JP5145270B2 - Light emitting device and semiconductor device using the same - Google Patents

Description

  The present invention relates to a light emitting device and a semiconductor device using the same.

  In recent years, the market related to light-emitting diodes (hereinafter sometimes referred to as “LEDs”) has advanced rapidly, and accordingly, high-performance and inexpensive sealing resins, and highly reliable LEDs using the same have been developed. Demand is also increasing. A light emitting device using an LED or the like generally has a structure in which a light emitting light source such as an LED is sealed with a sealing material. As a material for the sealing material, an epoxy resin is often used.

  As a material for the sealing material, a silicone resin has also been studied. In recent years, a hybrid type resin of an epoxy resin and a silicone resin has also been developed. Other hybrid type resins used for the sealing material include a resin composition in which an epoxy resin and a silicone resin condensed in advance are mixed (for example, see Patent Documents 1 and 2), an epoxy resin and a methoxysilane condensate. A resin composition obtained by mixing alcohols (see, for example, Patent Documents 3 and 4), and a resin composition obtained by mixing and condensing an epoxy resin and a tetramethoxysilane condensate (for example, patents) References 5 and 6), a resin obtained by hydrolytic condensation of an alkoxysilane compound having an organic group having a cyclic ether group and an alkoxysilane compound having an organic group having an aryl group (for example, Patent Document 7) ), And a modified methanol-reacted epoxy resin and γ-glycidoxypropylmethoxysilane. Phenoxy resin (e.g., see Patent Document 8.) It has been proposed.

JP 2006-241230 A JP 2006-225515 A JP 2005-179401 A JP 2003-246838 A International Publication No. 2005/081024 Pamphlet JP 2007-284621 A JP 2008-120443 A JP 2007-321130 A

  However, when an epoxy resin is used as the material for the sealing material of the light-emitting device, the epoxy resin is inferior in performance, particularly in light resistance, and therefore, the fields that can be used are limited. This tendency is particularly remarkable for epoxy resins having an aromatic ring such as bisphenol A glycidyl ether.

In the case where a silicone resin is used as the material for the sealing material of the light emitting device, the silicone resin has good light resistance and heat resistance, but the hardness and adhesiveness of the cured product are not sufficient. As a result, the risk of disconnection of the light emitting device is increased, and there may be a problem in reliability.
A hybrid type resin of an epoxy resin and a silicone resin is very expensive for performance and is not well accepted in the market.

  Therefore, the present invention has been made in view of the above circumstances, and an object thereof is to provide a light emitting device excellent in light resistance and reliability, and a semiconductor device using the light emitting device.

  As a result of intensive studies, the inventors of the present invention sealed light emitting light sources by using a resin composition obtained by cohydrolysis condensation of an epoxy resin and a specific alkoxysilane compound. The inventors have found that a light emitting device having excellent reliability and a semiconductor device using the light emitting device can be obtained, and have made the present invention.

That is, the present invention is as follows.
[1]
A light-emitting device comprising a light-emitting light source and a sealing material that seals the light-emitting light source,
The sealing material is
(A) an epoxy resin;
An alkoxysilane compound represented by the following general formula (1):
A resin composition obtained by cohydrolyzing and condensing

(In the formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group. The plurality of R ² may be the same or different, and may be a hydrogen atom or a carbon number of 1 to 8. Represents an alkyl group of
The alkoxysilane compound is
(B) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one cyclic ether group;
(C) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one aryl group;
And a resin composition in which the mixing index α of (B) and (C) represented by the following formula (2) is 0.001 to 19;
Mixing index α = (αc) / (αb) (2)
(Wherein, αb: content (mol%) of the component (B), αc: content (mol%) of the component (C)).
[2]
The light emitting device according to [1], wherein the (A) epoxy resin is a liquid having an epoxy equivalent (WPE) of 100 to 600 g / eq and a viscosity at 25 ° C. of 1000 Pa · s or less.
[3]
The light-emitting device according to [1] or [2], wherein the (A) epoxy resin is a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound.
[4]
As the alkoxysilane compound,
(D) The light emitting device according to any one of [1] to [3], further including at least one alkoxysilane compound in which n = 0 in the general formula (1).
[5]
The light emitting device according to any one of [1] to [4], wherein a mixing index β of the alkoxysilane compound represented by the following formula (3) is 0.01 to 1.4;
Mixing index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
(In formula (3),
β ⁿ² : content (mol%) of the alkoxysilane compound in which n = 2 in the general formula (1),
β ⁿ⁰ : the content (mol%) of the alkoxysilane compound in which n = 0 in the general formula (1),
β ⁿ¹ : content (mol%) of the alkoxysilane compound in which n = 1 in the general formula (1),
Here, 0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1).
[6]
The mixing index γ represented by the following formula (4) between the (A) epoxy resin and the alkoxysilane compound is 0.02 to 15 and described in any one of [1] to [5]. Light emitting device;
Mixing index γ = (γa) / (γs) (4)
(In formula (4),
γa: mass of epoxy resin (g),
γs: mass (g) of alkoxysilane compound in which n = 0 to 2 in the general formula (1)
[7]
The light emitting device according to any one of [1] to [6], wherein the light emitting light source is a light emitting diode.
[8]
A semiconductor device comprising the light-emitting device according to any one of [1] to [7].

  According to the present invention, a light emitting device excellent in light resistance and reliability is obtained by sealing a light emitting light source using a resin composition obtained by cohydrolyzing and condensing an epoxy resin and a specific alkoxysilane compound. Thus, a semiconductor device using the same can be obtained.

It is sectional drawing of one Embodiment whose light-emitting device of this embodiment is a bullet-type LED. It is sectional drawing of one Embodiment whose light-emitting device of this embodiment is SMD type LED.

  DESCRIPTION OF EMBODIMENTS Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail with reference to the drawings as necessary. The present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist. In the drawings, positional relationships such as up, down, left, and right are based on the positional relationships shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

The light emitting device of this embodiment includes a light emitting element and a sealing material that seals the light emitting element, and the sealing material contains the following resin composition.
(A) an epoxy resin;
An alkoxysilane compound represented by the following general formula (1):
Is a resin composition obtained by cohydrolysis condensation,

(In formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group. Also, the plurality of R ² are the same or different and are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Is shown.)
The alkoxysilane compound represented by the general formula (1) is (B) n = 1-2, and R ¹ has at least one cyclic ether group, and (C) n = 1 to 2 and R ¹ having at least one aryl group and at least one alkoxysilane compound, and represented by the following formula (2) (B) and (C) The resin composition whose mixing index | alpha (alpha) is 0.001-19.
Mixing index α = (αc) / (αb) (2)
(In the formula (2), αb is the content (mol%) of the component (B), and αc is the content (mol%) of the component (C).)

(Encapsulant)
((A) Epoxy resin)
The (A) epoxy resin contained in the encapsulant of the present embodiment refers to a compound having an oxirane ring, usually two or more oxirane rings in the molecule, excluding an alkoxysilane compound and its condensate described below, It does not specifically limit if the above-mentioned requirements are satisfied. These may be used alone or in combination.

The epoxy equivalent (WPE) of the epoxy resin is preferably 100 to 600 g / eq, more preferably 100 to 500 g / eq, and still more preferably 100 to 300 g / eq.
Depending on the composition balance with the alkoxysilane compound represented by the general formula (1), when the epoxy equivalent (WPE) is 100 g / eq or more, the storage stability of the resin composition is further improved, and 600 g / eq. It can suppress effectively that a crack generate | occur | produces between the sealing material of this embodiment, or a sealing material and outer-layer resin as it is below.

  In the resin composition of the present embodiment, the epoxy equivalent of the epoxy resin is preferably 100 to 300 g / eq.

The epoxy resin is preferably a liquid having a viscosity at 25 ° C. of 1000 Pa · s or less, more preferably 500 Pa · s or less, and still more preferably 100 Pa · s or less.
When the viscosity at 25 ° C. exceeds 1000 Pa · s, the fluidity as a liquid is lost, and the compatibility with the alkoxysilane compound described later tends to deteriorate.
When the viscosity at 25 ° C. exceeds 500 Pa · s and is 1000 Pa · s or less (500 Pa · s <viscosity ≦ 1000 Pa · s), it can be used by adjusting the temperature at the time of production, selecting a solvent, etc. However, since it tends to be somewhat limited, it is preferably 500 Pa · s or less.

  The type of epoxy resin is not particularly limited, and specific examples include alicyclic epoxy resins, aliphatic epoxy resins, polyfunctional epoxy resins that are glycidyl ethers of polyphenol compounds, and glycidyl ethers of various novolac resins. Polyfunctional epoxy resin, aromatic epoxy resin nuclear hydride, aliphatic epoxy resin, heterocyclic epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, epoxy glycidylated from halogenated phenols Examples thereof include resins.

  Among them, alicyclic epoxy resins and aliphatic epoxy resins are preferred from the viewpoint of being readily available and having good physical properties when the resin composition of the present embodiment is a cured product, and alicyclic An epoxy resin is more preferable. These epoxy resins may be used alone or in combination.

(Polyfunctional epoxy resin)
The polyfunctional epoxy resin which is a glycidyl etherified product of a polyphenol compound is not particularly limited, and specifically, bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, tetramethylbisphenol A, dimethyl Bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenylphenol, 1- (4-hydroxyphenyl)- 2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene -Bis (3-methyl-6-tert-butyl) Ruphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, 2,6-di (t-butyl) hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, 1,1-di (4-hydroxyphenyl) fluorene, etc. Examples thereof include phenols having a fluorene skeleton, polyfunctional epoxy resins which are glycidyl etherified products of polyphenol compounds of phenolized polybutadiene.

Among the above, many of the types that are excellent in transparency and fluidity are commercially available and can be obtained at low cost, and reliability when a light-emitting device is manufactured using the resin composition of this embodiment as a sealing material Because of its tendency to be excellent in properties, a polyfunctional epoxy resin that is a glycidyl etherified product of phenols having a bisphenol A skeleton is preferred.
Typical examples of polyfunctional epoxy resins that are glycidyl ethers of phenols having a bisphenol skeleton are shown below.

When a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound is used as the epoxy resin, these repeating units (n in the chemical formula showing the above representative examples) are not particularly limited, but preferably 50 Less, more preferably 0.001 to 10, and still more preferably 0.01 to 2.
When the repeating unit is less than 0.001, the reactivity with the alkoxysilane compound may be deteriorated, and when it exceeds 50, the fluidity is lowered, which may cause a practical problem. From the viewpoint of the balance between the above-described reactivity and fluidity, the repeating unit is particularly preferably from 0.01 to 2.

(Alicyclic epoxy resin)
The alicyclic epoxy resin is not particularly limited as long as it is an epoxy resin having an alicyclic epoxy group, and examples thereof include an epoxy resin having a cyclohexene oxide group, a tricyclodecene oxide group, a cyclopentene oxide group, and the like. Can be mentioned.
Specific examples of the alicyclic epoxy resin include 4-vinyl epoxycyclohexane, dioctyl epoxyhexahydrophthalate, and di-2-ethylhexyl epoxyhexahydrophthalate as monofunctional alicyclic epoxy compounds. Examples of the bifunctional alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloctyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4 -Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, bis (3,4-epoxy-6-methyl) (Cyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethyl Glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexane carboxylate), 1,2,8,9- diepoxylimonene, and the like. Examples of the polyfunctional alicyclic epoxy compound include 1,2-epoxy-4- (2-oxiranyl) cyclohexene adduct of 2,2-bis (hydroxymethyl) -1-butanol. Examples of the polyfunctional alicyclic epoxy compound include Epolide GT401, EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.), and the like.
Typical examples of alicyclic epoxy resins are shown below.

(Aliphatic epoxy resin)
The aliphatic epoxy resin is not particularly limited, and specifically, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, pentaerythritol, xylylene glycol derivatives, etc. Examples thereof include glycidyl ethers of polyhydric alcohols. Typical examples of aliphatic epoxy resins are shown below.

(Polyfunctional epoxy resin that is glycidyl etherified product of novolak resin)
The polyfunctional epoxy resin that is a glycidyl etherified product of novolak resin is not particularly limited, and examples thereof include phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, and naphthol. Glycidyl etherification products of various novolac resins such as novolak resins made from various phenols such as phenols, xylylene skeleton-containing phenol novolak resins, dicyclopentadiene skeleton-containing phenol novolak resins, biphenyl skeleton-containing phenol novolak resins, and fluorene skeleton-containing phenol novolak resins. Etc.
Typical examples of polyfunctional epoxy resins that are glycidyl etherified products of novolak resins are shown below.

