JP2003086848A - Curable composition for sealing light emitting diode, light emitting diode sealing material, its manufacturing method, and light emitting diode using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light emitting diode sealing compound that is reduced in viscosity and in overflow from a package. SOLUTION: This light emitting diode sealing compound is composed of a curable composition containing (A) an organic compound containing at least two carbon-carbon bonds having reactivity to SiH groups in one molecule, (B) a compound containing at least two SiH groups in one molecule, (C) a hydrosilylated catalyst, and (D) a cure retarder as an essential ingredient. The composition shows the minimum viscosity at a temperature (T1 ) which falls within the temperature range of 50-80 deg.C when the dynamic viscosity (η*) of melt/solidification viscoelasticity is measured at a frequency of 1 Hz under a temperature rising condition of 5 deg.C/min. In addition, the composition shows a dynamic viscosity which is 1,000 times as high as the viscosity at the temperature (T1 ) at a temperature (T2 ) which falls within the temperature range of 85-120 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for encapsulating a light emitting diode, and more specifically, a curable composition for encapsulating a light emitting diode in which resin overflow from a package is reduced, and a material for encapsulating a light emitting diode. The present invention relates to a method and a light emitting diode using the method.

[0002]

2. Description of the Related Art Conventionally, a transparent epoxy resin using an acid anhydride type curing agent has been widely used as a covering material (sealing material or molding material) for a light emitting element of a light emitting diode.
However, since the viscosity of the resin is high, the detail filling property is low,
Moreover, since the reactivity is low, there is a drawback that the resin overflows from the package. The package of the present invention is a concave form frame for arranging the light emitting element of the light emitting diode, and can be made by using various materials. In particular,
Polycarbonate resin, polyphenylene sulfide resin, epoxy resin, acrylic resin, silicone resin, AB
Examples include S resin, polyterephthalamide resin, and ceramics.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a curable composition for encapsulating a light emitting diode having a low viscosity and a reduced resin overflow, a material for encapsulating a light emitting diode, and a method for producing the same. A light emitting diode and a method for manufacturing the same are provided.

[0004]

[Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have conducted intensive studies and as a result, (A) at least two carbon-carbon double bonds reactive with a SiH group in one molecule. A curable composition containing an organic compound contained therein, (B) a compound containing at least two SiH groups in one molecule, (C) a hydrosilylation catalyst, and (D) a curing retarder as essential components. : 1Hz, temperature rising condition: 5 ° C
In the dynamic viscosity (η ^* ) measurement of melted / solidified viscoelasticity measured at 1 / min, the temperature (T ₁ ) giving the lowest viscosity is in the range of 50 ° C. to 80 ° C., and the viscosity at T ₁ is 1000 times the viscosity. The temperature (T ₂ ) that gives the dynamic viscosity is 85 ° C or higher.
The inventors have found that the above problem can be solved by using a curable composition for encapsulating a light emitting diode, which is in the range of 120 ° C., and has reached the present invention.

That is, the present invention relates to (A) an organic compound containing at least two carbon-carbon double bonds reactive with a SiH group in one molecule, and (B) at least two SiH in one molecule. A curable composition containing a group-containing compound, (C) hydrosilylation catalyst, and (D) curing retarder as essential components, frequency: 1 Hz, temperature rising condition: 5 ° C.
In the dynamic viscosity (η ^* ) measurement of the dynamic viscoelasticity measured at 1 / min, the temperature (T ₁ ) giving the minimum viscosity is 50 ° C to 8 ° C.
A curable composition for encapsulating a light emitting diode, which is in the range of 0 ° C. and has a temperature (T ₂ ) that gives a dynamic viscosity 1000 times the viscosity in T ₁ in the range of 85 ° C. to 120 ° C. (Claim 1), the component (A) is triallyl isocyanurate, and the component (B) is 1, 3, 5, 7
-The curable composition for encapsulating a light-emitting diode according to claim 1, which is a reaction product of tetramethyltetracyclosiloxane and triallyl isocyanurate, wherein the component (C) is platinum- A curable composition for encapsulating a light-emitting diode (claim 3) according to claim 1, which is a vinyl siloxane complex.
The component (D) is 1-ethynyl-1-cyclohexanol, which is the curable composition for encapsulating a light-emitting diode (claim 4) according to any one of claims 1 to 3, and claims 1 to 4 To the curable composition for encapsulating a light-emitting diode according to any one of items 1 to 4, and a carbon-carbon double bond reactive with the SiH group in the composition and a part or all of the SiH group are reacted. A light-emitting diode encapsulating material (Claim 5), which is cured by means of:
4 to 4 are mixed in advance with the curable composition for encapsulating a light-emitting diode according to any one of 4 to 4, and part or all of the carbon-carbon double bond and SiH group reactive with the SiH group in the composition. A method for producing a material for encapsulating a light emitting diode (Claim 6), comprising curing by reacting,
A light emitting diode (claim 7) using the light emitting diode sealing material according to claim 5.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

First, the component (A) in the present invention will be described.

Component (A) is not particularly limited as long as it is an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule. The organic compound does not include siloxane units (Si-O-Si) such as polysiloxane-organic block copolymers and polysiloxane-organic graft copolymers, but only C, H, N, O, S, and halogens as constituent elements. It is preferable that it contains. In the case of containing a siloxane unit, there are problems of gas permeability and repellency.

The bonding position of the carbon-carbon double bond having reactivity with the SiH group is not particularly limited, and it may exist anywhere in the molecule.

The organic compound as the component (A) can be classified into an organic polymer type compound and an organic monomer type compound.

