JP5698453B2 - Epoxy resin composition - Google Patents

Description

  The present invention relates to an epoxy resin composition suitable for use in electrical and electronic materials, particularly for use in optical semiconductors, and a cured product.

Conventionally, an epoxy resin composition has been employed as a sealing material for optical semiconductor elements such as LED products in terms of a balance between performance and economy. In particular, glycidyl ether type epoxy resin compositions typified by bisphenol A type epoxy resins having excellent balance of heat resistance, transparency and mechanical properties have been widely used.
However, as a result of the shortening of the emission wavelength of LED products (mainly the case of LED products emitting blue light of 480 nm or less), the sealing material is colored on the LED chip due to the influence of light of short wavelengths. However, it has been pointed out that the illuminance will eventually decrease as an LED product.
Therefore, alicyclic epoxy resins represented by 3,4-epoxycyclohexylmethyl-3 ′, 4 ′ epoxycyclohexyl carboxylate are more transparent than glycidyl ether type epoxy resin compositions having an aromatic ring. Since it is excellent, it has been actively studied as an LED sealing material. (Patent Documents 1 and 2)

  In recent years, LED products have become increasingly brighter for lighting, TV backlights, and the like, and when LEDs are turned on, they generate a lot of heat. Therefore, a resin composition using the alicyclic epoxy resin is used. Even an object causes coloring on the LED chip, and as a result, the illuminance is lowered as an LED product, leaving a problem in terms of durability. (Patent Document 3)

JP-A-9-213997 Japanese Patent No. 3618238 Tokushu 2005-100445

Because of the problem of durability of the epoxy resin, a resin having a siloxane skeleton (specifically, a skeleton having a Si—O bond) introduced as a silicone resin or a silicone-modified epoxy resin is used as a sealing material. Considerations are being made. (Patent Document 3)
In general, it is known that a resin having a siloxane skeleton introduced therein is more stable to heat and light than an epoxy resin. Therefore, when applied to the sealing material of LED products, it was said that it was superior to epoxy resin in terms of coloring on the LED chip. However, resins incorporating the siloxane skeleton are inferior in gas permeability resistance compared to epoxy resins. Therefore, when a silicone resin or a silicone-modified epoxy resin is used as the LED sealing material, coloring on the LED chip is not a problem, but there is a problem that internal components are deteriorated and coloring occurs. . In particular, when used in a living environment, various compounds are floating, and the penetration of such compounds into the interior triggers problems. For example, when used in lighting applications, gas in the environment or the like permeates the LED sealing material, so that the silver component plated on the metal lead frame, which is a component in the LED package (to increase reflectivity) Is subjected to discoloration or blackening, and ultimately the performance as an LED product is lowered.
In the market, a siloxane structure-containing epoxy resin composition having no problem in gas permeability resistance is desired.

As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention
(1)
An epoxy resin composition comprising an organopolysiloxane (A) and a polyvalent carboxylic acid (B) as essential components;
However, organopolysiloxane (A) and polyvalent carboxylic acid (B) satisfy the following conditions.
Organopolysiloxane (A):
An epoxy resin having at least a glycidyl group and / or an epoxycyclohexyl group in the molecule.
Polyvalent carboxylic acid (B):
A polyvalent carboxylic acid having two or more carboxyl groups and having an aliphatic hydrocarbon group as a main skeleton.
(2)
The epoxy resin composition according to item (1), which contains an acid anhydride (C),
(3)
Any of the preceding items (1) and (2), wherein the polyvalent carboxylic acid is a compound obtained by reacting a bifunctional or bifunctional polyhydric alcohol having 5 or more carbon atoms with a saturated aliphatic cyclic acid anhydride The epoxy resin composition according to claim 1,
(4)
Hardened | cured material formed by hardening | curing the epoxy resin composition of previous clause (3),
About.

  Since the epoxy resin composition of the present invention is excellent in corrosion gas resistance, it is extremely useful as an adhesive or sealing material for optical semiconductors (LED products, etc.) used in living environments such as lighting, among optical materials. Useful.

Hereinafter, the epoxy resin composition of the present invention will be described.
The epoxy resin composition of the present invention contains organopolysiloxane (A) and polyvalent carboxylic acid (B) as essential components.
Organopolysiloxane (A) is an epoxy resin having at least a glycidyl group and / or an epoxycyclohexyl group in the molecule, and is generally a sol--using a trialkoxysilane having a glycidyl group or an epoxycyclohexyl group as a raw material. Obtained by gel reaction.
Specifically, JP 2004-256609 A, JP 2004-346144 A, WO 2004/072150, JP 2006-8747, WO 2006/003990, JP 2006-104248, WO 2007 /. 135909, JP2004-10849, JP2004-359933, WO2005 / 100445, JP2008-174640, and the like have a three-dimensional network structure. Examples include silsesquioxane type organopolysiloxane.
The structure of the organopolysiloxane is not particularly limited. However, since a siloxane compound having a simple three-dimensional network structure is too hard, a structure that relaxes the hardness is desired. In the present invention, a block structure having the above-mentioned silsesquioxane structure obtained by a sol-gel reaction and a silicone segment in one molecule is particularly preferred (hereinafter referred to as block type siloxane compound (D)).

  The block type siloxane compound (D) is not a compound having a repeating unit in a straight chain as in a normal block copolymer, but has a network structure extending in three dimensions, with a silsesquioxane structure as a core. The chain-like silicone segment extends and becomes a structure in which it is bonded to the next silsesquioxane structure. This structure is effective in the sense of giving a balance between hardness and flexibility to the cured product of the curable composition of the present invention.