(Nuclear hydride of aromatic epoxy resin)
The nuclear hydride of the aromatic epoxy resin is not particularly limited, and examples thereof include glycidyl etherified products of phenol compounds (bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, etc.) or various phenols (phenols). , Cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc.) and hydrides of glycidyl ethers of novolac resins. Can be mentioned.

(Heterocyclic epoxy resin)
The heterocyclic epoxy resin is not particularly limited, and examples thereof include heterocyclic epoxy resins having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.

(Glycidyl ester epoxy resin)
The glycidyl ester-based epoxy resin is not particularly limited, and examples thereof include epoxy resins composed of carboxylic acids such as hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester.
The glycidylamine epoxy resin is not particularly limited. For example, an epoxy resin obtained by glycidylating amines such as aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivative, and diaminomethylbenzene derivative. Etc.

(Epoxy resin obtained by glycidylation of halogenated phenols)
Epoxy resins obtained by glycidylation of halogenated phenols are not particularly limited. For example, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated Examples thereof include epoxy resins obtained by glycidyl etherification of halogenated phenols such as bisphenol S and chlorinated bisphenol A.

The epoxy resin mentioned above can use a polyol together.
The polyol is not particularly limited as long as it is a compound having two or more hydroxyl groups in the molecule. For example, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,2-hexanediol, 1,6- Examples include hexanediol.

(Alkoxysilane compound)
The alkoxysilane compound in this embodiment shows the silicon compound which has 1-4 alkoxyl groups, and is represented by following General formula (1).

In formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group.
Moreover, several R < ² > is the same or different and shows a hydrogen atom or a C1-C8 alkyl group.

R ¹ in the general formula (1) represents a hydrogen atom or an organic group and is not particularly limited. Examples of the organic group include an organic group having a cyclic ether group and an organic group having an aryl group, which will be described later. Examples include an organic group having an alkyl group, a vinyl group, a methacryl group, a mercapto group, and an isocyanate group, and among them, an alkyl group is preferable.

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a butyl group (n-butyl, i-butyl, t-butyl, sec-butyl), a pentyl group (n-pentyl, i-pentyl, neopentyl etc.), hexyl group (n-hexyl, i-hexyl etc.), heptyl (n-heptyl, i-heptyl etc.), octyl group (n-octyl, i-octyl, t-octyl etc.), Nonyl (n-nonyl, i-nonyl, etc.), decyl group (n-decyl, i-decyl, etc.), dodecyl group (n-dodecyl, i-dodecyl, etc.) are mentioned, and these are linear or branched Any of these alkyl groups may be used.
Among these, an alkyl group having 10 or less carbon atoms is preferable, and a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, and n-hexyl group are more preferable. In addition, hydrogen atoms or a part or all of the main chain skeleton of these alkyl groups are ether groups, ester groups, carbonyl groups, siloxane groups, halogen atoms such as fluorine, methacryl groups, acrylic groups, mercapto groups, amino groups, It may be substituted with at least one group selected from the group consisting of hydroxyl groups.

Moreover, several R < ² > in the above-mentioned general formula (1) is the same or different, respectively, and shows a hydrogen atom or a C1-C8 alkyl group. R ² is not particularly limited as long as it satisfies the above requirements, but is preferably a methyl group or an ethyl group.

((B) component)
The component (B) of the alkoxysilane compound represented by the general formula (1) is at least one kind in the general formula (1), where n = 1 to 2 and R ¹ has at least one cyclic ether group. This is an alkoxysilane compound.

  The cyclic ether group refers to an organic group having an ether in which carbon of a cyclic hydrocarbon is substituted with oxygen, and usually means a cyclic ether group having a 3- to 6-membered ring structure. Among them, a 3-membered or 4-membered cyclic ether group having a large ring strain energy and high reactivity is preferable, and a 3-membered ether group is particularly preferable.

  Specific examples of the cyclic ether group include, for example, a glycidoxyalkyl group having oxyglycidyl groups having 4 or less carbon atoms such as β-glycidoxyethyl, γ-glycidoxypropyl, γ-glycidoxybutyl, and the like, glycidyl Group, β- (3,4-epoxycyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycycloheptyl) ethyl group, β- (3,4-epoxy (Cyclohexyl) propyl group, β- (3,4-epoxycyclohexyl) butyl group, β- (3,4-epoxycyclohexyl) pentyl group and the like substituted with an oxirane group having 5 to 8 carbon atoms An alkyl group etc. are mentioned.

  Among the above, glycidoxy in which an oxyglycidyl group is bonded to a C1-C3 alkyl group such as β-glycidoxyethyl group, γ-glycidoxypropyl group, β- (3,4-epoxycyclohexyl) ethyl group, etc. An alkyl group having 3 or less carbon atoms substituted with a C5-C8 cycloalkyl group having an alkyl group or an oxirane group is preferred.

  Specific examples of the component (B) include, for example, 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl (methyl) dibutoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2,3 -Epoxypropyl (phenyl) dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 2- (3,4-epoxy Hexyl) ethyl triethoxysilane, 2,3-epoxypropyl trimethoxysilane, 2,3-epoxy propyl triethoxy silane, and the like. These may be used alone or in combination.

((C) component)
The component (C) of the alkoxysilane compound represented by the general formula (1) is n = 1 to 2 in the general formula (1), and R ¹ has at least one aryl group. It is an alkoxysilane compound.

  An aryl group refers to a functional group or substituent derived from an aromatic hydrocarbon (simple aromatic ring or polycyclic aromatic hydrocarbon). The aryl group is not particularly limited as long as it matches this, but in consideration of steric hindrance in the higher order structure, a phenyl group, a benzyl group, and the like are preferable.

  Specific examples of the component (C) include, for example, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, phenyltriethoxysilane, trimethoxy [3- (phenylamino) propyl] silane, dimethoxydiphenylsilane, diphenyldiethoxysilane, phenyl Examples include trimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane. These may be used alone or in combination.

“(B) at least one alkoxysilane compound having general formula (1) where n = 1 to 2 and R ¹ having at least one cyclic ether group”, and “(C) general formula In (1), n = 1 to 2 and R ¹ has at least one aryl group, and the mixing ratio of “at least one alkoxysilane compound” is a mixing index calculated by the following formula (2): It is represented by α.

Mixing index α = (αc) / (αb) (2)
(Wherein, αb: content of component (B) (mol%), αc: content of component (C) (mol%)).

  In the present embodiment, the mixing index α is in the range of 0.001-19. When the mixing index α is less than 0.001, the fluidity and storage stability of the resin composition in the present embodiment are reduced, and when the mixing index α exceeds 19, the light emission of the present embodiment in which the resin composition is blended. The reliability of the device deteriorates. In particular, when a resin composition is used as a sealing material for a light emitting device, high reliability is required, so the mixing index α is preferably 0.2 to 5, more preferably 0.3 to 2. is there.

((D) component)
In addition to the components (A) to (C) described above, the composition according to the present embodiment has n = 0 indicating the number of R ¹ in the general formula (1) as a component (D), that is, (OR ² ) May be further cohydrolyzed and condensed.
Examples of the component (D) include tetramethoxysilane and tetraethoxysilane. These may be used alone or in combination.

(Other alkoxysilane compounds)
The composition in this embodiment may further cohydrolyze and condense the alkoxysilane compound represented by the general formula (1) other than the components (B) to (D) described above.
Examples of such compounds include dimethyldimethoxysilane, dimethylethoxysilane, hydroxymethyltrimethylsilane, methoxytrimethylsilane, methyltrimethoxysilane, mercaptomethyltrimethoxysilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, bis (2-chloro Ethoxy) methylsilane, ethoxytrimethylsilane, diethoxymethylsilane, ethyltriethoxysilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, ethoxydimethylvinylsilane, 3-chloropropyldimethoxymethylsilane, chloromethyldiethoxymethylsilane , Methyltris (ethylmethylketoxime) silane, trimethylpropoxysilane, trimethoxyisopropoxysilane, diethoxydi Tilsilane, 3- [dimethoxy (methyl) silyl] propane-1-thiol, trimethoxy (propyl) silane, (3-mercaptopropyl) trimethoxysilane, 3-aminopropyltrimethoxysilane, diethoxymethylvinylsilane, butoxytrimethylsilane, Butyltrimethoxysilane, methyltriethoxysilane, methoxyltriethoxysilane, triethoxyvinylsilane, diethoxydiethylsilane, dimethoxyldipropoxysilane, ethyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane Allyltriethoxysilane, 3-bromopropyltriethoxysilane, 3-allylaminopropyltrimethoxysilane, hexyloxytrimethylsilane, propyltriethoxysilane, Xyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (triethoxysilyl) propyl isocyanate, 3-ureidopropyltriethoxysilane, Methoxytripropylsilane, dibutoxydimethylsilane, methyltripropoxysilane, methyltriisopropoxysilane, octyloxytrimethylsilane, pentyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, hexyltriethoxysilane, Examples include 3-methacryloxypropyltriethoxysilane, octyltriethoxysilane, dodecyloxytrimethylsilane, and diethoxydodecylmethylsilane.

  In this embodiment, the mixing ratio of the “alkoxysilane compound where n = 2”, “alkoxysilane compound where n = 1” and “alkoxysilane compound where n = 0” of the alkoxysilane compound is expressed by the following formula ( It is represented by the mixture index β calculated in 3).

Mixing index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
In the above formula (3),
β ⁿ² : content (mol%) of the alkoxysilane compound in which n = 2 in the general formula (1),
β ⁿ⁰ : the content (mol%) of the alkoxysilane compound in which n = 0 in the general formula (1),
β ⁿ¹ : content (mol%) of an alkoxysilane compound in which n = 1 in the general formula (1),
And 0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1.

In the resin composition of the present embodiment, the mixing index β is preferably 0.01 to 1.4, more preferably 0.03 to 1.2, and still more preferably 0.05 to 1.0. Depending on the composition, if the mixing index β is less than 0.01, the fluidity of the resin composition may deteriorate, and if it exceeds 1.4, the reliability of the LED may deteriorate.
The mixing ratio of the (A) epoxy resin and the alkoxysilane compound “alkoxysilane compound where n = 0 to 2” in the present embodiment is represented by a mixing index γ calculated by the following formula (4).

Mixing index γ = (γa) / (γs) (4)
In the above formula (4),
γa: mass of epoxy resin (g),
γs: represents the mass (g) of the alkoxysilane compound in which n = 0 to 2 in the general formula (1).

  The mixing index γ is preferably 0.02 to 15, more preferably 0.04 to 7, and still more preferably 0.08 to 5. Depending on the composition, if the mixing index γ is less than 0.02, there may be a problem in the reliability of the LED manufactured by blending the resin composition, and if it exceeds 15, the light resistance may be deteriorated. is there.

(Cohydrolysis condensation process)
The resin composition of this embodiment can be obtained by first cohydrolyzing and condensing the above-described (A) epoxy resin and the above-described alkoxysilane compound represented by the formula (1).

The “cohydrolytic condensation” in the present embodiment means a hydrolysis condensation reaction performed in the presence of an epoxy resin, and is clearly distinguished from a reaction in the absence of an epoxy resin.
The “cohydrolytic condensation” in the present embodiment is composed of at least two steps of a reflux step without dehydration and a subsequent dehydration condensation step.

  The above-mentioned “refluxing process without dehydration” means that the reaction is carried out while returning the water and solvent blended for cohydrolysis and the water and solvent derived from the alkoxysilane compound generated during the reaction to the reaction solution. It is a process. Although the method is not particularly limited, the reaction is usually carried out while attaching a cooling pipe to the upper part of the reaction vessel and refluxing the generated water or solvent.

  The above-mentioned “dehydration condensation step” is a step of performing a condensation reaction while removing the blended water and solvent and the water and solvent generated in the above “refluxing step without dehydration”. The method is not particularly limited, but usually the reaction is carried out by distillation under reduced pressure using a rotary evaporator or the like.

The heating temperature during the cohydrolysis condensation reaction is preferably 130 ° C. or lower, more preferably 0 to 120 ° C., and still more preferably 0 to 100 ° C.
If it exceeds 130 ° C., the resin composition may be altered depending on the composition. The reaction time for cohydrolytic condensation is preferably 0.5 to 24 hours, more preferably 1 to 12 hours. If it is less than 0.5 hour, the remaining amount of unreacted substances may increase depending on the composition.

The resin composition of this embodiment may be performed by adding a hydrolysis-condensation catalyst during the co-hydrolysis condensation of the above-described (A) epoxy resin and alkoxysilane compound.
The hydrolysis condensation catalyst is not particularly limited as long as it promotes a conventionally known hydrolysis condensation reaction. For example, a metal (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, Strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth, etc., organic metals (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium) Strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth and other organic oxides, organic acid salts, organic halides, alkoxides, etc.), inorganic bases Magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.), organic base (Ammonia, tetramethylammonium hydroxide, etc.). Among the above organic metals, organic tin is preferable.