Examples of the organic polymer compound include polyether type, polyester type, polyarylate type, polycarbonate type, saturated hydrocarbon type, unsaturated hydrocarbon type,
Polyacrylic acid ester-based, polyamide-based, phenol-formaldehyde-based (phenol resin-based), and polyimide-based compounds can be used.

Examples of organic monomer compounds include
Examples thereof include phenolic, bisphenolic, aromatic hydrocarbon compounds such as benzene and naphthalene: straight chain compounds, aliphatic hydrocarbon compounds such as alicyclic compounds: heterocyclic compounds, and mixtures thereof.

The carbon-carbon double bond which is reactive with the SiH group of the component (A) is not particularly limited, but is represented by the following general formula (I).

[0014]

[Chemical 1] The group represented by (in the formula, R ¹ represents a hydrogen atom or a methyl group) is preferable from the viewpoint of reactivity. Also, from the ease of obtaining the raw materials,

[0015]

[Chemical 2] The groups shown are particularly preferred.

The carbon-carbon double bond reactive with the SiH group of the component (A) is represented by the following general formula (II)

[0017]

[Chemical 3] The alicyclic group represented by the formula (R ¹ represents a hydrogen atom or a methyl group) is preferable from the viewpoint of high heat resistance of the cured product. Also, from the ease of obtaining the raw materials,

[0018]

[Chemical 4] The alicyclic groups shown are particularly preferred.

The carbon-carbon double bond reactive with the SiH group may be directly bonded to the skeleton of the component (A) or may be covalently bonded via a divalent or higher valent substituent. The divalent or higher valent substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms, but C, H as constituent elements,
Those containing only N, O, S and halogen are preferable. Examples of these substituents include:

[0020]

[Chemical 5]

[0021]

[Chemical 6] Is mentioned. Further, two or more of these divalent or higher valent substituents may be connected by a covalent bond to form one divalent or higher valent substituent.

Examples of the group covalently bonded to the skeleton as described above include vinyl group, allyl group, methallyl group, acryl group, methacryl group, 2-hydroxy-3- (allyloxy) propyl group, 2-allylphenyl. Group, 3-allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4
-(Allyloxy) phenyl group, 2- (allyloxy)
Ethyl group, 2,2-bis (allyloxymethyl) butyl group, 3-allyloxy-2,2-bis (allyloxymethyl) propyl group,

[0023]

[Chemical 7] Is mentioned.

Specific examples of the component (A) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2,- Tetraaryloxyethane, diarylidene pentaerythritol, triallyl cyanurate, triallyl isocyanurate, 1,2,4
-Trivinylcyclohexane, divinylbenzenes (purity 50-100%, preferably 80-100)
%), Divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene,
And their oligomers, 1,2-polybutadiene (1, 2 ratio of 10 to 100%, preferably 1, 2
Ratio of 50 to 100%), allyl ether of novolac phenol, allylated polyphenylene oxide,

[0025]

[Chemical 8]

[0026]

[Chemical 9] In addition to the above, a conventionally known epoxy resin in which the glycidyl group is replaced with an allyl group may be used.

As the component (A), it is also possible to use a low molecular weight compound which is difficult to be expressed by dividing the skeleton portion and the alkenyl group as described above. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene, cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene, norbornadiene and other fatty acids. Examples thereof include a group cyclic polyene compound system and a substituted aliphatic cyclic olefin compound system such as vinylcyclopentene and vinylcyclohexene.

As the above-mentioned component (A), from the viewpoint of further improving the heat resistance, a carbon-carbon double bond reactive with a SiH group is added in an amount of 0.001 per 1 g of the component (A).
It may be 1 mol or more, but further 1
Those containing 0.005 mol or more per g are preferable, and those containing 0.008 mol or more are particularly preferable.

The number of carbon-carbon double bonds reactive with the SiH group of the component (A) may be at least two per molecule on average, but if the mechanical strength is desired to be improved, 2 is preferable. It is preferable that the number exceeds 3, and it is more preferable that the number is 3 or more. When the number of carbon-carbon double bonds having reactivity with the SiH group of the component (A) is 1 or less per molecule, even if it reacts with the component (B), only a graft structure is formed and a crosslinked structure is formed. I won't.

The component (A) is preferably one which has fluidity at a temperature of 100 ° C. or less in order to obtain uniform mixing with other components and good workability, and may be linear or branched. , The molecular weight is not particularly limited, but 50
Any of 100 to 100,000 can be preferably used. If the molecular weight is 100,000 or more, the raw material generally has a high viscosity and the workability is poor, and the effect of crosslinking due to the reaction between the alkenyl group and the SiH group is difficult to be exhibited.

Further, as the component (A), a compound having a small content of a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group is preferable from the viewpoint of suppressing coloring, particularly yellowing, and the phenolic hydroxyl group and / or Those that do not include a compound having a derivative of a phenolic hydroxyl group are preferable. The phenolic hydroxyl group in the present invention is a benzene ring, a naphthalene ring, a hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by the anthracene ring, and the phenolic hydroxyl group derivative is a hydrogen atom of the above-mentioned phenolic hydroxyl group. A group substituted with an alkyl group such as a methyl group and an ethyl group, an alkenyl group such as a vinyl group and an allyl group, and an acyl group such as an acetoxy group.

From the viewpoint of good optical properties such as low birefringence and low photoelastic coefficient, and good weather resistance, the weight ratio of the components in the component (A) of the aromatic ring is high. It is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight or less. Most preferred are those containing no aromatic hydrocarbon rings.

From the coloring properties and optical properties of the resulting cured product, the components (A) are vinylcyclohexene, dicyclopentadiene, triallyl isocyanurate, 2,2.
-Diallyl ether of bis (4-hydroxycyclohexyl) propane, 1,2,4-trivinylcyclohexane is preferable, triallyl isocyanurate, 2,2-
Particularly preferred is diallyl ether of bis (4-hydroxycyclohexyl) propane, 1,2,4-trivinylcyclohexane.