  The block type siloxane compound (D) is produced using, for example, an alkoxysilane compound (a) represented by the general formula (1) and a silicone oil (b) represented by the general formula (2) as raw materials as described below. If necessary, the alkoxysilane compound (c) represented by the general formula (3) can be used as a raw material. The chain-type silicone segment of the block-type siloxane compound (A) is formed from the silicone oil (b), and the three-dimensional networked silsesquioxane segment is an alkoxysilane (a) (optionally alkoxysilane (c) ). Hereinafter, each raw material will be described in detail.

The alkoxysilane compound (a) is represented by the following formula (1).
XSi (OR ₂ ) ₃ (1)
X in the general formula (1) is not particularly limited as long as it is an organic group having an epoxy group. For example, β-glycidoxyethyl, γ-glycidoxypropyl, γ-glycidoxybutyl and other glycidoxy having 1 to 4 carbon atoms, glycidyl group, β- (3,4-epoxycyclohexyl) ethyl group, γ -(3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycycloheptyl) ethyl group, β- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycyclohexyl) butyl group And an alkyl group having 1 to 5 carbon atoms substituted with a cycloalkyl group having 5 to 8 carbon atoms having an oxirane group such as β- (3,4-epoxycyclohexyl) pentyl group. Among these, an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group, an alkyl group having 1 to 3 carbon atoms substituted with a cycloalkyl group having 5 to 8 carbon atoms having an epoxy group, for example, β- A glycidoxyethyl group, a γ-glycidoxypropyl group, and a β- (3,4-epoxycyclohexyl) ethyl group are preferable, and a β- (3,4-epoxycyclohexyl) ethyl group is particularly preferable.

R ₂ in the general formula (1) represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. Can be mentioned. R ₂ is preferably a methyl group or an ethyl group, and particularly preferably a methyl group, from the viewpoint of reaction conditions such as compatibility and reactivity.

  Specific preferred examples of the alkoxysilane (a) include β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxy. Silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like, particularly β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane is preferred. These alkoxysilane compounds (a) may be used independently, may use 2 or more types, and can also be used together with the alkoxysilane (c) mentioned later.

Silicone oil (b) has the following formula (2)

（式中ｍは繰り返し数を表す。）

(In the formula, m represents the number of repetitions.)

Is a chain silicone oil having a silanol group at the end having a structure represented by:
In the formula of the general formula (2), a plurality of R ₃ may be the same or different from each other, and may be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or 2 to 10 carbon atoms. An alkenyl group of
Examples of the alkyl group having 1 to 10 carbon atoms include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, amyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, octyl group, 2-ethylhexyl Group, nonyl group, decyl group and the like. Among these, considering light resistance, a methyl group, an ethyl group, and a cyclohexyl group are preferable.
Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, and a xylyl group.
Examples of the alkenyl group having 2 to 10 carbon atoms include alkenyl groups such as vinyl group, 1-methylvinyl group, allyl group, propenyl group, butenyl group, pentenyl group, and hexenyl group.
R ₃ is preferably a methyl group, a phenyl group, a cyclohexyl group or an n-propyl group from the viewpoints of light resistance and heat resistance, and particularly preferably a methyl group or a phenyl group.

  M of the compound of General formula (2) shows 3-200 by an average value, Preferably it is 3-100, More preferably, it is 3-50. When m is less than 3, the cured product becomes too hard and the low elastic modulus characteristics are deteriorated. If m exceeds 200, the mechanical properties of the cured product tend to deteriorate, which is not preferable.

The weight average molecular weight (Mw) of the silicone oil (b) is preferably in the range of 300 to 18,000 (measured value by gel permeation chromatography (GPC)). Among these, those having a molecular weight of 300 to 10,000 are preferable in consideration of the elastic modulus at low temperature, and those having a molecular weight of 300 to 5,000 are more preferable in consideration of compatibility at the time of forming the composition. 1,000 is preferred. If the weight average molecular weight is less than 300, the properties of the chain silicone portion of the characteristic segment are difficult to be obtained, and the properties as a block type may be impaired. If it exceeds 18,000, a severe layer separation structure will be formed. When used as a material, the permeability becomes poor, making it difficult to use. In the present invention, the molecular weight of the silicone oil (b) can be calculated by polystyrene conversion and weight average molecular weight (Mw) measured under the following conditions using GPC.
Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

  The kinematic viscosity of the silicone oil (b) is preferably in the range of 10 to 200 cSt, more preferably 30 to 90 cSt. If it is less than 10 cSt, the viscosity of the block type siloxane compound (D) may be too low to be suitable as an optical semiconductor sealing agent. If it exceeds 200 cSt, the viscosity of the block type siloxane compound (D) may be Is unfavorable because it tends to cause an adverse effect on workability.

  Specific examples of preferable silicone oil (b) include the following product names. For example, as manufactured by Toray Dow Corning Silicone, PRX413, BY16-873, as manufactured by Shin-Etsu Chemical Co., Ltd., X-21-5841, KF-9701, as manufactured by Momentive, XC96-723, TSR160, YR3370, YF3800 , XF3905, YF3057, YF3807, YF3802, YF3897, YF3804, XF3905, manufactured by Gelest, DMS-S12, DMS-S14, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS -S33, DMS-S35, DMS-S42, DMS-S45, DMS-S51, PDS-0332, PDS-1615, PDS-9931 and the like. Among these, PRX413, BY16-873, X-21-5841, KF-9701, XC96-723, YF3800, YF3804, DMS-S12, DMS-S14, DMS-S15, DMS-S21 from the viewpoint of molecular weight and kinematic viscosity PDS-1615 is preferred. Among these, X-21-5841, XC96-723, YF3800, YF3804, DMS-S14, and PDS-1615 are particularly preferable from the viewpoint of molecular weight in order to give the silicone segment flexibility characteristics. These silicone oils (b) may be used alone or in combination of two or more.

