JP5487794B2 - Optical semiconductor sealing composition, cured body, optical semiconductor sealing material, and light emitting diode sealing material - Google Patents

Description

  The present invention relates to an optical semiconductor encapsulant composition, a cured body, an optical semiconductor encapsulant, and a light emitting diode encapsulant. More specifically, the present invention relates to an optical semiconductor sealing composition having curability, a cured product obtained by curing the composition, an optical semiconductor sealing material and a light emitting diode sealing material comprising the cured product.

  Conventionally, an epoxy compound mainly composed of bisphenol A glycidyl ether has been used as an optical semiconductor sealing resin. However, since such an epoxy compound has an aromatic ring, durability against ultraviolet rays (UV durability) is insufficient for sealing an optical semiconductor emitting blue or ultraviolet light.

  Then, in order to improve UV durability of resin for optical semiconductor sealing, using an alicyclic epoxy compound is proposed (refer patent document 1). However, even if an alicyclic epoxy compound is used, the UV durability is still not sufficient.

  On the other hand, it is known that a resin having a siloxane skeleton is excellent in weather resistance. In recent years, use of a resin having a main skeleton of polydimethylsiloxane as an optical semiconductor sealing material has been studied (Patent Document 2). reference). However, when the content of the linear siloxane component is increased, the crosslinking group (crosslinking point) is decreased, so that there is a problem that the curability is inferior. In addition, if a condensation reaction is used as a method for curing a siloxane-based material, volume change occurs before and after curing, causing cracks and the like, which is inferior in film formability on the order of mm required for an optical semiconductor sealing resin. There is also a problem.

  Therefore, the use of a silicon-based material having an epoxy group that cures in an addition reaction system as an optical semiconductor sealing resin has also been studied (see Patent Document 3). For example, as a method for curing a siloxane-based material, a method is proposed in which a silicon-based material having an epoxy group and an acid anhydride are used and cured using an addition reaction between an epoxy group and an acid anhydride group ( (See Patent Documents 4 and 5).

  However, even when an LED (Light Emitting Diode) chip is sealed using the materials described in Patent Documents 4 and 5, there is a problem that volume shrinkage occurs when the material is cured. Furthermore, when a siloxane-based material is used, there is a problem that the obtained cured body has low strength and becomes brittle.

Japanese Patent Laid-Open No. 2003-082062 JP 2007-270055 A JP 2007-302825 A JP 2007-016073 A JP 2008-179811 A

  The present invention seeks to solve the problems associated with the prior art as described above. For example, in Patent Documents 4 and 5, commercially available hexahydrophthalic anhydride is used as the acid anhydride that is a curing agent. However, since these acid anhydrides sublime at the time of curing, volume shrinkage of the cured product occurs.

  An object of the present invention is to provide a composition for encapsulating an optical semiconductor that can produce a cured product that is excellent in curability, has a small volume shrinkage rate and a small weight loss rate during curing, and is excellent in transparency and strength. is there. Moreover, it is providing the hardening body obtained by hardening | curing the said composition, and the optical semiconductor sealing material and light emitting diode (LED: Light Emitting Diode) sealing material which consist of this hardening body.

  The present inventors have intensively studied to solve the above problems. As a result, by using a siloxane compound having a specific weight average molecular weight and an acid anhydride structure as a curing agent for a silicon-based material having an epoxy group, the compound is prevented from sublimation during curing, and the volume The present inventors have found that the shrinkage can be suppressed and the transparency of the cured product is improved due to the excellent compatibility between the compound and the silicon-based material having an epoxy group, and the present invention has been completed. That is, the present invention relates to the following [1] to [10].

  [1] (A) A siloxane compound having a polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography of 100 to 1,000,000 and an epoxy equivalent of 50 to 500,000 g / eq., And (B) gel perme A composition for encapsulating an optical semiconductor, comprising a siloxane compound having a polystyrene-equivalent weight average molecular weight (Mw) of 100 to 1,000,000 and having at least one acid anhydride structure in the molecule. object.

  [2] The composition for optical semiconductor encapsulation according to [1], wherein the siloxane compound (B) is a siloxane compound represented by the following formula (B ′).

［式（Ｂ’）中、複数あるＲ^Aはそれぞれ独立に酸無水物構造を含有する有機基を示し、複数あるＲはそれぞれ独立に非置換または置換の１価の炭化水素基を示し、ｎは０〜１０００の整数を示す。］
［３］前記酸無水物構造を含有する有機基が、下記式（ｂ−１）で表される有機基であることを特徴とする前記［２］に記載の光半導体封止用組成物。

[In the formula (B ′), a plurality of R ^A each independently represents an organic group containing an acid anhydride structure, a plurality of R each independently represents an unsubstituted or substituted monovalent hydrocarbon group, n Represents an integer of 0 to 1000. ]
[3] The composition for optical semiconductor encapsulation according to [2], wherein the organic group containing the acid anhydride structure is an organic group represented by the following formula (b-1).

［式（ｂ−１）中、Ｚは−Ｏ−または−ＣＲ⁷Ｒ⁸−を示し、Ｒ¹〜Ｒ⁸はそれぞれ独立に水素、ハロゲン、または非置換もしくは置換の１価の炭化水素基を示し、＊−は結合手を示す。］
［４］前記シロキサン化合物（Ｂ）が、（ｂ１）分子中に水素−珪素結合を少なくとも１つ有するシロキサン化合物と、（ｂ２）炭素−炭素二重結合を有する酸無水物とを反応させることによって得られることを特徴とする前記［１］または［２］に記載の光半導体封止用組成物。

[In the formula (b-1), Z represents —O— or —CR ⁷ R ⁸ —, and R ^{1 to} R ⁸ each independently represents hydrogen, halogen, or an unsubstituted or substituted monovalent hydrocarbon group. *-Indicates a bond. ]
[4] By reacting the siloxane compound (B) with (b1) a siloxane compound having at least one hydrogen-silicon bond in the molecule and (b2) an acid anhydride having a carbon-carbon double bond. The composition for optical semiconductor encapsulation according to [1] or [2], which is obtained.