Next, the compound having a SiH group as the component (B) will be described.

The compound having a SiH group that can be used in the present invention is not particularly limited. For example, International Publication WO96.
/ 15194, compounds having at least two SiH groups in one molecule, and the like can be used.

Of these, chain and / or cyclic polyorganosiloxanes having at least two SiH groups in one molecule are preferable from the standpoint of availability, and have good compatibility with the component (A). From the viewpoint, further, the following general formula (III)

[0037]

[Chemical 10] (In the formula, R ² represents an organic group having 1 to 6 carbon atoms, and n is 3 to
Represents the number 10. A cyclic polyorganosiloxane having at least two SiH groups in one molecule represented by the formula (1) is preferable. In addition, the substituent R ² in the compound represented by the general formula (III) is preferably composed of C, H and O, and more preferably a hydrocarbon group.

From the viewpoint of having good compatibility with the component (A), a chain and / or cyclic polyorganosiloxane and an organic compound having a carbon-carbon double bond are selected. A reaction product with one or more compounds (hereinafter referred to as component (E)) is also preferable. In this case, in order to further improve the compatibility with the component (A) of the reaction product, it is possible to use a product obtained by removing unreacted siloxanes and the like from the reaction product by devolatilization.

The component (E) is an organic compound having an organic skeleton containing at least one carbon-carbon double bond reactive with a SiH group in one molecule, and the same explanation as the component (A) is given. Can also be used. The organic compound as the component (E) may be the same as or different from the organic compound as the component (A). Further, it is possible to use a single kind or a mixture of two or more kinds. When it is desired to increase the compatibility of the component (B) with the component (A),
The component (E) is preferably the same as the component (A).

The chain and / or cyclic polyorganosiloxane to be reacted with the organic compound as the component (E) is 1,3 from the viewpoint of industrial availability and good reactivity in the case of reaction. , 5,7-Tetramethyltetracyclosiloxane is preferred.

As the component (B), like the component (A),
It is preferable that the content of the compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group is small, especially from the viewpoint of suppressing yellowing, and that does not include a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group. Is preferred. The phenolic hydroxyl group in the present invention is a benzene ring, a naphthalene ring, a hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by the anthracene ring, and the phenolic hydroxyl group derivative is a hydrogen atom of the above-mentioned phenolic hydroxyl group. A group substituted with an alkyl group such as a methyl group and an ethyl group, an alkenyl group such as a vinyl group and an allyl group, and an acyl group such as an acetoxy group.

From the viewpoint of good optical properties such as low birefringence and low photoelastic coefficient and good weather resistance, the weight ratio of the components in the component (A) of the aromatic ring is high. It is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight or less. Most preferred are those containing no aromatic hydrocarbon rings.

More preferable component (B) from the viewpoint of good optical characteristics is a reaction product of 1,3,5,7-tetramethyltetracyclosiloxane and vinylcyclohexene, 1,3,5,7-tetra. Reaction product of methyltetracyclosiloxane and dicyclopentadiene, 1,3
Reaction product of 5,7-tetramethyltetracyclosiloxane and triallyl isocyanurate, 1,3,5,7-tetramethyltetracyclosiloxane and 2,2-bis (4-
Specific examples of the component (B) include a reaction product of a diallyl ether of hydroxycyclohexyl) propane and a reaction product of 1,3,5,7-tetramethyltetracyclosiloxane and 1,2,4-trivinylcyclohexane. Reaction product of 1,3,5,7-tetramethyltetracyclosiloxane and triallyl isocyanurate, 1,3,5
5,7-Tetramethyltetracyclosiloxane and 2,2
-A reaction product of diallyl ether of bis (4-hydroxycyclohexyl) propane, a reaction product of 1,3,5,7-tetramethyltetracyclosiloxane and 1,2,4-trivinylcyclohexane, and the like. The mixing ratio of the component (A) and the component (B) as described above is not particularly limited as long as the necessary strength is not lost, but Si in the component (B) is not limited.
The ratio of the number of H groups (Y) to the number of carbon-carbon double bonds (X) in the component (A) is preferably 2.0 ≧ Y / X ≧ 0.9, and 1.8 ≧ Y / X ≧ 1.0 is more preferable. When 2.0> Y / X, sufficient curability may not be obtained and sufficient strength may not be obtained, and Y / X <0.
In case of 9, the carbon-carbon double bond becomes excessive, which may cause coloring.

Next, a hydrosilylation catalyst which is the component (C)
Will be described. As a hydrosilylation catalyst, hydr
There is no particular limitation as long as it has catalytic activity for the rosilylation reaction.
However, for example, simple substance of platinum, alumina, silica, carbon
Solid platinum supported on black carrier, white chloride
Auric acid, chloroplatinic acid and alcohol, aldehyde, ketone, etc.
Complex with platinum, an olefin complex (for example, Pt (CH
₂= CH₂)₂(PPh₃) ₂, Pt (CH₂= CH₂)₂Cl
₂), A platinum-vinyl siloxane complex (for example, Pt (V
iMe₂SiOSiMe₂Vi)_n, Pt [(MeViS
iO)_Four]_m), A platinum-phosphine complex (eg, Pt
(PPh₃)_Four, Pt (PBu₃)_Four), Platinum-phosphite
Complex (for example, Pt [P (OPh)₃]_Four, Pt [P
(OBu)₃]_Four) (Wherein, Me is a methyl group, Bu is buty
Group, Vi is a vinyl group, Ph is a phenyl group, and n,
m represents an integer. ), Dicarbonyldichloroplatinum,
Karstedt catalyst, also ash
Ashby US Pat. No. 3,159,601 and
And platinum-carbonized water described in US Pat. No. 3,159,662.
Of the elementary complex, as well as of Lamoreaux
Platinum described in US Pat. No. 3,220,972
Examples include alcoholate catalysts. In addition, modic
(Modic) U.S. Pat. No. 3,516,946
The platinum chloride-olefin composite described in 1.
And is useful.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ ,
RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdC
l ₂ .2H ₂ O, NiCl ₂ , TiCl ₄ , and the like.