Organotin refers to those in which at least one organic group is bonded to a tin atom, and examples of the structure include monoorganotin, diorganotin, triorganotin, tetraorganotin, etc. Among them, Diorganotin is preferred.
Examples of the organic tin include tin tetrachloride, monobutyltin trichloride, monobutyltin oxide, monooctyltin trichloride, tetra n-octyltin, tetra n-butyltin, dibutyltin oxide, dibutyltin diacetate, dibutyltin dioctate, dibutyl Tin diversate, dibutyltin dilaurate, dibutyltin oxylaurate, dibutyltin stearate, dibutyltin dioleate, dibutyltin / silicon ethyl reactant, dibutyltin salt and silicate compound, dioctyltin salt and silicate compound, dibutyltin bis ( Acetylacetonate), dibutyltin bis (ethyl malate), dibutyltin bis (butylmalate), dibutyltin bis (2-ethylhexylmalate), dibutyltin bis (benzylmalate), dibutyltin bis Allyl malate), dibutyltin bis (oleylmalate), dibutyltin malate, dibutyltin bis (O-phenylphenoxide), dibutyltin bis (2-ethylhexylmercaptoacetate), dibutyltin bis (2-ethylhexylmercaptopropionate) Dibutyltin bis (isononyl 3-mercaptopropionate), dibutyltin bis (isooctylthioglycolate), dibutyltin bis (3-mercaptopropionate), dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate, Dioctyltin dioctate, dioctyltin didodecyl mercapto, dioctyltin versatate, dioctyltin distearate, dioctyltin bis (ethyl malate), dioctyltin bis (octylmalate), dioctyl Rutin malate, dioctyltin bis (isooctylthioglycolate), dioctyltin bis (2-ethylhexyl mercaptoacetate), dibutyltin dimethoxide, dibutyltin diethoxide, dibutyltin dibutoxide, dioctyltin dimethoxide, dioctyltin diethoxide, dioctyltin dibutoxide, Examples include tin octylate and tin stearate. Among these, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin diacetate, dibutyltin dimethoxide, dibutyltin diethoxide, dibutyltin dibutoxide, dioctyltin dimethoxide, dioctyltin diethoxide, dioctyltin dibutoxide are preferred.

  These hydrolytic condensation catalysts may be used alone or in combination. For example, organic acid tin and alkaline organic tin can be used in combination, or after reacting with an organic acid salt such as tin, treatment with an inorganic base is also possible. In this case, the inorganic base is preferably a hydroxide of a polyvalent cation such as magnesium hydroxide, calcium hydroxide, strontium hydroxide or barium hydroxide.

The addition amount of the hydrolysis-condensation catalyst is not particularly limited, but the preferable addition amount can be obtained from the mixing index δ which is a ratio to (OR ² ) in the above general formula (1). Here, the mixing index δ is expressed by the following formula (5).

Mixing index δ = (δe) / (δs) (5)
In formula (5),
δe: addition amount of hydrolytic condensation catalyst (mol number),
δs: Indicates the amount (mol number) of (OR ² ) in the general formula (1).

  The mixing index δ is preferably 0.0005 to 5, more preferably 0.001 to 1, and still more preferably 0.005 to 0.5. Depending on the composition of the resin composition, if the mixing index δ is less than 0.0005, the effect of promoting hydrolysis condensation may be difficult to obtain. If it exceeds 5, the ring opening of the cyclic ether group may be promoted. This is not preferable because it may lead to deterioration in storage stability of the resin composition.

In the step of obtaining the resin composition of the present embodiment by cohydrolysis condensation, the amount of water added is not particularly limited, but the preferred amount added is the ratio to (OR ² ) in the above general formula (1). Can be obtained from the mixing index ε. Here, the mixing index ε is expressed by the following formula (6).

Mixing index ε = (εw) / (εs) (6)
In formula (6),
εw: amount of water added (in mol),
εs: Indicates the amount (mol number) of (OR ² ) in the general formula (1).

  The mixing index ε is preferably 0.1 to 5, more preferably 0.2 to 3, and still more preferably 0.3 to 1.5. Depending on the composition of the resin composition, if the mixing index ε is less than 0.1, the hydrolysis reaction may not proceed. If it exceeds 5, the storage stability of the resin composition may be reduced.

  The addition of water in the co-hydrolysis condensation described above is mainly performed by hydrolysis of the alkoxysilane compound, and therefore needs to be performed in the “refluxing process without dehydration”. The timing of the addition is not particularly limited, and may be added first or gradually during the reaction using a feed pump or the like.

  The cohydrolysis condensation reaction of the present embodiment can be performed without a solvent or in a solvent. The solvent is not particularly limited as long as it is an organic solvent that can dissolve an epoxy resin and an alkoxysilane compound and is inactive to these, and for example, an aprotic polar solvent such as tetrahydrofuran or dioxane is preferably used. Can be used. Moreover, since it is easy to obtain, alcohol solvents such as methanol, ethanol, butanol, isopropanol, and n-butanol can be used. However, these promote the ring opening of the epoxy group. May not be suitable for use.

  The amount of the solvent added is preferably 0.01 to 20 times, more preferably 0.02 to 15 times, and more preferably 0.02 to 15 times the total mass of the epoxy resin and alkoxysilane compound subjected to the cohydrolysis condensation reaction. The amount is preferably 0.03 to 10 times. Since the molecular weight of the resin composition of the present embodiment can be controlled by the addition amount of the solvent, a resin composition having an appropriate molecular weight and thus an appropriate viscosity can be obtained by setting the addition amount in the above range. Can do.

The resin composition of this embodiment may further contain a predetermined (F) curing agent and (G) curing accelerator.
(F) The curing agent and (G) the curing accelerator will be described below.

(Curing agent)
A hardening | curing agent is a substance used in order to harden a resin composition, and is not specifically limited.
As the cured product, for example, acid anhydride compounds, amine compounds, amide compounds, phenol compounds and the like can be used, and in particular, aromatic acid anhydrides, cyclic aliphatic acid anhydrides, aliphatic acid anhydrides, and the like. An acid anhydride compound is preferred, and a carboxylic acid anhydride is more preferred.
The acid anhydride compounds include alicyclic acid anhydrides, and alicyclic carboxylic acid anhydrides are preferred among carboxylic acid anhydrides. These hardened | cured materials may be used individually or may be used in combination of 2 or more type.

  Specific examples of the curing agent include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride. , Methylhexahydrophthalic anhydride, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, tetraethylenepentamine, dimethylbenzylamine, ketimine compound, linolenic acid dimer and ethylenediamine Polyamide resin, bisphenols, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc. Biphenols such as polycondensates of aldehydes with various aldehydes, polymers of phenols with various diene compounds, polycondensates of phenols with aromatic dimethylol, or condensates of bismethoxymethylbiphenyl with naphthols or phenols And modified products thereof, imidazole, boron trifluoride-amine complex, guanidine derivatives and the like.

Specific examples of the alicyclic carboxylic acid anhydride include 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, “4-methylhexahydro Phthalic anhydride / hexahydrophthalic anhydride = 70/30 ”, 4-methylhexahydrophthalic anhydride,“ methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride / bicyclo [2.2. 1] heptane-2,3-dicarboxylic anhydride "and the like.
The addition amount of the curing agent is obtained from the mixed index ζ which is a ratio to the cyclic ether group contained in the above-described epoxy resin and alkoxysilane compound.
The mixing index ζ is expressed by the following formula (7).

Mixing index ζ = (ζf) / (ζk) (7)
In formula (7),
ζf: addition amount (number of moles) of curing agent,
ζk: Indicates the amount (mol number) of cyclic ether groups contained in the epoxy resin and the alkoxysilane compound.

The mixing index ζ is preferably 0.1 to 1.5, more preferably 0.2 to 1.3, and still more preferably 0.3 to 1.5.
If the mixing index ζ is less than 0.1, the curing rate may decrease, and if it exceeds 1.5, the moisture resistance as a cured product may deteriorate.

(Curing accelerator)
A curing accelerator is a curing catalyst used for the purpose of promoting the curing reaction.
As the curing accelerator, tertiary amines and salts thereof are preferable.
Specific examples of the curing accelerator include those shown in the following (1) to (8).
(1) Tertiary amines: benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, triethanolamine and the like.
(2) Imidazoles: 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-un Decylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl -4,5-di (hydroxymethyl) imidazole, 1- (2- Anoethyl) -2-phenyl-4,5-di [(2′-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) ) -2-Phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′) )] Ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methyl Imidazolyl- (1 ′)] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4-dia Roh-6- [2'-methylimidazolyl- - (1 ')] isocyanuric acid adduct of ethyl -s- triazine.
(3) Organophosphorus compounds: diphenylphosphine, triphenylphosphine, triphenyl phosphite and the like.
(4) Quaternary phosphonium salts: benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphos Phonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium o, o-diethylphosphorodithionate, tetra-n- Butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphenol Scan follower tetra Tsu tetraphenylborate and the like.
(5) Diazabicycloalkenes: 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof.
(6) Organometallic compounds: zinc octylate, tin actylate, aluminum acetylacetone complex, and the like.
(7) Quaternary ammonium salts: tetraethylammonium bromide, tetra-n-butylammonium bromide and the like.
(8) Metal halide compounds: Boron compounds such as boron trifluoride and triphenyl borate; zinc chloride, stannic chloride and the like.

The addition amount of a hardening accelerator is calculated | required from the following mixing parameter | index (eta) which is a ratio with respect to the mass of the above-mentioned epoxy resin and alkoxysilane compound.
The mixing index η is represented by the following formula (8).

Mixing index η = (ηg) / (ηk) × 100 (8)
In formula (8),
ηg: mass (g) of curing accelerator,
ηk: mass (g) of epoxy resin and alkoxysilane compound.

The mixing index η is preferably 0.01 to 5, more preferably 0.05 to 3, and still more preferably 0.1 to 1.
If the mixing index η is less than 0.01, curing may not proceed well, and if it exceeds 5, the light emission source may be colored.

Curing in the present embodiment means that a cured product is obtained by irradiating the resin composition used in the above-described embodiment with heat or energy rays to cause three-dimensional cross-linking between molecules. As the method, thermosetting is particularly preferable. In the present embodiment, the light emitting light source can be sealed by curing the resin composition.
First, thermosetting will be described.
Thermal curing is a method of obtaining a cured product by causing a chemical reaction by heat and generating three-dimensional cross-linking between molecules.
Examples of the thermosetting method include a method in which the resin composition contains a curing agent and a curing accelerator and heat-treats the resin composition, and a method in which the resin composition is thermally cured using a thermal cationic polymerization initiator. In particular, a method of heat-treating a curing agent or a curing accelerator in advance is preferable.

(Thermal cationic polymerization initiator)
The thermal cationic polymerization initiator is a compound that initiates polymerization by generating cationic species by heat. Examples thereof include various onium salts such as quaternary ammonium salts, sulfonium salts, phosphonium salts, and aromatic onium salts. These may be used alone or in combination of two or more. Although the usage method is not particularly limited, a method in which a thermal cationic polymerization initiator is contained in the resin composition and heat-treated is generally used.

  Examples of the quaternary ammonium salt include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium-p-toluenesulfonate, N, N-dimethyl. -N-benzylanilinium hexafluoroantimonate, N, N-dimethyl-N-benzylanilinium tetrafluoroborate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-diethyl-N-benzyl Trifluoromethanesulfonate, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoroantimonate, N, N-diethyl N-(4-methoxybenzyl) preparative Luigi hexafluoroantimonate and the like.

Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsinate, tris (4-methoxyphenyl) sulfonium hexafluoroarsinate, diphenyl (4-phenylthiophenyl). ) Sulfonium hexafluoroarsinate and the like.
Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.

  As specific examples of the aromatic onium salt, compounds exemplified in Japanese Patent Publication No. 52-14277, Japanese Patent Publication No. 52-14278, Japanese Patent Publication No. 52-14279, and the like can be used.

Next, energy beam curing will be described.
The energy ray curing is a cured product by irradiating the resin composition of the present embodiment with predetermined energy rays (in addition to light such as ultraviolet rays, near ultraviolet rays, visible light, near infrared rays, and infrared rays, electron beams, etc.). Is the way to get.
As the energy ray, light is preferable, and ultraviolet light is more preferable.