Next, the alkoxysilane (c) used if necessary will be described in detail. The alkoxysilane (c) has a structure of the following formula (3).
R ₄ (OR ₅ ) ₃ (3)
(In the formula, R ₄ represents a methyl group or a phenyl group.)

R ₅ in the general formula (3) represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. Can be mentioned. R ₅ is preferably a methyl group or an ethyl group from the viewpoint of reaction conditions such as compatibility and reactivity.

  Specific examples of preferred alkoxysilane (c) include methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and phenyltriethoxysilane. Of these, methyltrimethoxysilane and phenyltrimethoxysilane are preferred.

  In the present invention, the alkoxysilane (c) adjusts the molecular weight of the block-type siloxane compound (D), the compatibility with the composition, the heat resistance of the cured product, light resistance, low moisture permeability, low gas permeability, and the like. Therefore, it can be used in combination with alkoxysilane (a).

  When using alkoxysilane (c), it is preferable to use alkoxysilane (c) in the range of 5-70 mol% among the total mol of alkoxysilane (a) and (c), and 5-50 mol% is further. Preferably, 10 to 40 mol% is particularly preferable. If it is more than 70 mol%, the crosslink density of the cured product is lowered and the mechanical strength is lowered, which is not preferable.

As a reaction ratio of alkoxysilane (a), silicone oil (b), and alkoxysilane (c), alkoxysilane (a) (and used as necessary) with respect to 1 equivalent of silanol group of silicone oil (b). It is preferable to carry out the reaction between 1.5 and 200, preferably 2 to 200, particularly preferably 2 to 100, with the alkoxy group in alkoxysilane (c)) as an equivalent value.
When the equivalent value exceeds 200, the cured product using the block-type siloxane compound (D) becomes too hard and the desired low elastic modulus characteristic is lowered.

Hereinafter, a preferred method for producing the block type siloxane compound (D) will be specifically described.
As a manufacturing method of block type siloxane compound (D), it is preferable to pass through the manufacturing process shown by the following (i) and (ii).
Production step (i): Step of dealcoholization condensation of silanol-terminated silicone oil (b) and alkoxysilane-containing alkoxysilane (a) (and alkoxylane (c)) Production step (ii): Alcohol added with water Step of performing hydrolytic condensation between alkoxy groups of silane (a) (and alkoxysilane (c)) The production steps (i) and (ii) may be carried out in any order as long as they pass through the respective steps. Absent.

Specific examples of preferred production methods include the following three production methods.
<Manufacturing method (I)>
First, as a production step (i), the alkoxysilane modified product is obtained by modifying the terminal of the silicone oil with an alkoxysilane by a dealcoholization condensation reaction between the silicone oil (b) and the alkoxysilane (a) (and the alkoxysilane (c)). The step of obtaining (d) is performed.
Next, water is added to the alkoxysilane modified body (d) of the alkoxysilane (a) (and alkoxysilane (c)) and the silicone oil obtained in the manufacturing process (i) as the manufacturing process (ii), and the alkoxy groups are bonded together. A method for producing a block-type siloxane compound (D) by undergoing a step of performing a hydrolytic condensation reaction.
<Manufacturing method (b)>
First, as a production step (ii), a silsesquioxane having an alkoxy group in the molecule (by carrying out a hydrolysis-condensation reaction between alkoxy groups by adding water of alkoxysilane (a) (and alkoxysilane (c)) ( Step e) is obtained.
Next, through a step of dealcoholization condensation reaction between the alkoxy group and the silanol group remaining in the silsesquioxane structure by the reaction of the silicone oil (b) and the silsesquioxane (e) as the production step (i), Method for producing block-type siloxane compound (D) <Production method (c)>
First, as a production process (i), the alkoxysilane-modified product (i) is obtained by modifying the silicone oil terminal with alkoxysilane by a dealcoholization condensation reaction between silicone oil (b) and alkoxysilane (a) (and alkoxysilane (c)). After d), water is added to the system, and the alkoxysilane (a) (and alkoxysilane (c)) remaining as the production step (ii) in one pot, and the alkoxy group of the alkoxysilane-modified product (d) Method for producing block-type siloxane compound (D) by carrying out hydrolysis-condensation reaction between each other