Among these, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex and the like are preferable from the viewpoint of catalytic activity. Further, these catalysts may be used alone or in combination of two or more kinds.

The amount of the catalyst added is 0.3 with respect to the total amount of the above components (A) and (B) in order to ensure sufficient curability.
The range of 1 part by weight to 1 part by weight is preferable, and more preferably,
It is in the range of 0.2 to 0.8 parts by weight.

A cocatalyst may be used in combination with the above catalyst, and examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl maleate, and 2-hydroxy-2-. Examples thereof include acetylene alcohol compounds such as methyl-1-butyne, sulfur compounds such as elemental sulfur, and amine compounds such as triethylamine. The amount of the cocatalyst added is not particularly limited, but is preferably in the range of 10 ^-2 to 10 ² mol, and more preferably in the range of 10 ^-1 to 10 mol, per 1 mol of the catalyst.

Next, the curing retarder which is the component (D) will be described. Examples of the curing retarder include compounds containing an aliphatic unsaturated bond, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds and organic peroxides, and these may be used in combination. Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, en-yne compounds, maleic acid esters and the like. Examples of the organic phosphorus compound include triorganophosphines, diorganophosphines, organophosphines, triorganophosphites and the like.
Organic sulfur compounds include organomercaptans,
Examples thereof include diorganosulfides, hydrogen sulfide, benzothiazole, benzothiazole disulfide and the like.
Examples of the nitrogen-containing compound include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of the tin-based compound include stannous halide dihydrate and stannous carboxylate. Examples of organic peroxides include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

Among these curing retarders, 1-ethynyl-1-cyclohexanol, benzothiazole, thiazole, dimethylmalate and 3-hydroxy-3- are preferred from the viewpoint of good delay activity and good availability of raw materials. Methyl-1-butyne is preferred. From the viewpoint of optical properties, 1-ethynyl-1-cyclohexanol is preferable.

In order to secure a balance between storage stability and curability, the curing retarder is preferably in the range of 0.1 parts by weight to 1 part by weight with respect to the total amount of the above components (A) and (B), and more preferably The preferred range is 0.2 parts by weight to 0.8 parts by weight. As the composition of the present invention, various combinations can be used as described above, but from the viewpoint of good heat resistance, a cured product obtained by curing the composition has a Tg of 50 ° C. or higher. A temperature of 100 ° C. or higher is more preferable, and a temperature of 150 ° C. or higher is particularly preferable. The composition of the present invention preferably has an initial viscosity of 30 poises or less, more preferably 20 poises or less, and even more preferably 10 poises or less, as measured by an E-type viscometer, from the viewpoint of finely filling the package. Is particularly preferable. Triallyl isocyanurate as the component (A), a reaction product of 1,3,5,7-tetramethyltetracyclosiloxane and triallyl isocyanurate as the component (B), a platinum-vinylsiloxane complex as the component (C), (D When 1-ethynyl-1-cyclohexanol is used as the component), the component (C) is used in an amount of 0.2 parts by weight to 1 with respect to the total amount of the components (A) and (B) for the purpose of reducing resin overflow. By weight, the component (D) is preferably 0.1 parts by weight to 1 part by weight, and 0.3 to 0.8 parts by weight (component (C)) based on the total amount of the components (A) and (B). 0.2
To 0.8 parts by weight (component (D)) is more preferable, and
4-0.7 weight part ((C) component) and 0.3-0.5 weight part ((D) component) are especially preferable. Next, the melting / solidifying viscoelasticity measurement will be described. The melting / solidifying viscoelasticity measuring device is a device capable of evaluating A stage (monomer state) to B stage (state in which functional groups are partially reacted) to C stage (completely cured state) of the thermosetting resin, and stress. A control type (stress control type) or strain control type commercially available rheometer can be used. Here, the stress control type (stress control type) is superior to the strain control type because it can perform measurement under a minute stress. In the present invention, a CS / CVO stress control type rheometer manufactured by Borin Instruments Co., Ltd. was used as a melting / solidifying viscoelasticity measuring device. The measurement conditions were 35 ° C. to frequency: 1 Hz, and temperature rising condition: 5 ° C./min. In order to obtain a curable composition with reduced resin overflow, the temperature (T ₁ ) at which the minimum viscosity is given is obtained.
Is in the range of 50 ° C. to 80 ° C., and the temperature (T ₂ ) that gives a dynamic viscosity 1000 times the viscosity at T ₁ is 85 ° C.
Is preferably in the range of 120 to 120 ° C., and T ₁ is 60 ° C.
To 80 ° C., and T _{2 in} the range of 90 ° C. to 110 ° C. is particularly preferable.

If necessary, an inorganic filler may be added to the composition of the present invention to adjust the viscosity. Addition of an inorganic filler is effective in preventing the fluidity of the composition and increasing the strength of the material. As the inorganic filler, fine particles which do not deteriorate the optical properties are preferable, and alumina, aluminum hydroxide, fused silica, crystalline silica, ultrafine amorphous silica or hydrophobic ultrafine silica, talc, barium sulfate, etc. may be mentioned. You can

Examples of the method for adding the filler include hydrolyzable silane monomers or oligomers such as alkoxysilane, acyloxysilane and halogenated silane, and alkoxides, acyloxides and halides of metals such as titanium and aluminum. The method of adding to the composition of the invention and reacting in the composition or a partial reaction product of the composition to form an inorganic filler in the composition can also be mentioned.