Sources of energy rays include, for example, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, UV lamp, xenon lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, argon ion laser, helium cadmium laser. And various light sources such as a helium neon laser, a krypton ion laser, various semiconductor lasers, a YAG laser, an excimer laser, a light emitting diode, a CRT light source, a plasma light source, and an electron beam irradiator.
In the energy ray curing step, the polymerization initiator added to the resin composition is decomposed by energy ray stimulation to generate a polymerization initiating species, the polymerizable functional group of the target substance is polymerized, and curing proceeds.

The polymerization initiators can be roughly classified into the following three (1) to (3) depending on the generated active species. These polymerization initiators may be used alone or in combination of two or more.
(1) Those that generate radicals upon irradiation with energy rays.
(2) Those that generate cations by irradiation with energy rays (when the energy rays are light, they are called photoacid generators).
(3) Those that generate anions upon irradiation with energy rays (referred to as photobase generators when the energy rays are light).

  Examples of polymerization initiators used for energy ray curing include benzoins and benzoin alkyl ethers (benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, etc.), and acetophenones (acetophenone, 2,2-dimethoxy-2-phenyl). Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-monoforino-propane-1- ON, N, N-dimethylaminoacetophenone, etc.), anthraquinones (2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylan Laquinone, 2-aminoanthraquinone, etc.), thioxanthones (2,4-dimethylthiosantone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.), ketals (acetophenone dimethyl ketal, benzyldimethyl) Ketones, etc.), benzophenones (benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, etc.), xanthones, benzoates (ethyl 4-dimethylaminobenzoate, 2- (dimethyl) Amino) ethyl benzoate, etc.), amines (triethylamine, triethanolamine, etc.), iodonium salt compounds, sulfonium salt compounds, ammonium salt compounds, phosphonium salt compounds, al Salt compounds, stibonium salt compound, an oxonium salt compound, a selenonium salt compound, a stannonium salt compound and the like.

(Additive for resin composition)
In the resin composition of the present embodiment, various organic resins, inorganic fillers, colorants, leveling agents, lubricants, surfactants, silicone compounds, reactivity, as long as their functions are not impaired. Diluents, non-reactive diluents, antioxidants, light stabilizers and the like can be added as appropriate. In addition, plasticizers, flame retardants, stabilizers, antistatic agents, impact strengthening agents, foaming agents, antibacterial / antifungal agents, conductive fillers, antifogging agents, and crosslinks that are generally used as additives for resins An agent or the like can be blended.

  The organic resin is not particularly limited, and examples thereof include an epoxy resin, an acrylic resin, a polyester resin, and a polyimide resin. In particular, those having highly reactive organic groups such as epoxy resins are preferred.

  Examples of inorganic fillers include silicas (melted crushed silica, crystal crushed silica, spherical silica, fumed silica, colloidal silica, precipitated silica, etc.) silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, sulfuric acid Barium, calcium sulfate, mica, talc, clay, aluminum oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber And molybdenum disulfide. In particular, silicas, calcium carbonate, aluminum oxide, aluminum hydroxide, calcium silicate and the like are preferable, and silicas are more preferable in consideration of physical properties of the cured product. These inorganic fillers may be used alone or in combination of two or more.

  The colorant is not particularly limited as long as it is a substance used for the purpose of coloring. For example, phthalocyanine, azo, disazo, quinacridone, anthraquinone, flavantron, perinone, perylene, dioxazine, condensed azo, azomethine series Inorganic pigments such as titanium oxide, lead sulfate, chromium yellow, zinc yellow, chromium vermillion, valve shell, cobalt purple, bitumen, ultramarine, carbon black, chromium green, chromium oxide, cobalt green, and the like. These colorants may be used alone or in combination of two or more.

  The leveling agent is not particularly limited, and examples thereof include oligomers having a molecular weight of 4000 to 12000 made of acrylates such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, epoxidized soybean fatty acid, epoxidized abiethyl alcohol, Examples include hydrogenated castor oil and titanium-based coupling agents. These leveling agents may be used alone or in combination of two or more.

  The lubricant is not particularly limited, and examples thereof include hydrocarbon lubricants such as paraffin wax, microwax, and polyethylene wax, and higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. Lubricants, stearylamide, palmitylamide, oleylamide, higher fatty acid amide lubricants such as methylene bisstearamide, hardened castor oil, butyl stearate, ethylene glycol monostearate, pentaerythritol (mono- , Di-, tri-, or tetra-) stearate and other higher fatty acid ester lubricants, cetyl alcohol, stearyl alcohol, polyethylene glycol, polyglycerol and other alcohol lubricants, lauric acid, myristic acid, palmitic Natural waxes such as metal soaps such as magnesium, calcium, cadmium, barium, zinc, lead, etc., such as acid, stearic acid, arachidic acid, behenic acid, ricinoleic acid, naphthenic acid, carnauba wax, candelilla wax, beeswax, montan wax And the like. These lubricants may be used alone or in combination of two or more.

  The surfactant is an amphiphilic substance having a hydrophobic group having no affinity for the solvent in the molecule and an amphiphilic group (usually a hydrophilic group) having an affinity for the solvent. The type of the surfactant is not particularly limited, and examples thereof include silicone surfactants and fluorine surfactants. Surfactants may be used alone or in combination of two or more.

  The silicone compound is not particularly limited, and examples thereof include silicone resin, silicone condensate, silicone partial condensate, silicone oil, silane coupling agent, silicone oil, polysiloxane and the like. These may be modified by introducing organic groups into both ends, one end, or side chains. The modification method is not particularly limited. For example, amino modification, epoxy modification, alicyclic epoxy modification, carbinol modification, methacryl modification, polyether modification, mercapto modification, carboxyl modification, phenol modification, silanol modification, Examples include polyether modification, polyether / methoxy modification, and diol modification.

The reactive diluent is not particularly limited. For example, alkyl glycidyl ether, alkylphenol monoglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, alkanoic acid glycidyl ester, ethylene Examples include glycol diglycidyl ether and propylene glycol diglycidyl ether.
The non-reactive diluent is not particularly limited, and examples thereof include high-boiling solvents such as benzyl alcohol, butyl diglycol, and propylene glycol monomethyl ether.

  The antioxidant is not particularly limited, and examples thereof include organic phosphorus antioxidants such as triphenyl phosphate and phenylisodecyl phosphite, and organic sulfurs such as distearyl-3,3′-thiodipropinate. Examples of the antioxidant include phenolic antioxidants such as 2,6-di-tert-butyl-p-cresol.

  The light stabilizer is not particularly limited, and examples thereof include benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based, nickel-based, and triazine-based ultraviolet absorbers, hindered amine-based light stabilizers, and the like.

The following substances may be further added to the resin composition used as the sealing material in the present embodiment.
For example, solvents, oils and fats, processed oils, natural resins, synthetic resins, pigments, dyes, pigments, release agents, preservatives, adhesives, deodorants, flocculants, cleaning agents, deodorants, pH adjusters, photosensitive materials, Ink, electrode, plating solution, catalyst, resin modifier, plasticizer, softener, agrochemical, insecticide, fungicide, pharmaceutical raw material, emulsifier / surfactant, rust inhibitor, metal compound, filler, cosmetic / pharmaceutical raw material , Dehydrating agent, drying agent, antifreeze, adsorbent, colorant, rubber, foaming agent, colorant, abrasive, mold release agent, flocculant, antifoaming agent, curing agent, reducing agent, flux agent, film treatment agent, Casting raw materials, minerals, acids / alkalis, shot agents, antioxidants, surface coating agents, additives, oxidants, explosives, fuels, bleaches, fragrances, concrete, fibers (carbon fibers, aramid fibers, glass fibers, etc.) Glass, metal, excipient, disintegrant, binder, flow Agents, gelling agents, stabilizers, preservatives, buffering agents, suspending agents, thickeners, and the like.

(Light source)
In the light emitting device of this embodiment, the light emitting light source to be used is not particularly limited, and a known light source can be used. The light emitting light source is not particularly limited, and examples thereof include a light emitting diode (LED), a laser diode (LD), an incandescent bulb, a fluorescent lamp, and a high-intensity discharge lamp (HID lamp). Among these, a light emitting diode (LED) is preferable from the viewpoint of energy efficiency and durability.

  An LED is a kind of semiconductor element, and emits light when a current is passed. Two terminals, an anode and a cathode, are connected to the LED. When a positive voltage is applied to the anode and a negative voltage is applied to the cathode, a current flows at a voltage of several volts and light is emitted. As a light emission principle, an electroluminescence effect (EL effect) is used, and an organic EL is included in the LED in terms of classification.

  There are various types of LEDs, such as red, green, orange, and blue. If the three primary colors of light are used, it is possible to produce light of various colors including white by combining these. Moreover, you may mix | blend a fluorescent substance with the said LED. Thus, by absorbing light emitted from the LED chip and performing wavelength conversion, it is possible to provide an LED having a color tone different from the color tone of the LED chip at the site of the sealing material.

(Light emitting device)
The structure of the LED used in the present embodiment is not particularly limited, and includes, for example, a sealing material (sealing resin), an outer layer resin, an LED chip, a lead frame, a bonding wire, and the like.
The light emitting device of this embodiment may include other optical elements as necessary.

  The shape of the LED is not particularly limited and can be appropriately selected depending on the application. For example, a bullet type, a surface mount type (hereinafter referred to as SMD type), a Chip On Board type (hereinafter referred to as COB type). , Power LED type, plate shape, thin film shape and the like.

FIG. 1 shows an embodiment example in which the light emitting device of this embodiment is a bullet-type LED. Reference numeral 10 in FIG. 1 denotes a bullet-type LED. The LED chip 10 a of the bullet type LED 10 is encapsulated by a sealing material 12. The LED chip 10 a is mounted in a cup formed integrally with the lead frame 18, and its periphery is molded into a shell shape with the outer layer resin 16.
For example, in the case of a white LED, a resin in which a phosphor is dispersed is encapsulated in a cup of the lead frame 18, and the periphery thereof is molded into a bullet shape. In the LED of this embodiment, the LED chip 10a, the bonding wire 14 and the like can be sealed with the sealing material 12 and the lead electrode can be drawn out.

  FIG. 2 shows an embodiment in which the light-emitting device of this embodiment is an SMD type LED. Reference numeral 20 in FIG. 2 denotes an SMD type LED. The LED chip 20 a of the SMD type LED 20 is sealed with a sealing material 22. Since light is reflected by the reflector 28 inside the cavity, it has high directivity. The input / output electrodes and chip mounting electrodes of the anode 20A and the cathode 20B can be formed by plating the package substrate 26. In the LED of this embodiment, the LED chip 20a, the bonding wire 24, the reflection plate 28, and the like can be sealed with the sealing material 22 and the lead electrode can be drawn out.

  The above-described sealing material is a member having a function of protecting a predetermined target from factors (foreign substances) such as temperature, moisture, and dust, mainly in an airtight and liquidtight state. Foreign materials include sound, vibration, and erosion by chemical materials.

  The sealing material may be used in combination with another sealing resin made of epoxy resin, silicone resin, epoxy silicone resin, acrylic resin, urethane resin, urea resin, imide resin, glass or the like. Furthermore, you may mix | blend fluorescent substance with a sealing material. Thus, by absorbing light emitted from the light emitting light source and performing wavelength conversion, it is possible to provide an LED having a color tone different from the color tone of the light emitting light source at the site of the sealing material.

Moreover, as a use site | part of a sealing material, it is used in many cases, for example for protection of the junction part of a LED chip main body, a LED chip, a wire, and a lead wire. Further, it can also be used in a lead-free reflow mounting process corresponding to the RoHS directive (Restriction of Hazardous Substances), which is becoming the mainstream in place of the conventional lead solder process.
The above-mentioned phosphor absorbs energy such as a fluorescent substance, that is, electron beam, X-ray, ultraviolet ray, and electric field, and emits (emits) a part of the absorbed energy as visible light relatively efficiently. It is not particularly limited as long as it is a substance, and it can be adopted regardless of whether it is inorganic or organic.

The size of the inorganic phosphor is not particularly limited, but a powder having a particle size of 1 to several tens of μm is often used. In order to express the performance of the inorganic phosphor, a compound A called an activator (emission center) introduced into a compound A called a matrix is generally used. : Activator B ”.
The base A and the activator B are not particularly limited, but examples of the base A include oxides and nitrides. Examples of the activator B include rare earth elements such as europium (Eu) and cerium (Ce).

Examples of the above-described oxide phosphor include, for example, “YAG: Ce” in which the base A is yttrium aluminate (Y ₃ Al ₅ O ₁₂ : hereinafter referred to as “YAG”) and the activator B is cerium (Ce). “Phosphors” are well known. When “YAG: Ce phosphor” is irradiated with blue light (near 460 nm), yellow light emission occurs efficiently. In this phosphor, a part of Y of “Y ₃ Al ₅ O ₁₂ ” is replaced with another Gd, Tb, or the like, or a part of Al is replaced with Ga or the like to change the structure of the base A. Therefore, the emission peak position can be shifted to the long wavelength side or the short wavelength side, which is very useful.