  [5] The composition for optical semiconductor encapsulation according to [4], wherein the acid anhydride (b2) is an acid anhydride represented by the following formula (b2 ′).

［式（ｂ２’）中、Ｚは−Ｏ−または−ＣＲ⁷Ｒ⁸−を示し、Ｒ¹〜Ｒ⁸はそれぞれ独立に水素、ハロゲン、または非置換もしくは置換の１価の炭化水素基を示す。］
［６］前記シロキサン化合物（Ａ）と前記シロキサン化合物（Ｂ）とが、前記シロキサン化合物（Ａ）中のエポキシ基１モルに対する前記シロキサン化合物（Ｂ）中の酸無水物構造のモル数が０．２〜３．０となる量で含まれることを特徴とする前記［１］〜［５］の何れかに記載の光半導体封止用組成物。

[In the formula (b2 ′), Z represents —O— or —CR ⁷ R ⁸ —, and R ^{1 to} R ⁸ each independently represent hydrogen, halogen, or an unsubstituted or substituted monovalent hydrocarbon group. . ]
[6] The number of moles of the acid anhydride structure in the siloxane compound (B) in which the siloxane compound (A) and the siloxane compound (B) are 0.1 mole relative to 1 mole of the epoxy group in the siloxane compound (A). The composition for optical semiconductor encapsulation according to any one of [1] to [5], wherein the composition is contained in an amount of 2 to 3.0.

  [7] Any of the above [1] to [6], wherein the siloxane compound (A) has an organic group represented by any of the following formulas (a-1) to (a-4): A composition for sealing an optical semiconductor according to claim 1.

［式（ａ−１）中、Ｘはメチレン基、炭素数２〜１０の２価の直鎖状アルキレン基または炭素数３〜１０の２価の分岐鎖状アルキレン基を示す。］

[In the formula (a-1), X represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a divalent branched alkylene group having 3 to 10 carbon atoms. ]

［式（ａ−２）中、Ｘはメチレン基、炭素数２〜１０の２価の直鎖状アルキレン基または炭素数３〜１０の２価の分岐鎖状アルキレン基を示す。］

[In Formula (a-2), X represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a divalent branched alkylene group having 3 to 10 carbon atoms. ]

［式（ａ−３）中、Ｘはメチレン基、炭素数２〜１０の２価の直鎖状アルキレン基または炭素数３〜１０の２価の分岐鎖状アルキレン基を示す。］

[In Formula (a-3), X represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a divalent branched alkylene group having 3 to 10 carbon atoms. ]

［式（ａ−４）中、Ｘはメチレン基、炭素数２〜１０の２価の直鎖状アルキレン基または炭素数３〜１０の２価の分岐鎖状アルキレン基を示す。］
［８］前記［１］〜［７］の何れかに記載の光半導体封止用組成物を硬化して得られる硬化体。

[In Formula (a-4), X represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a divalent branched alkylene group having 3 to 10 carbon atoms. ]
[8] A cured product obtained by curing the composition for optical semiconductor encapsulation according to any one of [1] to [7].

[9] An optical semiconductor sealing material comprising the cured body according to [8].
[10] A light emitting diode sealing material comprising the cured body according to [8].

By using the composition for encapsulating an optical semiconductor according to the present invention, a cured product having excellent curability, a small volume shrinkage rate and a small weight loss rate during curing, and excellent transparency and strength can be obtained.
For example, (1) When the composition is cured, volume shrinkage due to scattering of volatile components can be reduced. (2) Ensuring sufficient curability even when forming a cured body having a film thickness of mm. (3) A composition for encapsulating an optical semiconductor capable of forming a cured body having high strength can be obtained.

  Moreover, the hardening body obtained by hardening | curing the said composition for optical semiconductor sealing can be used suitably as an optical semiconductor sealing material, especially a light emitting diode sealing material.

  Hereinafter, with regard to the composition for optical semiconductor encapsulation according to the present invention, a cured product obtained by curing the composition, and an optical semiconductor encapsulation material and a light-emitting diode encapsulation material comprising the cured product, these preferred embodiments are also included. A detailed explanation will be given.

[Composition for optical semiconductor encapsulation]
The composition for optical semiconductor encapsulation according to the present invention contains a siloxane compound (A) and a siloxane compound (B) described below. Moreover, the said composition may contain other hardening | curing agents other than the said siloxane compound (B), a hardening accelerator, an inorganic particle, adhesion | attachment adjuvant, etc.

<Siloxane compound (A)>
The siloxane compound (A) is a siloxane compound having a polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 100 to 1,000,000 and an epoxy equivalent of 50 to 500,000 g / eq. In this invention, the said siloxane compound (A) may be used individually by 1 type, and may mix and use 2 or more types.

  The siloxane compound (A) has a polystyrene-equivalent Mw measured by GPC of 100 to 1,000,000, preferably 200 to 500,000, particularly preferably 200 to 100,000. When Mw is in the above range, it is preferable from the viewpoints of curability and handleability of the siloxane compound (A).

