiconductor device according to an embodiment of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 ... Light emitting element; 12 ... Transparent resin; 13 ... Glass epoxy base material 14 ... Lead wire; 15 ... Electrode; 21 ... Light-emitting device; 22 ... Transparent resin layer 23 ... Conducting wire; 24 ... Substrate; 25b ... External electrode 26 ... Diode chip.

Claims (7)

A resin component, and a curing catalyst containing a phenol compound and an aluminum complex,
The resin component includes 70 to 95% by weight of an epoxy resin represented by the following general formula (1), and a both-end epoxidized silicone resin that occupies at least a part of the balance,
The phenol compound is represented by the following general formula (2):
The said aluminum complex contains at least 1 sort (s) represented by the following general formula (3a)-(3c), The resin composition characterized by the above-mentioned.

(In the general formula (1), R ⁰ is an organic group selected from alcohols, phenols, carboxylic acids, amines, and thiols and having n active hydrogens, and n is 2 to 100. (It is an integer.)

(In the general formula (2), Ar is a substituted or unsubstituted aromatic group or heteroaromatic group having 2 to 14 carbon atoms. R ¹⁰ may be the same or different, and may be a hydrogen atom or a carbon number. 1 to 30 substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group or heteroaromatic group, provided that the phenol compound is a substituted or unsubstituted alkyl group having 10 or more carbon atoms, or (At least one cyclic organic structure having a substituted or unsubstituted alkyl group having 10 or more carbon atoms is included in the molecule, k is an integer of 1 to 7, and j is an integer of 1 to 7.)

(In the above general formula, R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different and are each a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.) The resin composition according to claim 1, wherein the both-end epoxidized silicone resin is represented by the following general formula (4).

(In the general formula (4), R ¹ is a disubstituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and R ² is an aliphatic group having 1 to 10 carbon atoms. Is an integer from 0 to 20.)   The resin composition according to claim 1, wherein the aluminum complex contains at least one substituent having 10 or more carbon atoms in one ligand. A resin component, and a curing catalyst containing a phenol compound and an aluminum complex,
The resin component comprises at least 85% by weight of an alicyclic epoxy group-containing organopolysiloxane represented by the following general formula (A) and an epoxy resin having no remaining aromatic group or ester group,
The phenol compound is represented by the following general formula (2):
The said aluminum complex contains at least 1 sort (s) represented by the following general formula (3a)-(3c), The resin composition characterized by the above-mentioned.

(In the above compositional formula (A), R ⁴ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms containing an internal epoxy group, and R ⁵ is a hydrogen atom, a hydroxyl group, an alkoxy group, or a carbon number. (It is an alkyl group of 1 to 20. p and q are numerical values satisfying 0.001 ≦ p / (p + q) ≦ 0.1.)

(In the general formula (2), Ar is a substituted or unsubstituted aromatic group or heteroaromatic group having 2 to 14 carbon atoms. R ¹⁰ may be the same or different, and may be a hydrogen atom or a carbon number. 1 to 30 substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group or heteroaromatic group, provided that the phenol compound is a substituted or unsubstituted alkyl group having 10 or more carbon atoms, or (At least one cyclic organic structure having a substituted or unsubstituted alkyl group having 10 or more carbon atoms is included in the molecule, k is an integer of 1 to 7, and j is an integer of 1 to 7.)

(In the above general formula, R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different and are each a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.) The resin composition according to claim 4, wherein R ⁴ in the general formula (A) is a 2- (3,4-epoxycyclohexyl) ethyl group.   The resin composition according to claim 4 or 5, wherein the aluminum complex contains at least one substituent having 10 or more carbon atoms in one ligand.   7. A resin seal comprising a semiconductor element and a resin layer for sealing the semiconductor element, wherein the resin layer is obtained by curing the resin composition according to claim 1. Stop-type semiconductor device.

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