In the present invention, from the viewpoint of shortening the production process, it is preferable to use the above production method (c) in which the reaction is sequentially carried out in one pot.
Hereinafter, the production method (c) will be described more specifically.
When the reaction is carried out in one pot, the silanol having an alkoxy group formed in the production step (ii) is performed in the reverse order of the production method (c) described above, that is, when the production step (ii) is performed after the production step (ii). There is a high possibility that the sesquioxane oligomer and the silicone oil (b) are not compatible with each other, the dealcoholization condensation polymerization does not proceed in the subsequent production step (i), and the silicone oil is left behind. On the other hand, if a method in which the production step (ii) is performed in one pot after the production step (i) as in the production method (c) is used, the phase between the silicone oil (b) and the alkoxysilane (a) or (c) Since the solubility is relatively high, the problem that the reaction does not proceed without compatibility as described above can be avoided. Furthermore, since a large amount of unreacted low-molecular alkoxysilane is present with respect to the silanol group, it is preferable from the viewpoint of reactivity. When the reaction is carried out in one pot, first, in the production step (i), the silicone oil (b) and the alkoxysilane (a) (and the alkoxysilane (c)) are subjected to dealcohol condensation, and the terminal of the silicone oil is modified with alkoxysilyl. A modified alkoxysilane (d) is obtained. Since water is not added in the production step (i), hydrolysis condensation between alkoxy groups does not occur, and when the reaction is performed using 3 equivalents or more of alkoxy groups per 1 equivalent of silanol groups, the alkoxysilane modification The body (d) is considered to exist in a structure represented by the following formula (4).

(In the formula (4), R ₂ , R ₃ and m have the same meaning as described above, and R ₆ represents X or R _4. )

  In the production process (i), when an alkoxy group is reacted in an amount less than 1.0 equivalent with respect to 1 equivalent of a silanol group, since no alkoxy group exists at the end of the production process (i), the process proceeds to the production process (ii). When the alkoxy group is not reacted and the alkoxy group is reacted between 1.0 and 1.5 equivalents, two or more alkoxy groups in the alkoxysilane (a) (and the alkoxysilane (c)) are converted into silanol of the silicone oil (b). It will react with the group, and at the end of the production step (i), it becomes a polymer and gelation occurs. For this reason, it is necessary to make an alkoxy group react with 1.5 equivalent or more with respect to 1 equivalent of silanol groups. From the viewpoint of reaction control, 2.0 equivalents or more are preferable.

After completion of the production step (i), water is added as it is to carry out hydrolysis condensation between alkoxy groups (production step (ii)). Further, in the production step (ii), the following reactions (I) to (III) occur.
(I) Condensation reaction between alkoxy groups of alkoxysilane (a) (and alkoxysilane (c)) remaining in the system.
(II) A condensation reaction between alkoxy groups of the alkoxysilane-modified product (d) obtained in the production step (i) and the alkoxysilane (a) (and the alkoxysilane (c)).
(III) Condensation reaction between alkoxy groups of the partial condensate of alkoxysilane modified (d) obtained in production step (i) and alkoxysilane (a) (and alkoxysilane (c)) produced in (I) .
In the production step (ii), the above reaction occurs in combination, and the formation of the silsesquioxane segment and the condensation with the silicone oil-derived chain silicone segment are simultaneously performed.

Although the production of the block type siloxane compound (D) can be carried out without a catalyst, the reaction progresses slowly with no catalyst, and it is preferably carried out in the presence of a catalyst from the viewpoint of shortening the reaction time. As the catalyst that can be used, any compound that exhibits acidity or basicity can be used. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and oxalic acid. Examples of basic catalysts include sodium hydroxide, potassium hydroxide, lithium hydroxide, alkali metal hydroxides such as cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. Inorganic bases such as alkali metal carbonates, and organic bases such as ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used. Among these, an inorganic base is particularly preferable in terms of easy catalyst removal from the product, and sodium hydroxide and potassium hydroxide are particularly preferable. The amount of the catalyst added is usually 0.001 to 7.5% by weight, preferably 0.01 to 5% by weight, based on the total weight of alkoxysilane (a) (and alkoxysilane (c)) in the reaction system. is there.
As a method for adding the catalyst, it is added directly or used in a state dissolved in a soluble solvent or the like. Among them, it is preferable to add the catalyst in a state in which the catalyst is dissolved in advance in alcohols such as methanol, ethanol, propanol and butanol. At this time, the addition as an aqueous solution using water or the like, as described above, causes the condensation of alkoxysilane (a) (and alkoxysilane (c)) to proceed unilaterally, and the silsesquioxy produced thereby. The sun oligomer and the silicone oil (b) may not be compatible with each other and may become cloudy.

  The production of the block type siloxane compound (D) can be carried out without a solvent or in a solvent. Moreover, a solvent can also be added in the middle of a manufacturing process. The solvent for use is not particularly limited as long as it is a solvent that dissolves alkoxysilane (a), alkoxysilane (c), silicone oil (b), and alkoxysilane-modified product (d). Examples of such solvents include aprotic polar solvents such as dimethylformamide, dimethylacetamide, and tetrahydrofuran, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone, ethyl acetate, butyl acetate, ethyl lactate, and butanoic acid. Examples thereof include esters such as isopropyl, alcohols such as methanol, ethanol, propanol and butanol, hydrocarbons such as hexane, cyclohexane, toluene and xylene. In the present invention, reaction in alcohols is preferable from the viewpoint of reaction control, and methanol and ethanol are more preferable. The amount of the solvent used is not particularly limited as long as the reaction proceeds smoothly, but the total weight of the alkoxysilane (a) (and alkoxysilane (c)) and silicone oil (b) compounds is 100 parts. On the other hand, usually about 0 to 900 parts by weight are used. The reaction temperature is usually 20 to 160 ° C, preferably 40 to 140 ° C, particularly preferably 50 to 150 ° C, although it depends on the amount of catalyst. Moreover, reaction time is 1 to 40 hours normally in each manufacturing process, Preferably it is 5 to 30 hours.