  The siloxane compound (A) has an epoxy equivalent of 50 to 500,000 g / eq., Preferably 100 to 200,000 g / eq., Particularly preferably 100 to 100,000 g / eq. When the epoxy equivalent is in the above range, it is preferable from the viewpoint of the curability of the siloxane compound (A) and the strength of the cured product.

  The siloxane compound (A) preferably has an epoxy group-containing hydrocarbon group having 3 to 20 carbon atoms. The epoxy group-containing hydrocarbon group having 3 to 20 carbon atoms includes an organic group represented by the following formula (a-1) or (a-2); 3,4-epoxycyclopentyl group, 2- (3,4- Epoxycyclopentyl) ethyl group, 3,4-epoxycyclohexyl group, and epoxycycloalkyl groups such as organic groups represented by the following formula (a-3) or (a-4). Among these, an organic group represented by any one of the following formulas (a-1) to (a-4) is particularly preferable.

式（ａ−１）中、Ｘはメチレン基、炭素数２〜１０の２価の直鎖状アルキレン基または炭素数３〜１０の２価の分岐鎖状アルキレン基を示す。

In formula (a-1), X represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a divalent branched alkylene group having 3 to 10 carbon atoms.

式（ａ−２）中、Ｘはメチレン基、炭素数２〜１０の２価の直鎖状アルキレン基または炭素数３〜１０の２価の分岐鎖状アルキレン基を示す。具体的には、γ−グリシドキシプロピル基などが挙げられる。

In formula (a-2), X represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a divalent branched alkylene group having 3 to 10 carbon atoms. Specific examples include a γ-glycidoxypropyl group.

式（ａ−３）中、Ｘはメチレン基、炭素数２〜１０の２価の直鎖状アルキレン基または炭素数３〜１０の２価の分岐鎖状アルキレン基を示す。具体的には、２−（３，４−エポキシシクロヘキシル）エチル基などが挙げられる。

In formula (a-3), X represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a divalent branched alkylene group having 3 to 10 carbon atoms. Specific examples include 2- (3,4-epoxycyclohexyl) ethyl group.

式（ａ−４）中、Ｘはメチレン基、炭素数２〜１０の２価の直鎖状アルキレン基または炭素数３〜１０の２価の分岐鎖状アルキレン基を示す。

In formula (a-4), X represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a divalent branched alkylene group having 3 to 10 carbon atoms.

<Siloxane compound (B)>
The siloxane compound (B) is a siloxane compound having a polystyrene equivalent Mw measured by GPC of 100 to 1,000,000 and having at least one acid anhydride structure in the molecule. In this invention, the said siloxane compound (B) may be used individually by 1 type, and may mix and use 2 or more types.

  The Mw in terms of polystyrene measured by GPC of the siloxane compound (B) is in the range of 100 to 1,000,000, preferably 100 to 500,000, particularly preferably 100 to 100,000. When Mw is in the above range, it is preferable from the viewpoints of improvement in weight reduction rate, curability, viscosity, and handleability.

  In the present invention, the siloxane compound (B) also includes a low molecular weight siloxane compound. In the case of such a low molecular weight siloxane compound, the above Mw corresponds to the molecular weight.

  As the siloxane compound (B), a siloxane compound represented by the following formula (B ′) can be preferably used.

式（Ｂ’）中、複数あるＲ^Aはそれぞれ独立に酸無水物構造を含有する有機基を示し、複数あるＲはそれぞれ独立に非置換または置換の１価の炭化水素基を示し、ｎは０〜１０００の整数、好ましくは０〜５００の整数を示す。

In the formula (B ′), a plurality of R ^A each independently represents an organic group containing an acid anhydride structure, a plurality of R each independently represents an unsubstituted or substituted monovalent hydrocarbon group, and n is The integer of 0-1000, Preferably the integer of 0-500 is shown.

  In the above formula (B ′), the organic group containing the acid anhydride structure is preferably an organic group represented by the following formula (b-1).

式（ｂ−１）中、Ｚは−Ｏ−または−ＣＲ⁷Ｒ⁸−を示し、好ましくは−ＣＲ⁷Ｒ⁸−を示す。Ｒ¹〜Ｒ⁸はそれぞれ独立に水素、ハロゲン、または非置換もしくは置換の１価の炭化水素基を示し、好ましくは水素または非置換の１価の炭化水素基を示し、より好ましくは水素を示す。＊−は結合手を示す。前記結合手は、Ｒ¹またはＲ²が結合した炭素原子に結合している。

In formula (b-1), Z represents —O— or —CR ⁷ R ⁸ —, preferably —CR ⁷ R ⁸ —. R ^{1 to} R ⁸ each independently represent hydrogen, halogen, or an unsubstituted or substituted monovalent hydrocarbon group, preferably hydrogen or an unsubstituted monovalent hydrocarbon group, more preferably hydrogen. . *-Indicates a bond. The bond is bonded to the carbon atom to which R ¹ or R ² is bonded.

Examples of the halogen include fluorine, chlorine, bromine and iodine.
In the formula (B ′) and the formula (b-1), the unsubstituted monovalent hydrocarbon group is preferably a hydrocarbon group having 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group An alkyl group such as cyclopentyl group and cyclohexyl group; and an aromatic group such as phenyl group.

  In the formula (B ′) and the formula (b-1), the substituted monovalent hydrocarbon group is at least one hydrogen atom or carbon atom contained in the unsubstituted monovalent hydrocarbon group. Is a group substituted with a halogen atom, substituted or unsubstituted amino group, hydroxyl group, mercapto group, isocyanate group, glycidoxy group, 3,4-epoxycyclohexyl group, (meth) acryloxy group, ureido group, ammonium base, etc. Is mentioned.