As another example of the oxide phosphor, the base A is strontium barium silicate (Sr, Ba) ₂ SiO ₄ and europium (Eu) is introduced as the activator B, “(Sr, Ba) ₂ SiO ₄ : Eu phosphor ”is known. In this system, the emission color can be adjusted from green to orange by changing the composition ratio of Sr and Ba.
Examples of nitride phosphors include the following.

(1) α-Sialon Phosphor A matrix A is a crystal in which a metal ion such as Ca and aluminum and oxygen are dissolved in an α-type silicon nitride crystal, and “(M _p (Si, Al) ₁₂ (O, _{N) 16} is represented by "here, M is" _{Ca p (Si, Al) 12} (O, N) 16 is a metal ion, p specifically showing the amount of solid solution is:. include Eu ". .

(2) β-sialon phosphor _{Matrix A is represented by} a composition of “Si _6-q Al _q O _q N _{8 -q} ” in which aluminum and oxygen are dissolved in β-type silicon nitride crystal, q represents the amount of solid solution. Among these, “Si _6-q Al _q O _q N _{8 -q} : Eu” is well known.

(3) CaAlSiN ₃ phosphor The base A is a nitride crystal obtained by reacting calcium nitride, aluminum nitride, and silicon nitride at a high temperature of 1800 ° C., and specifically includes “CaAlSiN ₃ : Eu”.

Specific examples of the inorganic phosphor include, for example, “6MgO.As ₂ O5: Mn ⁴⁺ , Y (PV) O ₄ : Eu”, “CaLa _0.1 Eu ₀ , as those having a red emission color. _.9 Ga ₃ O ₇ ”,“ BaY _0.9 Sm _0.1 Ga ₃ O ₇ ”,“ Ca (Y _0.5 Eu _0.5 ) (Ga _0.5 In _0.5 ) ₃ O ₇ ”, “Y ₃ O ₃ : Eu, YVO ₄ : Eu”, “Y ₂ O ₂ : Eu”, “3.5MgO · 0.5MgF ₂ GeO ₂ : Mn ⁴⁺ ”, “(Y · Cd) BO ₂ : Eu” Etc.
Examples of blue light-emitting colors include “(Ba, Ca, Mg) ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ ”, “(Ba, Mg) ₂ Al ₁₆ O ₂₇ : Eu ²⁺ ”, “ ^{_{Ba 3 MgSi 2 O 8: Eu}} 2+ "," ^{_{BaMg 2 Al 16 O 27: Eu}} 2+ "," _{(Sr, Ca) 10 (PO} 4) 6 C l2: Eu 2+ "," (Sr, _{Ca) 10} ( _{PO 4) 6 C l2 · nB} 2 O 3: Eu 2+ "," _{Sr 10 (PO 4) 6 Cl} 2: Eu 2+ "," _{(Sr, Ba, Ca) 5} (PO 4) 3 Cl: Eu 2+ " , “Sr ₂ P ₂ O ₇ : Eu”, “Sr ₅ (PO ₄ ) ₃ Cl: Eu”, “(Sr, Ca, Ba) ₃ (PO ₄ ) ₆ Cl: Eu”, “SrO · P ₂ O ₅ · _B 2 _{O 5:} Eu "," _(BaCa) 5 ( O _{4) 3} Cl: Eu "," _SrLa 0.95 _Tm 0.05 _Ga 3 _{O 7} "," ZnS: Ag "," GaWO ₄ "," _Y 2 _SiO 6: Ce "," ZnS: Ag, Ga , Cl "," _Ca 2 _B 4 OCl: ^{Eu 2+} "," BaMgAl ₄ O _3: ^{Eu 2+} "," _{(M 1, Eu) 10 (} PO 4) 6 C l2 (M 1 are, Mg, Ca, Sr And at least one element selected from the group consisting of Ba) and the like.
Examples of green light-emitting colors include “Y ₃ Al ₅ O ₁₂ : Ce ³⁺ (YAG)”, “Y ₂ SiO ₅ : Ce ³⁺ , Tb ³⁺ ”, “Sr ₂ Si ₃ O ₈ .2SrCl”. ₂ : Eu ”,“ BaMg ₂ Al ₁₆ O ₂₇ : Eu ²⁺ , Mn ²⁺ ”,“ ZnSiO ₄ : Mn ”,“ Zn ₂ SiO ₄ : Mn ”,“ LaPO ₄ : Tb ”,“ SrAl ₂ O ₄ : Eu ”, “SrLa _0.2 Tb _0.8 Ga ₃ O ₇ ”, “CaY _0.9 Pr _0.1 Ga ₃ O ₇ ”, “ZnGd _0.8 Ho _0.2 Ga ₃ O ₇ ”, “SrLa _0.6 Tb _0.4 Al ₃ O ₇ , ZnS: Cu, Al ”,“ (Zn, Cd) S: Cu, Al ”,“ ZnS: Cu, Au, Al ”,“ Zn ₂ SiO ₄ : Mn ”,“ ZnSiO _4: Mn "," Zn : Ag, Cu "," (Zn · Cd) S: Cu "," ZnS: Cu "," GdOS: Tb, "" LaOS: Tb, "" YSiO _4: Ce · Tb "," ZnGeO _4: Mn " , “GeMgAlO: Tb”, “SrGaS: Eu ²⁺ ”, “ZnS: Cu · Co”, “MgO · nB ₂ O ₃ : Ge, Tb”, “LaOBr: Tb, Tm”, “La ₂ O ₂ S: Tb "and the like.
“YVO ₄ : Dy” having a white emission color, “CaLu _0.5 Dy _0.5 Ga ₃ O ₇ ” having a yellow emission color, and the like are also known.

Specific examples of the organic phosphor include, for example, 1,4-bis (2-methylstyryl) benzene (Bis-MSB), trans-4,4′-diphenylstilbene (DPS) having a blue emission color. ) And stilbene dyes such as 7-hydroxy-4-methylcoumarin (coumarin 4).
Examples of those having yellow to green fluorescent colors include Brilliantsulfoflavine FF, Basic yellow HG, SINLOIHI COLOR FZ-5005 (manufactured by SINLOIHI), and the like.
Examples of those having yellow to red fluorescent colors include Eosine, Rhodamine 6G, and Rhodamine B.

  As the above-mentioned outer layer resin, for example, an epoxy resin, a silicone resin, an epoxy-silicone hybrid resin, or the like is generally used. However, heat resistance and light resistance are not required as much as a sealing resin, and since the amount used is large, an epoxy resin is often used for cost reduction.

The LED chip is an element made of an element such as gallium (Ga), arsenic (As), indium (In), P (phosphorus), N (nitrogen), Al (aluminum), and the like. Light can be emitted in various colors. For example, by combining Ga, As, In, and P, it is possible to emit red to yellow light, and by combining In, Ga, and N, it is possible to emit blue to green light or ultraviolet light. it can. Therefore, in recent years, there is a great demand for InGaN-based devices because there is a high need for blue-based light that can be used as a light source for white LEDs depending on the combination with a phosphor. Specific examples of the material, emission color, and emission wavelength of typical LED chips include, for example, “GaInN (ultraviolet light to blue to green, about 370 to 530 nm)”, “InGaAlP / GaAs (green to yellow-green, about 560). ˜580 nm), “InGaAlP / GaP (yellow, about 590 nm)”, “InGaAlP (red, about 644 nm)”, “GaAlAs / GaAs (red, about 660 nm)”, “GaP / GaP (red, about 700 nm)” , “GaAlAs (infrared light, about 880 nm)”, “GaAs (infrared light, about 940 nm)” and the like.
The bonding wire is a wire for connecting the electrode of the LED chip and the lead electrode, and the material is not particularly limited as long as it is a conductive material, but usually copper (Cu), gold (Au), aluminum (Al), or a wire made of an alloy thereof. Moreover, the surface may be coat | covered with other electroconductive substances, such as silver (Ag).

(Semiconductor device)
The semiconductor device of the present embodiment is not particularly limited as long as it is a semiconductor package in which the optical device is incorporated, and can be applied to various uses as described below.

(Use of LED and semiconductor device of this embodiment)
Applications of the LED and the semiconductor device of the present embodiment are not particularly limited. For example, a backlight of a mobile phone, a display part of a business phone, a key panel, etc .; a head of an optical disk device; a large LCD, a small LCD, a television LCD backlights used in notebook computers, LCD monitors, flashlights, general lighting, environmental equipment lighting, street lights, indirect lighting, etc .; instrument panels, brake lamps, rear combination lamps, headlights, downlights, interior lighting Used for automobile lamps and display parts such as car stereos; traffic signal lamps; road display boards, LED display boards such as stations and airports, etc .; outdoor signboards and outdoor displays; gastric cameras, endoscopes, etc. Medical LED; LED for amusement machines such as pachinko machines and game machines; Copy / Fact Millimeters, can be used as a general display portion or the like of the appliances.

Although the Example which demonstrated this embodiment concretely is illustrated below, this embodiment is not limited to a following example, unless the summary is exceeded.
The physical properties in Examples and Comparative Examples were evaluated as follows.

<Epoxy equivalent (WPE)>
It was measured according to “JIS K 7236: 2001 (How to determine epoxy equivalent of epoxy resin)”.

<Viscosity>
Measurement was performed under the following conditions.
Rotating E-type viscometer: “TV-22” manufactured by Toki Sangyo Co., Ltd.
Rotor: 3 ° × R14 (Other rotors may be selected as necessary.)
Measurement temperature: 25 ° C
Sample volume: 0.4mL

<Calculation of mixing index α>
The mixing index α was calculated from the following formula (2).
Mixing index α = (αc) / (αb) (2)
here,
αb: (B) In the general formula (1), n = 1 to 2, and R ¹ is an alkoxysilane compound content (mol%) having at least one cyclic ether group,
αc: (C) Content (mol%) of an alkoxysilane compound having n = 1 to 2 and having at least one aryl group as R ¹ in the general formula (1).

<Calculation of mixing index β>
The mixing index β was calculated from the following formula (3).
Mixing index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
here,
β ⁿ² : content (mol%) of the alkoxysilane compound in which n = 2 in the general formula (1),
β ⁿ⁰ : the content (mol%) of the alkoxysilane compound in which n = 0 in the general formula (1),
β ⁿ¹ : content (mol%) of an alkoxysilane compound in which n = 1 in the general formula (1),
At this time, 0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1.

<Calculation of mixing index γ>
The mixing index γ was calculated from the following equation (4).
Mixing index γ = (γa) / (γs) (4)
here,
γa: mass of epoxy resin (g),
γs: Mass (g) of the alkoxysilane compound in which n = 0 to 2 in the general formula (1).

<Calculation of mixing index δ>
The mixing index δ was calculated from the following equation (5).
Mixing index δ = (δe) / (δs) (5)
here,
δe: addition amount of hydrolytic condensation catalyst (mol number),
δs: The amount (mol number) of (OR ² ) in the general formula (1).

<Calculation of mixing index ε>
The mixing index ε was calculated from the following equation (6).
Mixing index ε = (εw) / (εs) (6)
here,
εw: amount of water added (in mol),
.epsilon.s: The amount of the general formula ^{(1) (OR 2) (} mol number).

<Calculation of mixing index ζ>
The mixing index ζ was calculated from the following equation (7).
Mixing index ζ = (ζf) / (ζk) (7)
here,
ζf: addition amount (number of moles) of curing agent,
ζk: The amount (mol number) of cyclic ether groups contained in the epoxy resin and the alkoxysilane compound.

<Calculation of mixing index η>
The mixing index η was calculated from the following formula (8).
Mixing index η = (ηg) / (ηk) × 100 (8)
here,
ηg: mass (g) of curing accelerator,
ηk: mass (g) of epoxy resin and alkoxysilane compound.

<Calculation of storage stability index θ and storage stability of resin composition>
The storage stability in the resin composition was evaluated by a storage stability index θ represented by the following general formula (9).
Storage stability index θ = (storage viscosity) / (starting viscosity) (9)
The container containing the resin composition immediately after production was sealed and the temperature was adjusted at 25 ° C. for 2 hours, and then the viscosity at 25 ° C. was measured, which was defined as “starting viscosity”.
Further, the container containing the resin composition was sealed and stored in a constant temperature incubator at 25 ° C. for 2 weeks. After storage, the viscosity at 25 ° C. was measured, and this was designated as “storage viscosity”.
When the resin composition has fluidity (viscosity is 1000 Pa · s or less) and the storage stability index θ is 4 or less, it was judged to have storage stability.