  After completion of the reaction, the catalyst is removed by quenching and / or washing with water as necessary. When washing with water, depending on the type of solvent used, it is preferable to add a solvent that can be separated from water. Preferred solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone, esters such as ethyl acetate, butyl acetate, ethyl lactate and isopropyl butanoate, hydrocarbons such as hexane, cyclohexane, toluene and xylene. Can be illustrated.

In this reaction, the catalyst may be removed only by washing with water, but the reaction is carried out under acidic or basic conditions. It is preferable to remove the adsorbent by filtration after adsorbing the catalyst using
Any compound that is acidic or basic can be used for the neutralization reaction. Examples of the compound exhibiting acidity include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and oxalic acid. Examples of compounds showing basicity include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate. Inorganic bases such as alkali metal carbonates, phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, polyphosphates, phosphates such as sodium tripolyphosphate, ammonia, triethylamine, diethylenetriamine, n-butylamine, Organic bases such as dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used. Among these, in particular, inorganic bases or inorganic acids are preferable because they can be easily removed from the product, and phosphates that can more easily adjust the pH to near neutral are more preferable.

Examples of the adsorbent include activated clay, activated carbon, zeolite, inorganic / organic synthetic adsorbent, ion exchange resin, and the like, and specific examples include the following products.
As the activated clay, for example, Toshin Kasei Co., Ltd., activated clay SA35, SA1, T, R-15, E, Nikkanite G-36, G-153, G-168, manufactured by Mizusawa Chemical Industry, Galeon Earth, Mizuka Ace, etc. are listed. As the activated carbon, for example, CL-H, Y-10S, Y-10SF manufactured by Ajinomoto Fine-Techno Co., Ltd., S, Y, FC, DP, SA1000, K, A, KA, M, CW130BR are manufactured by Phutamura Chemical Co., Ltd. , CW130AR, GM130A, and the like. Examples of zeolite include, for example, molecular sieves 3A, 4A, 5A, and 13X, manufactured by Union Showa. As a synthetic adsorbent, for example, Kyoward 100, 200, 300, 400, 500, 600, 700, 1000, 2000 manufactured by Kyowa Chemical Co., Ltd., Amberlist 15JWET, 15DRY, manufactured by Rohm and Haas Co., Ltd. 16WET, 31WET, A21, Amberlite IRA400JCl, IRA403BLCl, IRA404JCl, Dow Chemical Co., Dowex 66, HCR-S, HCR-W2, MAC-3 and the like can be mentioned.
The adsorbent is added to the reaction solution, followed by treatment such as stirring and heating to adsorb the catalyst, and then the adsorbent is filtered and the residue is washed with water to remove the catalyst and adsorbent.

  After completion of the reaction or after quenching, it can be purified by conventional separation and purification means other than washing with water and filtration. Examples of the purification means include column chromatography, vacuum concentration, distillation, extraction and the like. These purification means may be performed singly or in combination.

  When the reaction is performed using a solvent mixed with water as a reaction solvent, the reaction solvent mixed with water is removed from the system by distillation or vacuum concentration after quenching, and then washed with a solvent that can be separated from water. It is preferable.

  After washing with water, the block siloxane compound (D) can be obtained by removing the solvent by vacuum concentration or the like.

The appearance of the block-type siloxane compound (D) thus obtained is usually colorless and transparent and is a liquid having fluidity at 25 ° C. The molecular weight is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,500 to 6,000 as the weight average molecular weight measured by GPC. When the weight average molecular weight is less than 800, the heat resistance may be lowered. When the weight average molecular weight is more than 20,000, the viscosity is increased and the workability is adversely affected. The molecular weight is adjusted by the equivalent ratio of alkoxysilane (a) (and alkoxysilane (c)) and silicone oil (b), the molecular weight of silicone oil (b), the amount of water added during the reaction, the reaction time, and the reaction temperature. Is possible.

The weight average molecular weight is a polystyrene-reduced weight average molecular weight (Mw) measured using GPC under the following conditions.
Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

  The epoxy equivalent of the block type siloxane compound (D) (measured by the method described in JIS K-7236) is preferably 300 to 1,600 g / eq, more preferably 400 to 1,000 g / eq, The thing of 450-900 g / eq is especially preferable. When the epoxy equivalent is less than 300 g / eq, the cured product is hard and the elastic modulus tends to be too high, and when it exceeds 1,600 g / eq, the mechanical properties of the cured product tend to deteriorate.

  The viscosity of the block-type siloxane compound (D) (E-type viscometer, measured at 25 ° C.) is preferably 50 to 20,000 mPa · s, more preferably 500 to 10,000 mPa · s, particularly 800 to 5 1,000 mPa · s is preferred. If the viscosity is less than 50 mPa · s, the viscosity may be too low to be suitable for use as an optical semiconductor encapsulant, and if it exceeds 20,000 mPa · s, the viscosity may be too high and workability may be poor. is there.

The proportion of silicon atoms bonded to three oxygens derived from silsesquioxane in the block-type siloxane compound (D) is preferably from 5 to 50 mol%, more preferably from 8 to 30 mol%, 10-20 mol% is especially preferable. When the ratio of silicon atoms bonded to three oxygens derived from silsesquioxane to all silicon atoms is less than 5 mol%, the cured product tends to be too soft as a characteristic of the chain silicone segment, and surface tack There are concerns about injury. On the other hand, if it exceeds 50 mol%, the cured product becomes too hard as a feature of the silsesquioxane segment, which is not preferable. This ratio can be determined by the equivalent ratio of alkoxysilane (a) (and alkoxysilane (c)) and silicone oil (b).
The proportion of silicon atoms present can be determined by ¹ H NMR, ²⁹ Si NMR, elemental analysis, etc. of the block siloxane compound (D).