  The siloxane compound (B) includes, for example, (b1) a siloxane compound having at least one hydrogen-silicon bond in the molecule (hereinafter also referred to as “siloxane compound (b1)”), and (b2) a carbon-carbon double. It can be obtained by reacting an acid anhydride having a bond (hereinafter also referred to as “acid anhydride (b2)”).

  More specifically, the siloxane compound (B) is synthesized by a coupling reaction between the siloxane compound (b1) and the acid anhydride (b2) in the presence of a transition metal catalyst. The coupling reaction is preferably performed in an organic solvent.

<< Siloxane compound (b1) >>
The siloxane compound (b1) is a siloxane compound having at least one hydrogen-silicon bond in the molecule. The siloxane compound (b1) may have a branched structure such as a star shape or a comb shape.

  As the siloxane compound (b1), a siloxane compound represented by the following formula (b1 ′) can be preferably used.

式（ｂ１’）中、複数あるＲはそれぞれ独立に非置換または置換の１価の炭化水素基を示し、ｎは０〜１０００の整数、好ましくは０〜５００の整数を示す。

In formula (b1 ′), a plurality of R's each independently represents an unsubstituted or substituted monovalent hydrocarbon group, and n represents an integer of 0 to 1000, preferably an integer of 0 to 500.

  In the above formula (b1 ′), examples of the unsubstituted or substituted monovalent hydrocarbon group include the groups exemplified as the unsubstituted or substituted monovalent hydrocarbon group in the above formula (B ′). Can do.

  As the siloxane compound (b1), commercially available polydimethylsiloxanes such as DMS-H03, DMS-H11, DMS-H21, HMS-013, and HMS-031 manufactured by Gelest can also be used.

  The siloxane compound (b1) has a polystyrene-equivalent Mw measured by GPC, preferably in the range of 100 to 1000000, more preferably 100 to 500000, and particularly preferably 100 to 100000.

  In the present invention, examples of the siloxane compound (b1) include low molecular weight siloxane compounds such as tetramethyldisiloxane. In the case of such a low molecular weight siloxane compound, the above Mw corresponds to the molecular weight.

≪Acid anhydride (b2) ≫
The acid anhydride (b2) is an acid anhydride having a carbon-carbon double bond. As the acid anhydride (b2), an acid anhydride represented by the following formula (b2 ′) can be preferably used.

式（ｂ２’）中、Ｚは−Ｏ−または−ＣＲ⁷Ｒ⁸−を示し、好ましくは−ＣＲ⁷Ｒ⁸−を示す。Ｒ¹〜Ｒ⁸はそれぞれ独立に水素、ハロゲン、または非置換もしくは置換の１価の炭化水素基を示し、好ましくは水素または非置換の１価の炭化水素基を示し、より好ましくは水素を示す。

In formula (b2 ′), Z represents —O— or —CR ⁷ R ⁸ —, preferably —CR ⁷ R ⁸ —. R ^{1 to} R ⁸ each independently represent hydrogen, halogen, or an unsubstituted or substituted monovalent hydrocarbon group, preferably hydrogen or an unsubstituted monovalent hydrocarbon group, more preferably hydrogen. .

  In the above formula (b2 ′), the halogen and the unsubstituted or substituted monovalent hydrocarbon group are the halogen and the unsubstituted or substituted monovalent hydrocarbon in the formula (b-1), respectively. The group illustrated as a group can be mentioned similarly.

  Specific examples of the acid anhydride (b2) include 5-norbornene-2,3-dicarboxylic acid anhydride, 5-methyl-5-norbornene-2,3-dicarboxylic acid anhydride, and 2-methyl-5-norbornene. -2,3-dicarboxylic anhydride. Among these, 5-norbornene-2,3-dicarboxylic acid anhydride and 2-methyl-5-norbornene-2,3-dicarboxylic acid anhydride are preferable.

≪Transition metal catalyst≫
The coupling reaction between the siloxane compound (b1) and the acid anhydride (b2) is usually a hydrosilylation reaction using a transition metal catalyst. In the present invention, a known hydrosilylation catalyst that promotes the hydrosilylation reaction that proceeds during the crosslinking of the addition-crosslinkable silicon material can be preferably used.

  Specifically, as the hydrosilylation catalyst, at least one metal selected from the group consisting of platinum, rhodium, palladium, ruthenium and iridium and a compound of the metal can be used. Of these, platinum is particularly preferred.

≪Organic solvent≫
The coupling reaction between the siloxane compound (b1) and the acid anhydride (b2) is preferably performed in an organic solvent. Examples of the organic solvent include alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like.

  Examples of the alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, i-butyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, Examples include ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, and diacetone alcohol.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene and the like.
Examples of the ethers include tetrahydrofuran and dioxane.
Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone.

  Examples of the esters include ethyl acetate, propyl acetate, butyl acetate, propylene carbonate, methyl lactate, ethyl lactate, normal propyl lactate, isopropyl lactate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate.

These organic solvents may be used individually by 1 type, and may mix and use 2 or more types.
Among these organic solvents, from the viewpoint of the solubility of the above components used in the coupling reaction, organic solvents other than alcohols are preferable, ketones and aromatic hydrocarbons are more preferable, methyl ethyl ketone, methyl isobutyl ketone , Toluene and xylene are particularly preferred.

  The organic solvent can be appropriately used for the purpose of controlling the coupling reaction. When an organic solvent is used, the amount used can be appropriately set according to desired conditions.