Further, various resins may be added for the purpose of modifying the characteristics of the composition of the present invention. Examples of the resin include polycarbonate resin, polyether sulfone resin, polyarylate resin, epoxy resin, cyanate resin, phenol resin, acrylic resin, polyimide resin, polyvinyl acetal resin, urethane resin and polyester resin, but are not limited thereto. Not something. Among these, the transparent epoxy resin is preferable from the viewpoint of high transparency and excellent practical properties such as adhesiveness. Examples of the transparent epoxy resin include bisphenol A diglycidyl ether, 2,2′-bis (4-glycidyloxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, vinylcyclohexenedioxide. , 2- (3,4-epoxycyclohexyl)-
5,5-spiro- (3,4-epoxycyclohexane)
Epoxy resins such as -1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester and triglycidyl isocyanurate are treated with hexahydrophthalic anhydride or methylhexahydrophthalic anhydride. , Trialkyltetrahydrophthalic anhydride, hydrogenated methyl nadic acid anhydride and the like that are cured with an aliphatic acid anhydride.

The composition of the present invention can be directly molded into a film or the like, but it is also possible to dissolve the composition in an organic solvent to form a varnish. The solvent that can be used is not particularly limited, and specific examples include hydrocarbon solvents such as benzene, toluene, hexane, and heptane, tetrahydrofuran, 1,4-dioxane, ether solvents such as diethyl ether, and acetone. A ketone-based solvent such as methyl ethyl ketone and a halogen-based solvent such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used. The solvent may be used as a mixed solvent of two or more kinds. As the solvent, toluene, tetrahydrofuran and chloroform are preferable. The amount of solvent used is 1 g of the reactive component (A) used.
It is preferably used in the range of 0 to 10 mL, and 0.5 to 5
It is more preferably used in the range of mL, and particularly preferably used in the range of 1 to 3 mL. If the amount used is small, it is difficult to obtain the effect of using a solvent such as viscosity reduction, and if the amount used is large, the solvent remains in the material and problems such as thermal cracking easily occur, and also in terms of cost. It becomes disadvantageous and the industrial utility value decreases.

In the composition of the present invention, in addition, an antiaging agent, a radical inhibitor, an ultraviolet absorber, an adhesiveness improving agent, a flame retardant, a surfactant, a storage stability improving agent, an ozone deterioration preventing agent, a light stabilizer. , Thickeners, plasticizers, coupling agents, antioxidants, heat stabilizers, conductivity imparting agents, antistatic agents, radiation blocking agents, nucleating agents, phosphorus-based peroxide decomposers, lubricants, pigments, metal-free agents. An activator, a physical property modifier, etc. can be added within a range that does not impair the objects and effects of the present invention.

Further, various additives for improving the characteristics of the light emitting diode may be added to the composition of the present invention. Examples of the additive include a phosphor such as yttrium-aluminum-garnet-based phosphor activated with cerium, which absorbs light from the light-emitting element and emits fluorescence having a longer wavelength,
Coloring agents such as bluing agents that absorb specific wavelengths, titanium oxide, aluminum oxide, silica, silica oxide such as silica glass, talc, calcium carbonate, melamine resin, CTU guanamine resin, benzoguanamine resin, etc. Examples thereof include various inorganic or organic diffusion materials, glass, metal oxides such as aluminosilicate, and heat conductive fillers such as metal nitrides such as aluminum nitride and boron nitride.

The additive for improving the characteristics of the light emitting diode may be contained uniformly or may be contained with a graded content. Such a filler-containing resin portion can be formed as a molding member on the rear side of the light emitting surface by pouring the resin for the molding member on the front surface of the light emitting surface into the mold, and subsequently, flowing the resin containing the filler. In addition, after forming the mold member, cover the lead terminals by attaching tape from both the front and back sides, and in this state, immerse the lower half of the mold member of the light emitting diode in the tank containing the resin containing the filler, and then pull it up. It may be dried to form the filler-containing resin portion.

The composition for optical materials of the present invention is premixed and cured by reacting a carbon-carbon double bond reactive with the SiH group in the composition with a part or all of the SiH group. You can

Various methods can be used as the mixing method. A method in which the component (A) is mixed with the component (C) and the component (B) is mixed with the component (D). Is preferred. It is difficult to control the reaction by the method of mixing the component (C) with the mixture of the component (A) and the component (B). When the method of mixing the component (A) with the mixture of the component (C) with the component (B) is used, the component (B) has reactivity with water in the presence of the component (C), and therefore, during storage, etc. It may be altered.

When the composition is reacted and cured, the necessary amounts of the respective components (A), (B), (C) and (D) may be mixed at once, and the reaction may be carried out. After mixing and reacting, only a part of the functional groups in the composition can be reacted by mixing the remaining amount and further reacting, or by controlling the reaction conditions after mixing and using the difference in reactivity of the substituents. It is also possible to adopt a method in which (B stage) is performed and then a treatment such as molding is performed to further cure. According to these methods, the viscosity adjustment during molding becomes easy.

As a method of reacting, the reaction can be carried out by simply mixing or by heating. The method of heating and reacting is preferable from the viewpoint that the reaction is fast and a material having high heat resistance is generally easily obtained.

Although the reaction temperature can be set variously, for example, a temperature of 30 to 300 ° C. can be applied, and 100 to 250 ° C.
Are more preferable, and 150-200 degreeC is still more preferable.
If the reaction temperature is low, the reaction time for sufficiently reacting becomes long, and if the reaction temperature is high, the molding process tends to be difficult. The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple stages or continuously if necessary. 60 ° C / 6 to reduce the overflow from the package
It is preferable to raise the temperature stepwise such as h, 70 ° C./1 h, 80 ° C./1 h, 120 ° C./1 h.