<Light resistance test of LED (cured product)>
It is difficult to cut out a sample after manufacturing the LED. Therefore, a cured product was prepared and evaluated by the following method, and the result of evaluation was substituted for the light resistance evaluation of the LED.
(1) The cured product solution prepared by the method described later was cured to produce a cured product of 20 mm × 10 mm × thickness 3 mm.
(2) The cured product was covered with a black mask of 25 mm × 15 mm × thickness 1.2 mm with a hole having a diameter of 5.5 mm to obtain a sample for light resistance test.
(3) A UV irradiation device (USHIO INC., “Spot Cure SP7-250DB”) is connected to the sample in a constant temperature incubator at 50 ° C. via an optical fiber so that the sample can be irradiated with UV light. Got ready.
(4) The sample was set in a constant temperature incubator at 50 ° C. with the black mask on top.
(5) UV light of 2 W / cm ² was irradiated for 96 hours from the top of the black mask so that UV light could be irradiated to a hole with a diameter of 5.5 mm.
(6) The UV-irradiated sample was measured with a spectrocolorimeter (Nippon Denshoku Industries Co., Ltd., “SD5000”) with an integrating sphere opening modified to a diameter of 10 mm.
(7) Yellowness (YI) was determined according to “ASTM D1925-70 (1988): Test Method for Yellowness Index of Plastics”. When this YI was 13 or less, it was judged as passing.

<LED reliability test (1) (continuous operation test: hereinafter referred to as “L test”)>
Ten LEDs are connected to "METHOD FOR SEMICONDUCTOR DEVICES", METOD 1026.5 (STEADY-STATE OPERATION LIFE), and "MIL-STD-883G (MICROCIRCUITS.5)". According to (STEADY-STATE LIFE), it evaluated on condition of the following.
Lighting was performed under the conditions of forward current (IF) = 20 mA, ambient temperature (Ta) = 25 ° C., 960 hours, and the total luminous flux (lm) before and after lighting was measured. Further, for each LED, “total luminous flux maintenance factor (%) = (total luminous flux after lighting) / (total luminous flux before lighting) × 100” is obtained, and the minimum value of the total luminous flux maintenance factor (%) of all LEDs is When it was 90% or more, it was judged to be acceptable.

<LED reliability test (2) (thermal shock test: hereinafter referred to as “TS test”)>
Ten LEDs were evaluated under the following conditions in accordance with test method 307 (thermal shock test) of “EIAJ ED-4701 / 300 (Semiconductor device environment and durability test method (strength test I)”).
“-10 ° C. (5 minutes) to 100 ° C. (5 minutes)” was set as one cycle, and after 100 cycles of thermal shock, the lighting of the LEDs was confirmed.

<LED reliability test (3) (temperature cycle test: hereinafter referred to as “TC test”)>
Ten LEDs were evaluated under the following conditions in accordance with test method 105 (temperature cycle test) of “EIAJ ED-4701 / 100 (Semiconductor device environment and durability test method (life test I)”).
“-40 ° C. (30 minutes) to 85 ° C. (5 minutes) to 100 ° C. (30 minutes) to 25 ° C. (5 minutes)” is taken as one cycle. When all 10 pieces were lit, it was judged as passing.
In evaluation of said LED, when all the light resistance and reliability tests (1)-(3) are passing, it was judged that it was a pass as comprehensive judgment.
About the raw material used by the Example and the comparative example, it shows to the following (1)-(12).

(1) Epoxy resin (1-1) Epoxy resin A1: Poly (bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as “Bis-A1 epoxy resin”)
・ Product name: “AER2600”, manufactured by Asahi Kasei Epoxy Corporation
Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
Epoxy equivalent (WPE): 188 g / eq
Viscosity (25 ° C.): 14.8 Pa · s
(1-2) Epoxy resin A2: Poly (bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as “Bis-A2 epoxy resin”)
・ Product name: “AER2500” manufactured by Asahi Kasei Epoxy Corporation
Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
Epoxy equivalent (WPE): 186 g / eq
Viscosity (25 ° C.): 10.2 Pa · s
(1-3) Epoxy resin A3: poly (bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as “Bis-A3 epoxy resin”)
・ Product name: “AER6071” manufactured by Asahi Kasei Epoxy Corporation
Moreover, the epoxy equivalent (WPE) measured by the above-mentioned method was as follows. However, since this epoxy resin A3 was solid at 25 ° C., the viscosity could not be measured.
Epoxy equivalent (WPE): 470 g / eq

(2) Alkoxysilane compound H: 3-glycidoxypropyltrimethoxysilane (hereinafter referred to as “GPTMS”)
・ Product name: “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.

(3) Alkoxysilane compound L: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (hereinafter referred to as “ECETMS”)
・ Product name: “KBM-303”, manufactured by Shin-Etsu Chemical Co., Ltd.

(4) Alkoxysilane compound I: phenyltrimethoxysilane (hereinafter referred to as “PTMS”)
・ Product name: “KBM-103” manufactured by Shin-Etsu Chemical Co., Ltd.

(5) Alkoxysilane compound J: Dimethyldimethoxysilane (hereinafter referred to as “DMDMS”)
・ Product name: “KBM-22” manufactured by Shin-Etsu Chemical Co., Ltd.

(6) Alkoxysilane compound K: tetraethoxysilane (hereinafter referred to as “TEOS”)
・ Product name: “KBE-04”, manufactured by Shin-Etsu Chemical Co., Ltd.

(7) Solvent (7-1) Tetrahydrofuran: Wako Pure Chemical Industries, Ltd., stabilizer-free type (hereinafter referred to as “THF”)
(7-2) tert-butanol: manufactured by Wako Pure Chemical Industries, Ltd., stabilizer-free type (hereinafter referred to as “t-BuOH”)

(8) Hydrolytic condensation catalyst (8-1) Dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as “DBTDL”)
(8-2) Dibutyltin dimethoxide (manufactured by Sigma-Aldrich, hereinafter referred to as “DBTDM”)

(9) Curing agent: “4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30”
-Product name: “Rikacid MH-700G” manufactured by Shin Nippon Rika Co., Ltd.

(10) Curing accelerator: Amine-based compound-Trade name: "U-CAT 18X" manufactured by Sun Apro Co., Ltd.

(12) Silicone resin ・ Product name: “EG6301 (liquid A / liquid B)” manufactured by Toray Dow Corning Co., Ltd.

[Synthesis Example 1]
The resin composition was manufactured by the following process.
(1) Preparation: A circulating water bath was set at 5 ° C. and refluxed to the cooling pipe. Further, an oil bath at 80 ° C. was placed on the magnetic stirrer.
(2) According to the composition ratio shown in Table 1 below, the Bis-A1 epoxy resin, the alkoxysilane compound, and THF are placed in a flask containing a stirrer and mixed and stirred in an atmosphere at 25 ° C. Water and a hydrolysis condensation catalyst were added and mixed and stirred.
(3) Subsequently, a cooling tube was set on the flask, and the flask was immediately immersed in an oil bath at 80 ° C. to start stirring, and reacted for 20 hours while refluxing (refluxing step).
(4) After completion of the reaction, the cooling tube was removed from the flask after cooling to 25 ° C.
(5) The solution after completion of the refluxing process was distilled off at 400 Pa and 50 ° C. for 1 hour using an evaporator, and then further subjected to a dehydration condensation reaction while being distilled off at 80 ° C. for 10 hours (dehydration condensation). Process).
(6) After completion of the dehydration condensation reaction, the mixture was cooled to 25 ° C. to obtain a resin composition.
(7) The above-mentioned mixing indices α1 to ε1 of this resin composition are shown in Table 3 below.
(8) Furthermore, according to the above-mentioned method, the epoxy equivalent (WPE), the starting viscosity and the storage viscosity of the resin composition obtained in the above (6) were measured. Furthermore, the storage stability index θ1 was obtained and shown in Table 3.
The resin composition of Synthesis Example 1 had an epoxy equivalent (WPE) of 230 g / eq, and showed an appropriate value. Further, the starting viscosity = 33.7 Pa · s <1000 Pa · s and the storage viscosity = 47.0 Pa · s <1000 Pa · s, both were fluid liquids. The storage stability index θ1 = 1.39 ≦ 4, and it was found that the resin composition had storage stability.

[Synthesis Example 2]
Resin compositions were produced according to Tables 1 and 2 in the same manner as in Synthesis Example 1. Table 3 shows the results of evaluation by the same method as in Synthesis Example 1, the mixing indices α2 to ε2, and the storage stability index θ2.
As shown in Table 3, the resin composition of Synthesis Example 2 had an epoxy equivalent (WPE) = 231 g / eq, and showed an appropriate value. Further, the starting viscosity = 13.2 Pa · s <1000 Pa · s and the storage viscosity = 19.1 Pa · s <1000 Pa · s, both were fluid liquids. In addition, the storage stability index θ2 = 1.45 ≦ 4, and it was found that the resin composition had storage stability.

[Synthesis Example 3]
Resin compositions were produced according to Tables 1 and 2 in the same manner as in Synthesis Example 1. Table 3 shows the results of evaluation by the same method as in Synthesis Example 1, the mixing indices α3 to ε3, and the storage stability index θ3.
As shown in Table 3, the resin composition of Synthesis Example 3 was epoxy equivalent (WPE) = 242 g / eq, and showed an appropriate value. Further, the starting viscosity = 14.5 Pa · s <1000 Pa · s and the storage viscosity = 16.2 Pa · s <1000 Pa · s, both were fluid liquids. Further, the storage stability index θ3 = 1.12 ≦ 4, and it was found that the resin composition had storage stability.

[Synthesis Example 4]
Resin compositions were produced according to Tables 1 and 2 in the same manner as in Synthesis Example 1. Table 3 shows the results of evaluation by the same method as in Synthesis Example 1, the mixing indices α4 to ε4, and the storage stability index θ4.
As shown in Table 3, the resin composition of Synthesis Example 4 had an epoxy equivalent (WPE) of 245 g / eq, and showed an appropriate value. Further, the starting viscosity = 14.8 Pa · s <1000 Pa · s and the storage viscosity = 21.0 Pa · s <1000 Pa · s, both of which were fluid liquids. The storage stability index θ4 = 1.42 ≦ 4, and it was found that the resin composition had storage stability.

[Synthesis Example 5]
Resin compositions were produced according to Tables 1 and 2 in the same manner as in Synthesis Example 1. Table 3 shows the results evaluated by the same method as in Synthesis Example 1, the mixing indexes α5 to ε5, and the storage stability index θ5.
As shown in Table 3, the resin composition of Synthesis Example 5 had an epoxy equivalent (WPE) of 228 g / eq, and showed an appropriate value. Further, the starting viscosity = 38.2 Pa · s <1000 Pa · s and the storage viscosity = 61.1 Pa · s <1000 Pa · s, both were fluid liquids. Further, the storage stability index θ5 = 1.60 ≦ 4, and it was found that the resin composition had storage stability.

[Synthesis Example 6]
Resin compositions were produced according to Tables 1 and 2 in the same manner as in Synthesis Example 1 except that the time for the refluxing process was 7 hours. Table 3 shows the results evaluated by the same method as in Synthesis Example 1, the mixing indices α6 to ε6, and the storage stability index θ6.
As shown in Table 3, the resin composition of Synthesis Example 6 had an epoxy equivalent (WPE) of 214 g / eq, and showed an appropriate value. In addition, the starting viscosity = 4.9 Pa · s <1000 Pa · s and the storage viscosity = 9.4 Pa · s <1000 Pa · s, both of which were fluid fluids. The storage stability index θ6 = 1.91 ≦ 4, and it was found that the resin composition had storage stability.

[Synthesis Example 7]
Resin compositions were produced according to Tables 1 and 2 in the same manner as in Synthesis Example 1. Table 3 shows the results of evaluation by the same method as in Synthesis Example 1, the mixing indices α7 to ε7, and the storage stability index θ7.
As shown in Table 3, the resin composition of Synthesis Example 7 was epoxy equivalent (WPE) = 214 g / eq, and showed an appropriate value. In addition, the starting viscosity = 13.1 Pa · s <1000 Pa · s and the storage viscosity = 15.9 Pa · s <1000 Pa · s, both were fluid liquids. In addition, the storage stability index θ7 = 1.21 ≦ 4, and it was found that the resin composition had storage stability.