≪Coupling reaction≫
In this coupling reaction, the siloxane compound (b1) and the acid anhydride (b2) are a hydrogen-silicon bond in the siloxane compound (b1) / a carbon-carbon double bond (molar ratio) in the acid anhydride (b2). ) Is preferably 100/1 to 1/100, more preferably 50/1 to 1/50, and particularly preferably 20/1 to 1/20.

The temperature of the coupling reaction is preferably −10 to 110 ° C., more preferably 0 to 100 ° C., and further preferably 10 to 100 ° C .; the reaction time is about 10 to 150 hr.
The coupling reaction may be carried out by charging each of the above components into a reaction vessel at once, or may be carried out while intermittently or continuously adding the other component to one component.

<Composition of composition for optical semiconductor sealing>
The composition for optical-semiconductor sealing which concerns on this invention contains the said siloxane compound (A) and the said siloxane compound (B). The siloxane compound (A) and the siloxane compound (B) are the number of moles of acid anhydride structure (acid anhydride group) in the siloxane compound (B) with respect to 1 mol of the epoxy group in the siloxane compound (A). Is preferably contained in an amount of 0.2 to 3.0, more preferably 0.3 to 2.5, and particularly preferably 0.5 to 2.0.

  Moreover, the composition for optical semiconductor encapsulation according to the present invention is preferably 1 to 10,000 parts by weight, more preferably 5 to 10,000 parts by weight of the siloxane compound (B) with respect to 100 parts by weight of the siloxane compound (A). Part, particularly preferably 5 to 1000 parts by weight.

<Other ingredients>
The composition for optical semiconductor encapsulation according to the present invention may further contain a curing agent other than the siloxane compound (B), a curing accelerator, inorganic particles, an adhesion aid and the like.

≪Other curing agents≫
In addition to the siloxane compound (B), the composition for optical semiconductor encapsulation according to the present invention is a component that is known as a curing agent for an epoxy compound or an epoxy resin (hereinafter referred to as “a curing agent”) as long as the intended effect of the present invention is not impaired. It may be further referred to as “other curing agent”.

  Other curing agents include phenols; dicyandiamides; organic hydrazides such as adipic hydrazide and phthalic hydrazide. Another hardening agent may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  In the composition for optical semiconductor encapsulation according to the present invention, the other curing agent is preferably contained in an amount of 50 parts by weight or less, based on 100 parts by weight of the siloxane compound (B), and 30 parts by weight or less. More preferably, it is included in an amount.

≪Curing accelerator≫
The composition for optical semiconductor encapsulation according to the present invention may further contain a curing accelerator. A hardening accelerator is a component which accelerates | stimulates hardening reaction of the epoxy group which the said siloxane compound (A) etc. have, and the acid anhydride group which the said siloxane compound (B) etc. have.

As the curing accelerator,
Tertiary amines: benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, triethanolamine;
Special amine: U-CAT 410 (San Apro Co., Ltd.);
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-undecylimidazole 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-sia Ethyl) -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-diamy 6- [2'-methylimidazolyl- - (1 ')] isocyanuric acid adduct of ethyl -s- triazine;
Organic phosphorus compounds: diphenylphosphine, triphenylphosphine, triphenyl phosphite;
Quaternary phosphonium salt: benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium Bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetrabutylphosphonium acetate, tetra-n-butylphosphonium o, o-diethylphosphorodithionate , Methyltributylphosphonium dimethyl phosphate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetrafluoro Rate, tetra -n- butyl phosphonium tetraphenyl borate, tetraphenyl phosphonium tetraphenyl borate, triphenyl benzyl phosphonium tetraphenyl borate, tetra -n- butyl phosphonium tetrafluoroborate;
Diazabicycloalkene: 1,8-diazabicyclo [5.4.0] undecene-7, its organic acid salt;
Organic metal compounds: zinc octylate, tin octylate, aluminum acetylacetone complex;
Quaternary ammonium salt: tetraethylammonium bromide, tetra-n-butylammonium bromide, U-CAT 18X (San Apro Co., Ltd.), the following formula (in formula (11), R _{1 to} R ₄ are each independently hydrogen, halogen, Or an unsubstituted or substituted monovalent hydrocarbon group.);

・ホウ素化合物：三フッ化ホウ素、ホウ酸トリフェニル；
・金属ハロゲン化合物：塩化亜鉛、塩化第二錫；
・潜在性硬化促進剤：ジシアンジアミドやアミンと、エポキシ樹脂との付加物などのアミン付加型促進剤などの高融点分散型潜在性硬化促進剤；前記イミダゾール類、有機リン化合物および４級フォスフォニウム塩などの硬化促進剤の表面をポリマーで被覆したマイクロカプセル型潜在性硬化促進剤；アミン塩型潜在性硬化剤促進剤；ルイス酸塩、ブレンステッド酸塩などの高温解離型の熱カチオン重合型潜在性硬化促進剤
などが挙げられる。

Boron compounds: boron trifluoride, triphenyl borate;
Metal halide compounds: zinc chloride, stannic chloride;
-Latent curing accelerator: high melting point dispersion type latent curing accelerator such as amine addition accelerator such as adduct of dicyandiamide or amine and epoxy resin; imidazoles, organophosphorus compounds and quaternary phosphonium Microcapsule type latent curing accelerator with polymer coating on the surface of curing accelerator such as salt; amine salt type latent curing accelerator; high temperature dissociation type thermal cationic polymerization type such as Lewis acid salt and Bronsted acid salt Examples include latent curing accelerators.