The reaction time can be set variously, and the pressure during the reaction can be set variously according to need, and the reaction can be carried out under normal pressure, high pressure, or reduced pressure.

If necessary, various treatments can be performed during molding. For example, centrifugation or reduced pressure of a composition or a partially reacted composition for suppressing voids generated during molding,
It is also possible to apply a treatment for defoaming by pressure or the like.

The light emitting diode of the present invention can be manufactured by coating the light emitting element with the curable composition as described above.

In this case, the light emitting element is not particularly limited, and a light emitting element used in a conventionally known light emitting diode can be used. As such a light emitting element, for example, M
Examples include those prepared by laminating a semiconductor material on a substrate provided with a buffer layer such as GaN or AlN, if necessary, by various methods such as an OCVD method, an HDVPE method, and a liquid phase growth method. As the substrate in this case, various materials can be used, for example, sapphire, spinel,
Examples thereof include SiC, Si, ZnO, and GaN single crystal.
Of these, sapphire is preferably used from the viewpoint that GaN having good crystallinity can be easily formed and has high industrial utility value.

GaA is used as the laminated semiconductor material.
s, GaP, GaAlAs, GaAsP, AlGaIn
P, GaN, InN, AlN, InGaN, InGaA
1N, SiC, etc. are mentioned. Of these, from the viewpoint of obtaining high brightness, a nitride-based compound semiconductor (I
nx GayAlz N) is preferred. Such a material may contain an activator or the like.

The structure of the light emitting element is MIS junction, p
Examples include an n-junction, a homojunction having a PIN junction, a heterojunction, and a double hetero structure. Also, a single or multiple quantum well structure can be adopted.

The light emitting element may or may not be provided with a passivation layer.

Electrodes can be formed on the light emitting device by a conventionally known method.

Various emission wavelengths of the light emitting element can be used from the ultraviolet region to the infrared region, and the effect of the present invention is particularly remarkable when the main emission peak wavelength is 550 nm or less.

One type of light emitting element may be used for single color light emission, or a plurality of light emitting elements may be used for single color or multicolor light emission.

The electrodes on the light emitting element can be electrically connected to lead terminals and the like by various methods. The electrical connection member preferably has good ohmic mechanical connectivity with the electrodes of the light emitting element, and examples thereof include bonding wires using gold, silver, copper, platinum, aluminum or alloys thereof. . A conductive adhesive or the like in which a conductive filler such as silver or carbon is filled with a resin can also be used. Among these, it is preferable to use an aluminum wire or a gold wire from the viewpoint of good workability.

The lead terminal used in the light emitting diode of the present invention is preferably one having good adhesion to an electrical connecting member such as a bonding wire and good electrical conductivity.
The electric resistance of the lead terminal is preferably 300 μΩ-cm or less, more preferably 3 μΩ-cm or less.
Examples of these lead terminal materials include iron, copper, iron-containing copper, tin-containing copper, and those obtained by plating these with silver, nickel, or the like. The glossiness of these lead terminals may be adjusted appropriately in order to obtain good light spread.

The light emitting diode of the present invention can be manufactured by coating the light emitting element with the above-mentioned curable composition. In this case, the coating is not limited to the one which directly seals the light emitting element. Including the case of indirectly coating. Specifically, the light emitting device may be sealed with the curable composition of the present invention directly by various methods conventionally used, or conventionally used epoxy resin, silicone resin, acrylic resin, urea resin, imide resin, etc. After encapsulating the light emitting element with the encapsulating resin or glass, the top or the periphery thereof may be coated with the curable composition of the present invention. Further, the light emitting element may be sealed with the curable composition of the present invention and then molded with a conventionally used epoxy resin, silicone resin, acrylic resin, urea resin, imide resin or the like. It is possible to provide various effects such as a lens effect by the difference in refractive index and specific gravity by the above method.

Various methods can be applied as a sealing method. For example, a liquid curable composition may be injected into a cup, a cavity, a package recess or the like having a light emitting element arranged at the bottom by a dispenser or other method and cured by heating, or a solid or high viscosity liquid. The curable composition may be heated to make it flow, and similarly, it may be injected into the concave portion of the package and further heated to be cured. The package in this case can be made using various materials, and examples thereof include polycarbonate resin, polyphenylene sulfide resin, epoxy resin, acrylic resin, silicone resin, ABS resin and the like. Alternatively, a method of injecting a curable composition into a mold form in advance, immersing a lead frame or the like having a light emitting element fixed therein and then curing the composition may be applied. The sealing layer of the curable composition may be molded and cured by injection with a dispenser, transfer molding, injection molding, or the like. further,
A curable composition which is simply in a liquid or fluid state may be dropped or coated on the light emitting element to be cured.
Alternatively, the curable resin can be molded and cured by stencil printing, screen printing, or application through a mask on the light emitting element. In addition, a method of fixing a curable composition which is partially cured or cured in advance into a plate shape or a lens shape on the light emitting element may be used. Further, it can be used as a die bonding agent for fixing the light emitting element to a lead terminal or a package, or can be used as a passivation film on the light emitting element. It can also be used as a package substrate.

The shape of the covered portion is not particularly limited and can be various shapes. Examples thereof include a lens shape, a plate shape, a thin film shape, and the shape described in JP-A-6-244458. These shapes may be formed by molding and curing the curable composition, or may be formed by post-processing after curing the curable composition.