[Synthesis Example 8]
Resin compositions were produced according to Tables 1 and 2 in the same manner as in Synthesis Example 1. Table 3 shows the results of evaluation by the same method as in Synthesis Example 1, the mixing indices α8 to ε8, and the storage stability index θ8.
As shown in Table 3, the resin composition of Synthesis Example 8 had an epoxy equivalent (WPE) of 238 g / eq, and showed an appropriate value. Further, the starting viscosity = 18.9 Pa · s <1000 Pa · s and the storage viscosity = 28.7 Pa · s <1000 Pa · s, both were fluid liquids. The storage stability index θ8 = 1.52 ≦ 4, and it was found that the resin composition had storage stability.

[Synthesis Example 9]
Resin compositions were produced according to Tables 1 and 2 in the same manner as in Synthesis Example 1. Table 3 shows the results of evaluation by the same method as in Synthesis Example 1, the mixing indices α9 to ε9, and the storage stability index θ9.
As shown in Table 3, the resin composition of Synthesis Example 9 was epoxy equivalent (WPE) = 213 g / eq, and showed an appropriate value. In addition, the starting viscosity = 11.2 Pa · s <1000 Pa · s and the storage viscosity = 16.1 Pa · s <1000 Pa · s, both were fluid liquids. The storage stability index θ9 = 1.44 ≦ 4, and it was found that the resin composition had storage stability.

[Synthesis Example 10]
Resin compositions were produced according to Tables 1 and 2 in the same manner as in Synthesis Example 1. Table 3 shows the results of evaluation by the same method as in Synthesis Example 1, the mixing indices α10 to ε10, and the storage stability index θ10.
As shown in Table 3, the resin composition of Synthesis Example 10 had an epoxy equivalent (WPE) of 253 g / eq, and showed an appropriate value. Further, the starting viscosity = 26.8 Pa · s <1000 Pa · s and the storage viscosity = 39.1 Pa · s <1000 Pa · s, both were fluid liquids. Further, the storage stability index θ10 = 1.46 ≦ 4, and it was found that the resin composition had storage stability.

[Comparative Synthesis Example 1]
Resin compositions were produced according to Tables 1 and 2 in the same manner as in Synthesis Example 1. Table 3 shows the results of evaluation by the same method as in Synthesis Example 1, the mixing indices α11 to ε11, and the storage stability index θ11.
As shown in Table 3, the resin composition of Comparative Synthesis Example 1 was epoxy equivalent (WPE) = 295 g / eq, and showed an appropriate value. Further, the starting viscosity = 33.4 Pa · s <1000 Pa · s and the storage viscosity = 48.2 Pa · s <1000 Pa · s, both were fluid liquids. The storage stability index θ11 = 1.44 ≦ 4, and it was found that the resin composition had storage stability.

[Comparative Synthesis Example 2]
Resin compositions were produced according to Tables 1 and 2 in the same manner as in Synthesis Example 1. Table 3 shows the results of evaluation by the same method as in Synthesis Example 1, the mixing indices α12 to ε12, and the storage stability index θ12.
As shown in Table 3, the resin composition of Comparative Synthesis Example 2 was epoxy equivalent (WPE) = 295 g / eq, and showed an appropriate value. Further, the starting viscosity = 29.0 Pa · s <1000 Pa · s, which was a fluid liquid. However, storage viscosity> 1000 Pa · s, no fluidity, storage stability index θ12> 35, the resin composition of Comparative Synthesis Example 2 has poor storage stability, and a sample for LED evaluation can be produced. There wasn't.

[Comparative Synthesis Example 3]
According to Table 1, epoxy resin A2 and epoxy resin A3 were added to the reaction vessel, immersed in an oil bath at 85 ° C., stirred and dissolved, and further P-MS and DBTDL were added and mixed.
Further, while purging with nitrogen, the temperature of the oil bath was raised to 105 ° C., and the dealcoholization reaction was performed for 8 hours.
Next, after cooling to 60 ° C., the pressure was reduced to 12000 Pa to remove the dissolved alcohol to obtain a resin composition. Table 3 shows the results of evaluation by the same method as in Example 1 and the storage stability index θ11.
Epoxy equivalent (WPE) of the resin composition of Comparative Synthesis Example 3 was 282 g / eq, which was an appropriate value. Further, the starting viscosity was 1.89 Pa · s <1000 Pa · s, and the storage viscosity was 2.03 Pa · s <1000 Pa · s, both of which were fluid liquids. In addition, the storage stability index θ13 = 1.07 ≦ 4, indicating that the resin composition has storage stability.

[Example 1]
A cured product was produced using the resin composition of Synthesis Example 1 stored at 25 ° C. for 2 weeks, and a light resistance test was performed. The results are shown in Table 3.
(1) The above-mentioned resin composition, curing agent and curing accelerator were mixed and stirred in a 25 ° C. atmosphere according to the composition ratios in Table 2, and degassed under vacuum to obtain a cured product solution.
(2) A 3 mm thick, U-shaped silicon rubber was sandwiched between two stainless steel plates coated with a release agent to prepare a molding jig.
(3) The above-mentioned solution for cured product was poured into this molding jig and subjected to curing treatment at 120 ° C. for 1 hour and further at 150 ° C. for 1 hour to produce a cured product.
(4) After the oven internal temperature fell to 30 ° C. or lower, the cured product was taken out, and a sample for light resistance test was prepared according to the method described above.
(5) Table 3 shows the results of the light resistance test performed by the above-described method using the sample. YI = 10.1 ≦ 13, which is an index of the light resistance test of the cured product, and the light resistance was judged to be acceptable.
Next, using the resin composition of Synthesis Example 1, a bullet-type LED having the structure shown in FIG. 1 was manufactured according to the following procedure, and reliability tests (1) to (3) were performed. The results are shown in Table 3.
(6) The cured product solution of (1) was injected as a sealing resin into the cup portion of a bullet-shaped mold frame having a diameter of 5 mm.
(7) An LED chip having an emission wavelength of 400 nm was die-bonded with a silver paste, and a lead frame connected with a bonding wire (gold wire) was immersed therein.
(8) After defoaming in vacuum, curing treatment was performed at 90 ° C. for 1 hour and further at 110 ° C. for 5 hours.
(9) Furthermore, as the outer layer resin, 46.6% by mass of a curing agent and 0.2% by mass of a curing accelerator are added to 53.2% by mass of Bis-A1 epoxy resin, and the mixture is stirred and mixed under vacuum. What was deaerated in was poured into a mold frame and cured at 130 ° C. for 1 hour and further at 150 ° C. for 6 hours to obtain a bullet-type LED.

As a result of performing the above-mentioned “reliability test (1) (L test)”, the minimum value of all LEDs was a total luminous flux maintenance factor (%) = 94% ≧ 90%, and was judged to be acceptable.
Next, as a result of performing the above-mentioned “reliability test (2) (TS test)”, even after 100 cycles of thermal shock, all the LEDs were turned on, and it was judged as passing.
Furthermore, as a result of performing the above-mentioned “reliability test (3) (TC test)”, even after 100 temperature cycles were applied, all the LEDs were lit, and it was judged as passing.
From the above results, the LED of Example 1 passed all of the light resistance test and reliability tests (1) to (3), and was judged to be acceptable as a comprehensive judgment.

[Example 2]
Instead of the resin composition of Synthesis Example 1, the resin composition of Synthesis Example 2 was used to produce a cured product and an LED in the same manner as in Example 1, and the light resistance test and reliability test (1 ) To (3) were performed. The results are shown in Table 3.
YI = 8.1 ≦ 13, which is an index of light resistance test, and light resistance was judged to be acceptable.
As a result of performing the above-mentioned “reliability test (1) (L test)”, the minimum value of all LEDs was determined to be a total luminous flux maintenance factor (%) = 96% ≧ 90%.
Next, as a result of performing the above-mentioned “reliability test (2) (TS test)”, even after 100 cycles of thermal shock, all the LEDs were turned on, and it was judged as passing.
Furthermore, as a result of performing the above-mentioned “reliability test (3) (TC test)”, even after 100 temperature cycles were applied, all the LEDs were lit, and it was judged as passing.
From the above results, the LED of Example 2 passed all of the light resistance test and the reliability tests (1) to (3), and was judged to be acceptable as a comprehensive judgment.

[Example 3]
Using the resin composition of Synthesis Example 3 instead of the resin composition of Synthesis Example 1, a cured product and an LED are produced in the same manner as in Example 1, and a light resistance test and a reliability test (1 ) To (3) were performed. The results are shown in Table 3.
YI = 8.9 ≦ 13, which is an index of light resistance test, and light resistance was judged to be acceptable.
As a result of performing the above "reliability test (1) (L test)", the minimum value of all LEDs was determined to be a total luminous flux maintenance factor (%) = 95% ≧ 90%, which was acceptable.
Next, as a result of performing the above-mentioned “reliability test (2) (TS test)”, even after 100 cycles of thermal shock, all the LEDs were turned on, and it was judged as passing.
Furthermore, as a result of performing the above-mentioned “reliability test (3) (TC test)”, even after 100 temperature cycles were applied, all the LEDs were lit, and it was judged as passing.
From the above results, the LED of Example 3 passed all of the light resistance test and reliability tests (1) to (3), and was determined to be acceptable as a comprehensive judgment.

[Example 4]
Using the resin composition of Synthesis Example 4 instead of the resin composition of Synthesis Example 1, a cured product and an LED are produced in the same manner as in Example 1, and a light resistance test and a reliability test (1 ) To (3) were performed. The results are shown in Table 3.
YI = 8.3 ≦ 13, which is an index of light resistance test, and light resistance was judged to be acceptable.
As a result of performing the above-mentioned “reliability test (1) (L test)”, the minimum value of all LEDs was a total luminous flux maintenance factor (%) = 92% ≧ 90%, and was judged to be acceptable.
Next, as a result of performing the above-mentioned “reliability test (2) (TS test)”, even after 100 cycles of thermal shock, all the LEDs were turned on, and it was judged as passing.
Furthermore, as a result of performing the above-mentioned “reliability test (3) (TC test)”, even after 100 temperature cycles were applied, all the LEDs were lit, and it was judged as passing.
From the above results, the LED of Example 4 passed all of the light resistance test and the reliability tests (1) to (3), and was judged to be acceptable as a comprehensive judgment.

[Example 5]
Using the resin composition of Synthesis Example 5 instead of the resin composition of Synthesis Example 1, a cured product and an LED were produced in the same manner as in Example 1, and a light resistance test and a reliability test (1 ) To (3) were performed. The results are shown in Table 3.
YI = 7.5 ≦ 13, which is an index of the light resistance test, and the light resistance was judged to be acceptable.
As a result of performing the above-mentioned “reliability test (1) (L test)”, the minimum value of all LEDs was determined to be a total luminous flux maintenance factor (%) = 96% ≧ 90%.
Next, as a result of performing the above-mentioned “reliability test (2) (TS test)”, even after 100 cycles of thermal shock, all the LEDs were turned on, and it was judged as passing.
Furthermore, as a result of performing the above-mentioned “reliability test (3) (TC test)”, even after 100 temperature cycles were applied, all the LEDs were lit, and it was judged as passing.
From the above results, the LED of Example 5 passed all of the light resistance test and the reliability tests (1) to (3), and was judged to be acceptable as a comprehensive judgment.

[Example 6]
Example of Example except that the resin composition of Synthesis Example 6 was used instead of the resin composition of Synthesis Example 1 and the curing treatment temperature of the cured product and the LED sealing resin was changed to 110 ° C. for 4 hours. A cured product and an LED were produced in the same manner as in No. 1, and a light resistance test and reliability tests (1) to (3) were performed. The results are shown in Table 3.
YI = 8.8 ≦ 13, which is an index of light resistance test, and light resistance was judged to be acceptable.
As a result of performing the above-mentioned “reliability test (1) (L test)”, the minimum value of all LEDs was determined to be a total luminous flux maintenance factor (%) = 96% ≧ 90%.
Next, as a result of performing the above-mentioned “reliability test (2) (TS test)”, even after 100 cycles of thermal shock, all the LEDs were turned on, and it was judged as passing.
Furthermore, as a result of performing the above-mentioned “reliability test (3) (TC test)”, even after 100 temperature cycles were applied, all the LEDs were lit, and it was judged as passing.
From the above results, the LED of Example 6 passed all of the light resistance test and reliability tests (1) to (3), and was judged to be acceptable as a comprehensive judgment.

[Example 7]
Using the resin composition of Synthesis Example 7 instead of the resin composition of Synthesis Example 1, a cured product and an LED were produced in the same manner as in Example 1, and the light resistance test and reliability test (1 ) To (3) were performed. The results are shown in Table 3.
YI = 12.4 ≦ 13, which is an index of the light resistance test, and the light resistance was judged to be acceptable.
As a result of performing the above-mentioned “reliability test (1) (L test)”, the minimum value of all LEDs was a total luminous flux maintenance factor (%) = 97% ≧ 90%, and was judged to be acceptable.
Next, as a result of performing the above-mentioned “reliability test (2) (TS test)”, even after 100 cycles of thermal shock, all the LEDs were turned on, and it was judged as passing.
Furthermore, as a result of performing the above-mentioned “reliability test (3) (TC test)”, even after 100 temperature cycles were applied, all the LEDs were lit, and it was judged as passing.
From the above results, the LED of Example 7 passed all of the light resistance test and reliability tests (1) to (3), and was judged to be acceptable as a comprehensive judgment.