  Among these curing accelerators, imidazoles, quaternary phosphonium salts, diazabicycloalkenes, organometallic compounds, and quaternary ammonium salts are colorless and transparent, and a cured product that is difficult to discolor even when heated for a long time is obtained. This is preferable.

The said hardening accelerator may be used individually by 1 type, and may mix and use 2 or more types.
When using a hardening accelerator in the composition for optical semiconductor sealing which concerns on this invention, a hardening accelerator may be contained in the quantity of 0.1-20 weight part with respect to 100 weight part of siloxane compounds (B). Preferably, it is contained in an amount of 0.1 to 10 parts by weight.

≪Inorganic particles≫
The composition for optical semiconductor encapsulation according to the present invention may further contain inorganic particles.
Examples of the inorganic particles include silica particles and phosphors.

-Silica particles-
When silica particles are blended as inorganic particles, they can be used in the form of a powder or a solvent-based sol or colloid dispersed in a polar solvent such as isopropyl alcohol or a nonpolar solvent such as toluene. In the case of a solvent-based sol or colloid, the solvent may be distilled off after the silica particles are blended in the solvent. In order to improve the dispersibility of the silica particles, surface-treated silica particles may be used.

  The primary particle diameter of these silica particles is usually 0.0001 to 1 μm, preferably 0.001 to 0.5 μm, and particularly preferably 0.002 to 0.2 μm. The primary particle size of the silica particles is determined by laser diffraction using a particle size distribution measuring device (for example, Nanotrack particle size distribution measuring device UPA-150 manufactured by Nikkiso Co., Ltd.) in a state where the silica particles are dispersed in an organic solvent. Measured.

  When silica particles are used in the form of a solvent-based sol or colloid, the solid content concentration of the silica particles is usually more than 0% by weight and not more than 50% by weight, preferably 0, with respect to 100% by weight of the sol or colloid. 0.01 wt% or more and 40 wt% or less.

  Examples of the powdery silica whose surface is not treated include OX50, # 50, # 150, # 200, and # 300 manufactured by Nippon Aerosil Co., Ltd .; Examples include R972, R974, R976, RX50, RX200, RX300, RY50, RY200S, RY300, R106 manufactured by Tosoh Corporation, SS50A and SS30V manufactured by Tosoh Corporation, Silo Hovic 100 manufactured by Fuji Silysia Chemical Co., and Silo Hovic 200.

Solvent-based colloidal silica particles (solvent-dispersed colloidal silica) include alcohol-based solvent-dispersed colloidal silica such as isopropyl alcohol manufactured by Nissan Chemical Industries, ketone-based solvent-dispersed colloidal silica such as methylisobutyl, and toluene. And nonpolar solvent-dispersed colloidal silica.
Silica particles may be added together with the above components when preparing the composition for optical semiconductor encapsulation, or may be added to the mixture at any time after mixing the above components.

-Phosphor-
The composition for optical semiconductor encapsulation according to the present invention may further contain a phosphor.
As a specific example of the phosphor,
Y ₂ O ₃ : Eu ³⁺ , Y ₂ SiO ₅ : Eu ³⁺ , Y ₃ Al ₅ O ₁₂ : Eu ³⁺ , YVO ₄ : Eu ³⁺ , (Y, Gd) BO ₃ : Eu ³⁺ , Zn ₃ (PO ₄ ) ₂ : red phosphor such as Mn;
Green phosphors such as Zn ₂ SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, BaMgAl ₁₄ O ₂₃ : Mn, LaPO ₄ : (Ce, Tb), Y ₃ (Al, Ga) ₅ O ₁₂ : Tb;
Y ₂ SiO ₅ : Ce, BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , BaMgAl ₁₄ O ₂₃ : Eu ²⁺ , (Ca, Sr, Ba) ₁₀ (PO ₄ ) ₆ C ₁₂ : Eu ²⁺ , (Zn, Cd) S: blue phosphor such as Ag;
Is mentioned.

  When inorganic particles are used in the composition for optical semiconductor encapsulation according to the present invention, the inorganic particles are 0 in terms of solid content with respect to a total of 100 parts by weight of the siloxane compound (A) and the siloxane compound (B). It is preferably contained in an amount exceeding 80 parts by weight and more preferably not less than 5 parts by weight and not more than 50 parts by weight.

≪Adhesion aid≫
The composition for optical semiconductor encapsulation according to the present invention may further contain an adhesion assistant.
Examples of the adhesion assistant include epoxy group-containing polysiloxanes other than the siloxane compound (A), oxetane compounds, thiol compounds, compounds having an isocyanuric ring structure, alkoxysilanes, alkoxysilane hydrolysates, alkoxysilane hydrolysis condensates. Etc.

  Examples of the epoxy group-containing polysiloxane other than the siloxane compound (A) include an epoxy-modified product of an alkoxysilane hydrolysis condensate represented by the following formula (12), an epoxy group-containing polydimethylsiloxane not containing a silanol group, and the like. Can be mentioned.

R ¹¹ _g Si (OR ¹² ) _4-g (12)
In the formula (12), R ¹¹ and R ¹² each independently represent an unsubstituted or substituted monovalent hydrocarbon group, and g is an integer of 0 to 2. Here, as the unsubstituted or substituted monovalent hydrocarbon group, the groups exemplified as the unsubstituted or substituted monovalent hydrocarbon group in the above formula (B ′) can be similarly exemplified.

  Examples of the oxetane compound include compounds represented by any of the following formulas (O-1) to (O-10).