The polyvalent carboxylic acid (B) is a compound having at least two or more carboxyl groups and having an aliphatic hydrocarbon group as a main skeleton.
As the polyvalent carboxylic acid (B), a bifunctional to hexafunctional carboxylic acid is preferable, and a compound obtained by a reaction of a C6-C6 bifunctional polyhydric alcohol and an acid anhydride is more preferable. Furthermore, the polycarboxylic acid whose said acid anhydride is a saturated aliphatic cyclic acid anhydride is preferable.
As the 2- to 6-functional polyhydric alcohol, the alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1.3-propanediol, neopentyl glycol, Diols such as tricyclodecane dimethanol and norbornenediol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, pentaerythritol, ditrimethylo Tetraols such as propane, and the like hexaol such as dipentaerythritol.

  Particularly preferred alcohols are alcohols having 5 or more carbon atoms, particularly 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 2, Compounds such as 4-diethylpentanediol, 2-ethyl-2-butyl-1.3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol are preferred, and 2-ethyl-2-butyl-1. Alcohols having a branched chain structure or a cyclic structure such as 3-propanediol, neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, norbornenediol are more preferable.

Examples of acid anhydrides include methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane- 2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and the like are preferable, Of these, methylhexahydrophthalic anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride are preferable.
Although there is no particular designation as a condition for the addition reaction, one specific reaction condition is that the acid anhydride and polyhydric alcohol are reacted in a non-catalytic and solvent-free condition at 40 to 150 ° C. and heated to react. After completion, take it out as it is. It is a technique. However, it is not limited to this reaction condition.

  As the polyvalent carboxylic acid (B), in particular, the following formula (5)

（式中、複数存在するＱは、水素原子、メチル基、カルボキシル基の１種以上を表す。Ｐは前述の多価アルコール由来の炭素数２〜２０の鎖状、環状の脂肪族基である。ｎは多価アルコールの価数を表す。）
で表される化合物が好ましい。

(In the formula, multiple Qs represent one or more of a hydrogen atom, a methyl group, and a carboxyl group. P is a chain-like, cyclic aliphatic group having 2 to 20 carbon atoms derived from the aforementioned polyhydric alcohol. N represents the valence of the polyhydric alcohol.)
The compound represented by these is preferable.

The epoxy resin composition of the present invention preferably contains an acid anhydride (C). Specific examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride Acid, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3- And acid anhydrides such as dicarboxylic acid anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride.
In particular, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid An acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and the like are preferable.
Particularly preferably, the following formula (6)

（式中、Ｒ^３は、水素原子、メチル基、カルボキシル基の１種以上を表す。）
で表されるヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、シクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物が好ましく、中でもメチルヘキサヒドロ無水フタル酸、シクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物が好ましい。

(In the formula, R ³ represents one or more of a hydrogen atom, a methyl group, and a carboxyl group.)
And preferably hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride represented by the formula: methylhexahydrophthalic anhydride, cyclohexane-1,3, 4-Tricarboxylic acid-3,4-anhydride is preferred.

When using an acid anhydride (C), it is preferable that the use ratio with polyvalent carboxylic acid (B) is the following range.

W1 / (W1 + W2) = 0.05-0.70

However, W1 shows the mixing | blending weight part of polyhydric carboxylic acid (B), W2 shows the mixing | blending weight part of an acid anhydride (C). The range of W1 / (W1 + W2) is more preferably 0.05 to 0.60, still more preferably 0.10 to 0.55, and particularly preferably 0.15 to 0.4. If it is less than 0.05, the volatilization of the acid anhydride tends to increase during curing, which is not preferable. If it exceeds 0.70, the viscosity becomes high and handling becomes difficult.

  The epoxy resin composition of the present invention contains an organopolysiloxane (A) as an epoxy resin, a polycarboxylic acid (B) as an essential component as a curing agent, and an acid anhydride (C) as an optional component. Epoxy resins and other curing agents can also be included.

  When other epoxy resins are used in combination, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 60% by weight or more, particularly preferably 70% by weight or more.

  Examples of other epoxy resins that can be used include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins, and the like. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetaldehyde Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols Solid or liquid epoxy resins such as chemical compounds, alicyclic epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins and the like are not limited thereto. These may be used alone or in combination of two or more.

In particular, the epoxy resin composition of the present invention is mainly used for optical applications. When used for optical applications, the combined use of alicyclic epoxy resins is preferred. In the case of an alicyclic epoxy resin, a compound having an epoxycyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is particularly preferable.
These epoxy resins include esterification reaction of cyclohexene carboxylic acid and alcohols or esterification reaction of cyclohexene methanol and carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980), etc.) Described), or Tyschenko reaction of cyclohexene aldehyde (method described in JP-A-2003-170059, JP-A-2004-262871, etc.), and further transesterification of cyclohexene carboxylic acid ester (JP-A-2006-052187). And the like, which are obtained by oxidizing a compound that can be produced by the method described in Japanese Patent Publication No.
The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentane. Diol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1.3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol, etc. Diols, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, triols such as 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol, ditrimethylolpropane, etc. And the like. Examples of carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.