The light emitting diode of the present invention may be of various types, for example, any type such as a lamp type, an SMD type and a chip type. Various types of SMD type and chip type package substrates are used, such as epoxy resin, BT resin,
Examples include ceramics.

In addition, various conventionally known methods can be applied to the light emitting diode of the present invention. For example, a method in which a layer for reflecting or condensing light is provided on the back surface of the light emitting element, a method in which a complementary color coloring portion is formed on the bottom in response to yellowing of the sealing resin,
A method in which a thin film that absorbs light of a wavelength shorter than the main emission peak is provided on the light emitting element, a method in which the light emitting element is sealed with a soft or liquid encapsulating material and then the surroundings are molded with a hard material, and light from the light emitting element is A method in which a light emitting element is sealed with a material containing a phosphor that absorbs and emits fluorescence of a longer wavelength, and then the periphery is molded, a method in which a material containing the phosphor is molded in advance and then molded with the light emitting element. -244458, a molding material having a special shape to improve light emission efficiency, a method in which a package is formed into a two-step recess for reducing uneven brightness, a method in which a light emitting diode is inserted and fixed in a through hole, and light emission is performed. By a method of forming a thin film that absorbs light of a wavelength shorter than the main emission wavelength on the element surface, flip-chip connection of the light emitting element using solder bumps, etc. Method in which light is taken out from the substrate direction by connecting the lead member or the like Te, and the like.

The light emitting diode of the present invention can be used in various conventionally known applications. Specifically, examples thereof include a backlight, an illumination, a sensor light source, a vehicle instrument light source, a signal light, an indicator light, a display device, a light source of a planar light emitter, a display, a decoration, and various lights.

[0082]

EXAMPLES Examples and comparative examples of the present invention will be shown below, but the present invention is not limited thereto. (Synthesis example 1) A magnetic stir bar and a cooling tube were set in a 200 mL two-necked flask. Toluene 50 in this flask
g, a xylene solution of a platinum vinyl siloxane complex (containing 3 wt% as platinum) 11.3 μL, 5.0 g of triallyl isocyanurate, 37.04 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and 90 ° C. The mixture was heated and stirred in the oil bath for 30 minutes. Further, it was heated under reflux in an oil bath at 130 ° C. for 2 hours. 1-ethynyl-
176 mg of 1-cyclohexanol was added. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. ^{By 1} H-NMR, it was found that this product was obtained by reacting a part of SiH groups of 1,3,5,7-tetramethylcyclotetrasiloxane with triallyl isocyanurate (referred to as partial reaction product A). . (Example 1) 1.0 g of triallyl isocyanurate and a xylene solution of a platinum vinyl siloxane complex (3 as platinum)
(wt% content) 17 mg (0.7 parts by weight), partial reaction product A 1.4 g synthesized in Synthesis Example 1, 1-ethynyl-1-cyclohexanol 7.1 mg, and Aerosil 130 47 mg manufactured by Nippon Aerosil Co., Ltd. The mixture was stirred for 1.5 minutes and defoamed for 3.0 minutes. The viscosity was 9 poise. The melting / solidifying viscoelastic behavior of this product was measured using a CS / CVO stress control type rheometer manufactured by Borin Instruments. The measurement conditions were 35 ° C. to frequency: 1 Hz, and temperature rising condition: 5 ° C./min. The chart is shown in FIG. The temperature giving the lowest viscosity (T ₁ ) was 66 ° C., and the temperature giving a dynamic viscosity 1000 times the viscosity at T ₁ (T ₂ ) was 99 ° C. This product was filled in a polyamide package (2.5 × 2.0 × 1.0 mmt) using a dispenser, and the temperature was 60 ° C./6 hours, 70 ° C./1 hour, 80 ° C.
Heating was performed for 1 hour and 120 ° C. for 1 hour. No resin overflow from the package was observed after curing. Comparative Example 1 1.0 g of triallyl isocyanurate and 1.4 g of the partial reaction product A synthesized in Synthesis Example 1 were stirred in the cup for 1.5 minutes and degassed for 3.0 minutes. The viscosity was 5 poise. The melting / solidifying viscoelastic behavior of this product was measured using a CS / CVO stress control type rheometer manufactured by Borin Instruments. Measurement conditions are from 35 ℃ to frequency: 1H
z, temperature rising condition: 5 ° C./min. The chart is shown in FIG. The temperature giving the lowest viscosity (T ₁ ) was 95 ° C, and the temperature giving a dynamic viscosity 1000 times the viscosity at T ₁ (T ₂ ) was 138 ° C.

This product was filled in a polyamide package (2.5 × 2.0 × 1.0 mmt) using a dispenser, and the temperature was 60 ° C./6 hours, 70 ° C./1 hour, 80 ° C.
Heating was performed for 1 hour and 120 ° C. for 1 hour. After curing, resin overflow from the package was seen. (Example 2) The sheet-shaped cured product prepared in Example 1 is cut into an appropriate shape and fixed to a light transmitting window portion provided on a can type metal cap. On the other hand, MOCVD
An InGaN active layer doped with Si and Zn formed on a sapphire substrate by a (metal organic chemical vapor deposition) method is used.
A light-emitting element having a double hetero structure sandwiched between a p-type and a p-type AlGaN cladding layer is prepared. Then, after mounting this light emitting element on a can type metal stem,
The electrodes are wire-bonded to the respective leads with Au wires. This is hermetically sealed with the can type metal cap described above. In this way, a can type light emitting diode can be produced. (Example 3) MOCVD on a cleaned sapphire substrate
An n-type GaN layer that is an undoped nitride semiconductor, a GaN layer that forms an n-type contact layer by forming an Si-doped n-type electrode, and an n-type GaN that is an undoped nitride semiconductor by the (metal organic chemical vapor deposition) method. Layer, then a GaN layer that will become a barrier layer that constitutes the light emitting layer, and InGaN that constitutes a well layer
Layer, a GaN layer (quantum well structure) serving as a barrier layer, and an AlGa layer as a p-type cladding layer doped with Mg on the light emitting layer.
Ga which is an N layer and a p-type contact layer doped with Mg
N layers are sequentially stacked. The surface of each pn contact layer is exposed on the same side of the nitride semiconductor on the sapphire substrate by etching. Al is vapor-deposited on each contact layer by a sputtering method to form positive and negative electrodes, respectively. After the scribe line is drawn on the completed semiconductor wafer, it is divided by an external force to form a light emitting element which is a light emitting element.