チオール化合物としては、３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルトリエトキシシラン、３−メルカプトプロピルトリ−ｎ−プロポキシシラン、３−メルカプトプロピルトリ−ｉ−プロポキシシラン、３−メルカプトプロピルトリ−ｎ−ブトキシシラン、３−メルカプトプロピルトリ−ｓｅｃ−ブトキシシランなどが挙げられる。

Examples of the thiol compound include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, and 3-mercaptopropyltri-n. -Butoxysilane, 3-mercaptopropyltri-sec-butoxysilane and the like.

  Examples of the compound having an isocyanuric ring structure include isocyanuric acid tris (3-trimethoxysilyl-n-propyl), isocyanuric acid tris (2-hydroxyethyl), isocyanuric acid triglycidyl, isocyanuric acid tris (2-carboxyethyl) and the like. Can be mentioned.

  As alkoxysilane, its hydrolyzate, and its hydrolysis condensate, the alkoxysilane represented by the said Formula (12), its hydrolyzate, its hydrolysis condensate, etc. are mentioned, respectively.

  Examples of the hydrolysis condensate of alkoxysilane represented by the above formula (12) include the above-mentioned single alkoxysilane condensates and condensates of two or more alkoxysilanes. Specific examples include tetramethoxysilane oligomers, tetraethoxysilane oligomers, methyltrimethoxysilane oligomers, and condensates of methyltrimethoxysilane and dimethyldimethoxysilane.

The adhesion assistant may be used alone or in combination of two or more.
When using the adhesion assistant in the composition for optical semiconductor encapsulation according to the present invention, the adhesion assistant is 0.1 to 20 weights with respect to 100 parts by weight of the mixture of the siloxane compound (A) and the siloxane compound (B). It is preferably contained in an amount of parts, more preferably 0.1 to 10 parts by weight.

[Hardened body and optical semiconductor encapsulant]
The hardening body which concerns on this invention is obtained by hardening | curing the said composition for optical semiconductor sealing. The composition for optical semiconductor sealing can be cured by a known method. For example, after applying the composition for optical semiconductor sealing on a substrate to form a coating film, the coating film is cured by heating at 100 to 180 ° C. for 3 to 13 hours to produce a cured body. Can do. Further, curing may be performed in a process (step cure) in which the temperature is raised stepwise.

  Such a cured body can be suitably used as an optical semiconductor sealing material. Examples of the optical semiconductor include LED lamps, LED chips, semiconductor lasers, photocouplers, and photodiodes. In these, the said hardening body is especially suitable as LED sealing materials, such as a LED lamp and a LED chip.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. In the examples and comparative examples, “parts” and “%” indicate “parts by weight” and “% by weight” unless otherwise specified.
Various measurement methods in Examples and Comparative Examples are shown below.

(1) GPC measurement The weight average molecular weight (Mw) of the said siloxane compound (A) and the said siloxane compound (B) was measured on the following conditions by gel permeation chromatography (GPC), and was shown as a polystyrene conversion value.
Apparatus: HLC-8120C (manufactured by Tosoh Corporation)
Column: TSK-gel Multipore H _XL- M (manufactured by Tosoh Corporation)
Eluent: THF (tetrahydrofuran), flow rate 0.5 mL / min,
Load 5.0%, 100μL

(2) Epoxy equivalent (g / eq.)
Based on JIS C2105, the epoxy equivalent (g / eq.) Of the siloxane compound (A) was measured.

(3) Weight reduction rate The compositions obtained in the following examples and comparative examples were poured into a polyimide resin container, and the weight of the composition in the container was calculated from the weight of the resin container measured in advance. Is the initial weight. The composition placed in the container was dried in an oven at 100 ° C. for 2 hours, and then heated at 150 ° C. for 3 hours to prepare a cured body. The total weight of the cured body and the container was measured, the weight of the cured body was calculated in the same manner as the initial weight, and the weight reduction ratio was calculated.

(4) Curability The compositions obtained in the following Examples and Comparative Examples were poured into a Teflon (registered trademark) petri dish so that the dry film thickness was 2 mm, dried in an oven at 100 ° C. for 2 hours, and then at 150 ° C. for 3 hours. Heated to produce a cured body. The curability of this cured product was evaluated according to the following criteria.
A: There is no fluidity and no tack.
B: There is no fluidity, but there is a slight tack.
C: It has fluidity.

(5) Transparency After coating the composition obtained in the following Examples and Comparative Examples on quartz glass so that the dry film thickness was 1 mm, the coating film was dried at 100 ° C. for 2 hours. And then heated at 150 ° C. for 3 hours to prepare a cured product. About this hardening body, the spectral transmittance of wavelength 400-700nm was measured with the ultraviolet visible spectrophotometer, and the following reference | standard evaluated.
A: Light transmittance is over 90%.
B: Light transmittance is 70 to 90%.
C: Light transmittance is less than 70%.

(6) Strength (Izod impact strength)
The compositions obtained in the following Examples and Comparative Examples were placed in a Teflon (registered trademark) container so that the length was 80 ± 2 mm, the thickness was 10 ± 0.2 mm, and the width was 4 ± 0.2 mm. It was dried at 2 ° C. for 2 hours and then heated at 150 ° C. for 3 hours to prepare a cured product. A notch is added to the cured body so that the distance is 40 ± 1 mm, the tip radius is 0.25 ± 0.05 mm, the groove angle is 45 ± 1 degree, and the remaining thickness is 8 ± 0.2 mm. A hammer lifted to an angle of 150 ° was struck and the Izod impact strength was measured.