Furthermore, the acetal compound by the acetal reaction of a cyclohexene aldehyde derivative and an alcohol form is mentioned.
Specific examples of these epoxy resins include ERL-4221, UVR-6105, ERL-4299 (all trade names, all manufactured by Dow Chemical), Celoxide 2021P, Eporide GT401, EHPE3150, EHPE3150CE (all trade names, all Daicel). (Chemical Industry) and dicyclopentadiene diepoxide, and the like, but are not limited to these (Reference: Review Epoxy Resin Basic Edition I p76-85).
These may be used alone or in combination of two or more.

When other curing agents are used in combination as the curing agent, the proportion of the total amount of the polyvalent carboxylic acid (B) and the acid anhydride (C) in the total curing agent is preferably 30% by weight or more, particularly 40% by weight. The above is preferable.
Examples of the curing agent that can be used in combination include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Specific examples of curing agents that can be used include amines and polyamide compounds (diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from ethylenediamine and dimer of linolenic acid, etc.) , Reaction product of acid anhydride and silicone alcohol (phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, anhydrous Nadic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] Hep Reaction products of acid anhydrides such as cyclohexane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and silicone alcohols such as carbinol-modified silicone ), Polyhydric phenols (bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, Phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydride Xylbenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl)- 1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4′-bis (chloromethyl) benzene, 1,4′-bis (methoxymethyl) benzene and the like Polycondensates and modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, condensates of terpenes and phenols), and others (imidazole, trifluoroborane-amine complexes, guanidine derivatives, etc.) But, It is not limited to these. These may be used alone or in combination of two or more.

  In the epoxy resin composition of the present invention, the blending ratio of the epoxy resin and the curing agent is preferably 0.7 to 1.2 equivalents of the curing agent with respect to 1 equivalent of the epoxy groups of all epoxy resins. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

  In the epoxy resin composition of the present invention, a curing catalyst can be used together with the curing agent. Specific examples of the curing accelerator that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole. 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methyl Imidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2 ′ -Methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxy Various imidazoles of methylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and imidazoles and phthalic acid, isophthalic acid, Salts with polyvalent carboxylic acids such as terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4.0) undecene Diaza compounds such as -7 and their teto Salts such as phenyl borate and phenol novolak, salts with the above polycarboxylic acids or phosphinic acids, ammonium salts such as tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide, triphenylphosphine, tri (toluyl) Phosphines such as phosphine, tetraphenylphosphonium bromide and tetraphenylphosphonium tetraphenylborate, phosphonium compounds, phenols such as 2,4,6-trisaminomethylphenol, metal compounds such as amine adducts and tin octylate, and the like Examples thereof include a microcapsule-type curing catalyst in which a curing catalyst is used as a microcapsule. Which of these curing catalysts is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions. A curing catalyst is normally used in 0.001-15 weight part with respect to 100 weight part of epoxy resins.

  The epoxy resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric acid esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes A phosphorus-containing product obtained by reacting with Poxy compounds, red phosphorus and the like can be mentioned, and phosphoric esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The phosphorus-containing compound content is preferably phosphorus-containing compound / total epoxy resin = 0.1 to 0.6 (weight ratio). If it is 0.1 or less, the flame retardancy is insufficient, and if it is 0.6 or more, there is a concern that it may adversely affect the hygroscopicity and dielectric properties of the cured product.

  Furthermore, a binder resin can also be mix | blended with the epoxy resin composition of this invention as needed. Examples of the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. However, it is not limited to these. The blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 100 parts by weight in total of the epoxy resin and the curing agent, 0.05 to 20 parts by weight is used as necessary.

  If necessary, an inorganic filler can be added to the epoxy resin composition of the present invention. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These fillers may be used alone or in combination of two or more. The content of these inorganic fillers is 0 to 95% by weight in the epoxy resin composition of the present invention. Furthermore, a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, various compounding agents such as pigments, and various thermosetting resins are added to the epoxy resin composition of the present invention. be able to.

  When the epoxy resin composition of the present invention is used for an optical material, particularly an optical semiconductor encapsulant, as the particle size of the inorganic filler used, the transparency can be improved by using a nano-order level filler. It is possible to supplement mechanical strength without hindering. As a standard for the nano-order level, it is preferable from the viewpoint of transparency to use a filler having an average particle size of 500 nm or less, particularly an average particle size of 200 nm or less.

When the epoxy resin composition of the present invention is used for an optical material, particularly an optical semiconductor encapsulant, a phosphor can be added as necessary. For example, the phosphor has a function of forming white light by absorbing part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in advance in the curable resin composition, the optical semiconductor is sealed. There is no restriction | limiting in particular as fluorescent substance, A conventionally well-known fluorescent substance can be used, For example, rare earth element aluminate, thio gallate, orthosilicate, etc. are illustrated. More specifically, phosphors such as a YAG phosphor, a TAG phosphor, an orthosilicate phosphor, a thiogallate phosphor, and a sulfide phosphor can be mentioned, and YAlO ₃ : Ce, Y ₃ Al ₅ O ₁₂ : Ce, Y ₄ Al ₂ O ₉ : Ce, Y ₂ O ₂ S: Eu, Sr ₅ (PO ₄ ) ₃ Cl: Eu, (SrEu) O.Al ₂ O _{3 and the} like are exemplified. As the particle size of the phosphor, those having a particle size known in this field are used, and the average particle size is preferably 1 to 250 μm, particularly preferably 2 to 50 μm. When using these fluorescent substance, the addition amount is 1-80 weight part with respect to 100 weight part with respect to the resin component, Preferably, 5-60 weight part is preferable.