The above light emitting element is die-bonded onto the cup bottom surface of a mount lead made of iron-plated copper whose surface is plated with silver using an epoxy resin composition as a die-bonding resin. This is heated at 170 ° C. for 75 minutes to cure the epoxy resin composition and fix the light emitting element. Next, the positive and negative electrodes of the light emitting element and the mount lead and the inner lead are wire-bonded with an Au wire to establish electrical conduction.

The curable composition prepared in the same manner as in Example 1 is poured into a casting case which is a shell type frame. A part of the mount lead and the inner lead in which the above light emitting device is arranged in the cup is inserted into the casting case, and initial curing is performed at 100 ° C. for 1 hour. The light emitting diode is extracted from the casting case and cured at 120 ° C. for 1 hour in a nitrogen atmosphere. Thereby, a lamp type light emitting diode such as a shell type can be produced. Example 4 A curable composition and a light emitting device are prepared by the method described in Example 1.

By forming a pair of copper foil patterns on the glass epoxy resin by etching, a substrate having lead electrodes is formed. The light emitting element is die-bonded onto a glass epoxy resin using an epoxy resin. Each electrode of the light emitting element and each lead electrode are wire-bonded with an Au wire to establish electrical continuity. A glass epoxy resin having a through hole as a mask and a side wall is fixedly arranged on the substrate by the epoxy resin. In this state, the curable composition is dispensed on the glass epoxy resin substrate on which the light emitting element is disposed while being disposed in the vacuum device,
The curable composition is filled in the cavity using the through holes. In this state, it is cured at 100 ° C. for 1 hour and further at 150 ° C. for 1 hour. A chip type light emitting diode can be produced by dividing each light emitting diode chip. Example 5 A curable composition and a light emitting device are prepared by the method described in Example 1.

A chip type light emitting diode package is formed using PPS resin by insert molding. The package has an opening in which a light emitting element is arranged, and a silver-plated copper plate is arranged as an external electrode. The light emitting element is fixed inside the package by die-bonding with an epoxy resin. An Au wire, which is a conductive wire, is wire-bonded to each electrode of the light emitting element and each external electrode provided on the package to be electrically connected.
A curable composition is filled in the package opening as a mold member. In this state, 100 ℃ for 1 hour, then 15
Cure at 0 ° C. for 1 hour. In this way, a chip type light emitting diode can be manufactured.

[0088]

The curable composition used in the light emitting diode of the present invention has a low viscosity and a reduced resin overflow, and thus can be used as a sealant for a light emitting diode.

[Brief description of drawings]

FIG. 1 is a diagram showing a molten / solidified viscoelastic behavior of Example 1.

FIG. 2 is a diagram showing a molten / solidified viscoelastic behavior of Comparative Example 1.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 23/31 F term (reference) 4J002 CP041 DE149 DG049 DJ019 DJ049 EA026 EA036 EA046 EC037 EC038 ED026 EH006 EH146 EJ036 EU186 EU196FD0 FD207 GP00 GQ05 4M109 AA01 BA04 CA05 EA03 EB04 EB09 EC11 EC20 GA01 5F041 AA31 CA04 CA05 CA34 CA40 CA53 CA57 CA65 DA07 DA12 DA18 DA43 DA64 DB01 DB06

Claims (7)

[Claims] 1. An organic compound containing (A) at least two carbon-carbon double bonds reactive with a SiH group in one molecule, and (B) containing at least two SiH groups in one molecule. A curable composition containing a compound, (C) a hydrosilylation catalyst, and (D) a curing retarder as essential components,
In the dynamic viscosity (η ^* ) measurement of melting / solidifying viscoelasticity measured at a frequency of 1 Hz and a temperature rising condition of 5 ° C./min, the temperature (T ₁ ) giving the minimum viscosity is in the range of 50 ° C. to 80 ° C. And a temperature (T ₂ ) at which a dynamic viscosity 1000 times the viscosity at T ₁ is applied is in the range of 85 ° C to 120 ° C. 2. The component (A) is triallyl isocyanurate, and the component (B) is a reaction product of 1,3,5,7-tetramethyltetracyclosiloxane and triallyl isocyanurate. The curable composition for encapsulating a light emitting diode according to claim 1. 3. The curable composition for encapsulating a light emitting diode according to claim 1, wherein the component (C) is a platinum-vinylsiloxane complex. 4. The curable composition for encapsulating a light emitting diode according to claim 1, wherein the component (D) is 1-ethynyl-1-cyclohexanol. 5. A curable composition for encapsulating a light emitting diode according to claim 1, which is mixed in advance,
A light-emitting diode encapsulating material obtained by curing a carbon-carbon double bond reactive with a SiH group in the composition by reacting a part or all of the SiH group. 6. A curable composition for encapsulating a light emitting diode according to claim 1, which is previously mixed,
A method for producing a light-emitting diode encapsulating material obtained by curing a carbon-carbon double bond reactive with a SiH group in a composition by reacting a part or all of the SiH group. 7. A light emitting diode using the light emitting diode encapsulating material according to claim 5.