[Example 8]
Instead of the resin composition of Synthesis Example 1, the resin composition of Synthesis Example 8 was used to produce a cured product and an LED in the same manner as in Example 1, and the light resistance test and reliability test (1 ) To (3) were performed. The results are shown in Table 3.
YI = 7.2 ≦ 13, which is an index of the light resistance test, and the light resistance was judged to be acceptable.
As a result of performing the above-mentioned “reliability test (1) (L test)”, the minimum value of all LEDs was a total luminous flux maintenance factor (%) = 92% ≧ 90%, and was judged to be acceptable.
Next, as a result of performing the above-mentioned “reliability test (2) (TS test)”, even after 100 cycles of thermal shock, all the LEDs were turned on, and it was judged as passing.
Furthermore, as a result of performing the above-mentioned “reliability test (3) (TC test)”, even after 100 temperature cycles were applied, all the LEDs were lit, and it was judged as passing.
From the above results, the LED of Example 8 passed all of the light resistance test and reliability tests (1) to (3), and was judged to be acceptable as a comprehensive judgment.

[Example 9]
Using the resin composition of Synthesis Example 9 instead of the resin composition of Synthesis Example 1, a cured product and an LED were produced in the same manner as in Example 1, and a light resistance test and a reliability test (1 ) To (3) were performed. The results are shown in Table 3.
YI = 7.8 ≦ 13 which is an index of the light resistance test, and the light resistance was judged to be acceptable.
As a result of performing the above-mentioned “reliability test (1) (L test)”, the minimum value of all LEDs was a total luminous flux maintenance rate (%) = 93% ≧ 90%, and was judged to be acceptable.
Next, as a result of performing the above-mentioned “reliability test (2) (TS test)”, even after 100 cycles of thermal shock, all the LEDs were turned on, and it was judged as passing.
Furthermore, as a result of performing the above-mentioned “reliability test (3) (TC test)”, even after 100 temperature cycles were applied, all the LEDs were lit, and it was judged as passing.
From the above results, the LED of Example 9 passed all of the light resistance test and reliability tests (1) to (3), and was judged to be acceptable as a comprehensive judgment.

[Example 10]
Instead of the resin composition of Synthesis Example 1, using the resin composition of Synthesis Example 10, a cured product and an LED were produced in the same manner as in Example 1, and a light resistance test and a reliability test (1 ) To (3) were performed. The results are shown in Table 3.
YI = 9.2 ≦ 13 which is an index of the light resistance test, and the light resistance was judged to be acceptable.
As a result of performing the above-mentioned “reliability test (1) (L test)”, the minimum value of all LEDs was a total luminous flux maintenance factor (%) = 92% ≧ 90%, and was judged to be acceptable.
Next, as a result of performing the above-mentioned “reliability test (2) (TS test)”, even after 100 cycles of thermal shock, all the LEDs were turned on, and it was judged as passing.
Furthermore, as a result of performing the above-mentioned “reliability test (3) (TC test)”, even after 100 temperature cycles were applied, all the LEDs were lit, and it was judged as passing.
From the above results, the LED of Example 10 passed all of the light resistance test and reliability tests (1) to (3), and was judged to be acceptable as a comprehensive judgment.

[Example 11]
Using the resin composition of Synthesis Example 2, an SMD type LED having a size of 2.5 mm × 2.5 mm having the structure shown in FIG. 2 was manufactured according to the following procedure, and it was confirmed that the LED was lit.
(1) On the glass epoxy board | substrate with which the metal pattern was formed, the silver paste was apply | coated and the LED chip was die-bonded.
(2) The substrate was placed in an electric furnace and cured.
(3) A bonding wire (gold wire) was bonded to the die-bonded LED chip to form a circuit.
(4) A substrate was placed on the mold, and the resin composition of Synthesis Example 2 was injected, followed by curing at 90 ° C. for 1 hour and further at 110 ° C. for 5 hours.
(5) The LEDs on the substrate were cut one by one to produce SMD type LEDs.
From the above results, it was determined that the LEDs of Examples 1 to 11 were excellent in light resistance and reliability and passed as a comprehensive judgment.

[Comparative Example 1]
Using the resin composition of Comparative Synthesis Example 1 instead of the resin composition of Synthesis Example 1, a cured product and an LED are produced in the same manner as in Example 1, and a light resistance test and a reliability test ( 1) to (3) were performed. The results are shown in Table 3.
YI = 8.4 ≦ 13, which is an index of the light resistance test, and the light resistance was judged to be acceptable.
As a result of performing the above "reliability test (1) (L test)", 2/10 LEDs were not lit, the total luminous flux maintenance factor (%) was not measurable, and it was judged as rejected.
Next, as a result of performing the above "reliability test (2) (TS test)", after 100 cycles of thermal shock, only 6/10 of the LEDs were turned on, and it was judged as rejected.
Furthermore, as a result of performing the above-mentioned “reliability test (3) (TC test)”, after applying a temperature cycle of 100 cycles, only 6/10 LEDs were turned on, and it was judged as unacceptable.
From the above results, although the LED of Comparative Example 1 had good light resistance, it was judged that all of the reliability tests (1) to (3) were rejected and rejected as a comprehensive judgment.

[Comparative Example 2]
Using the resin composition of Comparative Synthesis Example 2 instead of the resin composition of Synthesis Example 1, a cured product and an LED were produced in the same manner as in Example 1, and a light resistance test and a reliability test ( Attempts were made to implement 1) to (3), but the storage stability of the resin composition was poor, and it was impossible to produce cured products and LEDs. Therefore, it judged that it was unacceptable as comprehensive judgment.

[Comparative Example 3]
Instead of the resin composition of Synthesis Example 1, Bis-A1 epoxy resin was used to produce a cured product and an LED in the same manner as in Example 1, and a light resistance test and a reliability test (1) to (1) to (3) was performed. The results are shown in Table 3.
YI = 17.2> 13, which is an index of the light resistance test, and the light resistance was judged to be unacceptable.
As a result of performing the above-mentioned “reliability test (1) (L test)”, the minimum value of all LEDs was a total luminous flux maintenance factor (%) = 97% ≧ 90%, and was judged to be acceptable.
Next, as a result of performing the above-mentioned “reliability test (2) (TS test)”, even after 100 cycles of thermal shock, all the LEDs were turned on, and it was judged as passing.
Furthermore, as a result of performing the above-mentioned “reliability test (3) (TC test)”, even after 100 temperature cycles were applied, all the LEDs were lit, and it was judged as passing.
From the above results, although the LED of Comparative Example 3 was excellent in reliability, it was judged that the light resistance was poor and it was rejected as a comprehensive judgment.

[Comparative Example 4]
Instead of the resin composition of Synthesis Example 1, the above-mentioned silicone resin in which the liquid A and the liquid B were mixed and stirred at a mass ratio of 1: 1 was used. A cured product and an LED were produced in the same manner as in Example 1 except that the curing treatment temperature of the cured product and the LED sealing resin was changed to 70 ° C. for 1 hour and further 150 ° C. for 5 hours. And reliability tests (1) to (3) were conducted. The results are shown in Table 3.
YI = 2.0 ≦ 13, which is an index of the light resistance test, and the light resistance was judged to be acceptable.
As a result of performing the above-mentioned “reliability test (1) (L test)”, 3/10 LEDs were not turned on, and the total luminous flux maintenance rate (%) was not measurable, and was judged to be unacceptable.
Next, as a result of performing the above-mentioned “reliability test (2) (TS test)”, after 100 cycles of thermal shock, only 4/10 of the LEDs were turned on, and it was judged as rejected.
Furthermore, as a result of performing the above-mentioned “reliability test (3) (TC test)”, after applying a temperature cycle of 100 cycles, only 6/10 LEDs were turned on, and it was judged as unacceptable.
From the above results, although the LED of Comparative Example 1 had good light resistance, it was judged that all of the reliability tests (1) to (3) were rejected and rejected as a comprehensive judgment.

[Comparative Example 5]
Using the resin composition of Comparative Synthesis Example 3 instead of the resin composition of Synthesis Example 1, a cured product and an LED were produced in the same manner as in Example 1, and a light resistance test and a reliability test ( 1) to (3) were performed. The results are shown in Table 3.
Although the hardened | cured material for a light resistance test was produced, since the crack produced and it was impossible to measure, light resistance was judged to be disqualified.
As a result of the above "reliability test (1) (L test)", 4/10 LEDs were not turned on, the total luminous flux maintenance rate (%) was not measurable, and it was judged as rejected.
Next, as a result of performing the “reliability test (2) (TS test)”, only 5 out of 10 LEDs were turned on after a thermal shock of 100 cycles, and it was judged as rejected.
Furthermore, as a result of performing the above-mentioned “reliability test (3) (TC test)”, after applying the temperature cycle of 100 cycles, only 7/10 of the LEDs were turned on, and it was judged as unacceptable.
From the above results, it was determined that the LED of Comparative Example 1 failed in light resistance and reliability tests (1) to (3) and failed as a comprehensive judgment.

The LEDs of Examples 1 to 11 had excellent results for all of light resistance, L test, TS test, and TC test. On the other hand, in Comparative Examples 1 to 5, at least one of storage stability, light resistance, L test, TS test, and TC test was defective.
As mentioned above, according to the present Example, it was shown that LED of this embodiment is excellent in light resistance and reliability.

10, 20 Light emitting diode (LED)
10a, 20a LED chip 10A, 20A Anode electrode 10C, 20C Cathode electrode 12, 22 Sealing material 14, 24 Bonding wire 16 Outer layer resin 18 Lead frame 26 Package substrate 28 Reflector

  The light emitting device and the semiconductor device of the present embodiment include, for example, a backlight of a mobile phone, a head of an optical disk device, an LCD backlight, a lighting fixture, an automobile lamp and a display part, a traffic signal lamp, an LED display board, and an outdoor signboard. It has industrial applicability as a general display part of an outdoor display, a medical LED, an amusement device LED, a copy / facsimile or a home appliance.

Claims (8)

A light-emitting device comprising a light-emitting light source and a sealing material that seals the light-emitting light source,
The sealing material is
(A) an epoxy resin;
An alkoxysilane compound represented by the following general formula (1):
A resin composition obtained by cohydrolyzing and condensing

(In the formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group. The plurality of R ² may be the same or different, and may be a hydrogen atom or a carbon number of 1 to 8. Represents an alkyl group of
The alkoxysilane compound is
(B) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one cyclic ether group;
(C) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one aryl group;
And a resin composition in which the mixing index α of (B) and (C) represented by the following formula (2) is 0.001 to 19;
Mixing index α = (αc) / (αb) (2)
(Wherein, αb: content (mol%) of the component (B), αc: content (mol%) of the component (C)).   2. The light emitting device according to claim 1, wherein the (A) epoxy resin is a liquid having an epoxy equivalent (WPE) of 100 to 600 g / eq and a viscosity at 25 ° C. of 1000 Pa · s or less.   The light emitting device according to claim 1, wherein the (A) epoxy resin is a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound. As the alkoxysilane compound,
(D) The light emitting device according to any one of claims 1 to 3, further comprising at least one alkoxysilane compound in which n = 0 in the general formula (1). The light-emitting device according to claim 1, wherein a mixing index β of the alkoxysilane compound represented by the following formula (3) is 0.01 to 1.4;
Mixing index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
(In formula (3),
β ⁿ² : content (mol%) of the alkoxysilane compound in which n = 2 in the general formula (1),
β ⁿ⁰ : the content (mol%) of the alkoxysilane compound in which n = 0 in the general formula (1),
β ⁿ¹ : content (mol%) of the alkoxysilane compound in which n = 1 in the general formula (1),
Here, 0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1). The light emission according to any one of claims 1 to 5, wherein a mixture index γ of the (A) epoxy resin and the alkoxysilane compound represented by the following formula (4) is 0.02 to 15. apparatus;
Mixing index γ = (γa) / (γs) (4)
(In formula (4),
γa: mass of epoxy resin (g),
γs: mass (g) of alkoxysilane compound in which n = 0 to 2 in the general formula (1)   The light emitting device according to claim 1, wherein the light emitting light source is a light emitting diode.   A semiconductor device provided with the light-emitting device as described in any one of Claims 1-7.