[Synthesis Example 1 of Siloxane Compound (B) Having Acid Anhydride Structure]
In a reactor equipped with a stirrer, 68.7 parts of an acid anhydride having a norbornene skeleton (manufactured by Wako Pure Chemical Industries, Ltd., trade name: 5-norbornene-2,3-dicarboxylic acid anhydride) and tetramethyldi 31.3 parts of siloxane (manufactured by Shin-Etsu Chemical Co., Ltd., reagent name: LS7040) and 200 parts of toluene were added and stirred.

To this solution, 0.71 part of a 0.3% isopropyl alcohol solution of a platinum-divinyltetramethyldisiloxane complex was added, and an addition reaction was performed at 65 ° C. for 72 hours.
After confirming the consumption of hydrogen atoms bonded to the double bond carbon in the acid anhydride by ¹ H-NMR, the solvent was distilled off to obtain a siloxane compound (B1) having an acid anhydride structure (molecular weight 462) Got.

[Synthesis Example 2 of Siloxane Compound (B) Having Acid Anhydride Structure]
In a reactor equipped with a stirrer, 21.2 parts of an acid anhydride having a norbornene skeleton (manufactured by Wako Pure Chemical Industries, Ltd., trade name: 5-norbornene-2,3-dicarboxylic acid anhydride), and hydrogen-silicon 78.8 parts of polydimethylsiloxane having a bond at the end (manufactured by Gelest, product name: DMS-H11) and 200 parts of toluene were added and stirred.

To this solution, 0.71 part of a 0.3% isopropyl alcohol solution of a platinum-divinyltetramethyldisiloxane complex was added, and an addition reaction was performed at 65 ° C. for 96 hours.
After confirming the consumption of hydrogen atoms bonded to the double bond carbon in the acid anhydride by ¹ H-NMR, the solvent was distilled off to obtain a siloxane compound (B2) having an acid anhydride structure (weight average molecular weight). 1500).

[Example 1]
The above siloxane synthesized in Synthesis Example 1 with respect to 100 parts of polydimethylsiloxane (A1) (weight average molecular weight 1500, epoxy equivalent 360) having 2- (3,4-epoxycyclohexane-1-yl) ethyl groups at both ends. 45 parts of the compound (B1) and 0.13 part of a curing accelerator (trade name U-CAT 18X, manufactured by San Apro Co., Ltd.) were added and stirred sufficiently to obtain a composition. About the said composition, the weight decreasing rate, sclerosis | hardenability, transparency, and intensity | strength were evaluated by the said method. The evaluation results are shown in Table 1.

[Example 2, Comparative Example 1]
In Example 1, it carried out like Example 1 except having prepared the composition according to the composition of Table 1. The evaluation results are shown in Table 1.

Claims (8)

(A) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography is 1500 or less , the epoxy equivalent is 360 g / eq. Or less , and epoxy groups containing 3 to 20 carbon atoms at both ends Polydimethylsiloxane having a hydrocarbon group, and (B) a polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography is 1500 or less , and has two acid anhydride structures in the molecule, Siloxane compound represented by the formula (B ′)
In an amount such that the number of moles of the acid anhydride structure in the siloxane compound (B) with respect to 1 mole of the epoxy group in the polydimethylsiloxane (A) is 0.5 to 0.7. A composition for sealing an optical semiconductor.

[In the formula (B ′), a plurality of R ^A each independently represents an organic group containing an acid anhydride structure, a plurality of R each independently represents an unsubstituted or substituted monovalent hydrocarbon group, n Represents an integer of 0 to 1000. ] The composition for optical semiconductor encapsulation according to claim 1 , wherein the organic group containing the acid anhydride structure is an organic group represented by the following formula (b-1).

[In the formula (b-1), Z represents —O— or —CR ⁷ R ⁸ —, and R ^{1 to} R ⁸ each independently represents hydrogen, halogen, or an unsubstituted or substituted monovalent hydrocarbon group. *-Indicates a bond. ] The siloxane compound (B) is
(B1) a siloxane compound having two hydrogen-silicon bonds in the molecule and represented by the following formula (b1 ′) ;
(B2) The composition for optical semiconductor encapsulation according to claim 1 , which is obtained by reacting with an acid anhydride having a carbon-carbon double bond.

[In the formula (b1 ′), a plurality of R's each independently represents an unsubstituted or substituted monovalent hydrocarbon group, and n represents an integer of 0 to 1000. ] The composition for optical semiconductor encapsulation according to claim 3 , wherein the acid anhydride (b2) is an acid anhydride represented by the following formula (b2 ′).

[In the formula (b2 ′), Z represents —O— or —CR ⁷ R ⁸ —, and R ^{1 to} R ⁸ each independently represent hydrogen, halogen, or an unsubstituted or substituted monovalent hydrocarbon group. . ] The light according to any one of claims 1 to 4 , wherein the polydimethylsiloxane (A) has an organic group represented by any one of the following formulas (a-1) to (a-4). Semiconductor sealing composition.

[In the formula (a-1), X represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a divalent branched alkylene group having 3 to 10 carbon atoms. ]

[In Formula (a-2), X represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a divalent branched alkylene group having 3 to 10 carbon atoms. ]

[In Formula (a-3), X represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a divalent branched alkylene group having 3 to 10 carbon atoms. ]

[In Formula (a-4), X represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a divalent branched alkylene group having 3 to 10 carbon atoms. ] The hardening body obtained by hardening | curing the composition for optical semiconductor sealing in any one of Claims 1-5 . An optical semiconductor sealing material comprising the cured body according to claim 6 . The light emitting diode sealing material which consists of a hardening body of Claim 6 .