  When the epoxy resin composition of the present invention is used for an optical material, particularly an optical semiconductor encapsulant, thixo including silica fine powder (also called Aerosil or Aerosol) is used for the purpose of preventing sedimentation of various phosphors upon curing. A tropicity-imparting agent can be added. Examples of such silica fine powder include Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R972, Aerosil R974, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil Aerosil R805, RY200, RX200 (made by Nippon Aerosil Co., Ltd.), etc. are mentioned.

The epoxy resin composition of the present invention contains an optical material, particularly an optical semiconductor encapsulant, which contains an amine compound as a light stabilizer or a phosphorus compound and a phenol compound as an antioxidant for the purpose of preventing coloring. Can do.
Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-6- Totramethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3 , 9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed ester, decanedioic acid bis (2,2,6 , 6-Tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6, -tetrame Ru-4-piperidyl methacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy -2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] bu Lumalonate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, N, N ′, N ", N"'-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl)- 4,7-diazadecane-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexa Polycondensate of methylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-Triazine- , 4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], dimethyl succinate And 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7-oxa- 3,20-diazadispiro [5 · 1 · 11 · 2] heneicosan-21-one, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl) -dodecyl ester / tetradecyl ester N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa 3,20-diazadispiro [5,1,11,2] heneicosane-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11,2] -Heneicosane-20-propanoic acid dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 2,2,6,6-tetramethyl-4-piperidinol higher fatty acid ester, 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) Hindered amines such as octabenzone, benzophenone compounds such as octabenzone, 2- (2H-benzotriazol-2-yl) -4- (1,1,3, -Tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimido-methyl) -5-methylphenyl Benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazole, Reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol, 2- (2H-benzotriazol-2-yl)- Benzotriazole compounds such as 6-dodecyl-4-methylphenol, 2,4 Benzoate series such as di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5 Examples include triazine compounds such as [(hexyl) oxy] phenol, and hindered amine compounds are particularly preferable.

The following commercially available products can be used as the amine compound that is the light stabilizer.
The commercially available amine compound is not particularly limited. 62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like.

  The phosphorus compound is not particularly limited, and for example, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Dicyclohexylpentaerythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) Hosuf Ite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butyl) Phenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-ethylidenebis (4-methyl-6-tert-butyl) Phenyl) (2-tert-butyl-4-methylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4 ′ -Biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenyl Range phosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylene diphospho Knight, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis ( 2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butyl) Enyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl -Phenylphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl Examples include phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate and the like.

  A commercial item can also be used for the said phosphorus compound. It does not specifically limit as a phosphorus compound marketed, For example, as a product made from ADEKA, Adeastab PEP-4C, Adeastab PEP-8, Adeastab PEP-24G, Adeastab PEP-36, Adeastab HP-10, Adeastab 2112, Adeastab 260 Adasterast 522A, Adasterab 1178, Adasterab 1500, Adasterab C, Adasterab 135A, Adasterab 3010, Adasterab TPP, and the like.

  The phenol compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol and n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,4-di-tert-butyl-6-methylphenol, 1,6-hexanediol-bis -[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythrine Lithyl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis- [2- [3- (3-tert-butyl-4-hydroxy-5- Methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol-bis [3- (3-t-butyl-5 -Methyl-4-hydroxyphenyl) propionate], 2,2'-butylidenebis (4,6-di-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) 2), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenol acrylate, 2- [1- (2-hydroxy-3,5-di-) tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6) -Tert-butylphenol), 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,4-di-tert-pentylphenol, 4,4'-thiobis (3-methyl-6) -Tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), bis- [3 3-bis- (4′-hydroxy-3′-tert-butylphenyl) -butanoic acid] -glycol ester, 2,4-di-tert-butylphenol, 2,4-di-tert-pentylphenol, 2 -[1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, bis- [3,3-bis- (4'-hydroxy- 3'-tert-butylphenyl) -butanoic acid] -glycol ester and the like.

  A commercial item can also be used for the said phenolic compound. There are no particular limitations on the commercially available phenolic compounds. For example, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114 IRGANOX 1098, Adekas 1520L AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, ADK STAB AO-330, SUMITOMO CHEMICAL CO., LTD., Sumilizer GA-80, Sumizer MDP-S, Sumili er BBM-S, Sumilizer GM, Sumilizer GS (F), and the like Sumilizer GP.

  In addition, commercially available additives can be used as an anti-coloring agent for the resin. For example, THINUVIN 328, THINUVIN 234, THINUVIN 326, THINUVIN 120, THINUVIN 477, THINUVIN 479, CHIMASSORB 2020FDL, CHIMASSORB 119FL and the like can be cited as those manufactured by Ciba Specialty Chemicals.

  It is preferable to contain at least one of the phosphorus compounds, amine compounds, and phenol compounds, and the amount of the compound is not particularly limited, but is 0.005 with respect to the epoxy resin composition of the present invention. The range is ˜5.0% by weight.

  The epoxy resin composition of this invention is obtained by mixing each component uniformly. The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, an epoxy resin component, a curing agent component, and a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, a compounding agent, and the like, if necessary, uniformly using an extruder, kneader, roll, planetary mixer, etc. Mix thoroughly until the epoxy resin composition is obtained. If the resulting epoxy resin composition is liquid, the substrate is impregnated with a potting or casting, or poured into a mold and cast. Or cured by heating. When the obtained epoxy resin composition is solid, it is molded using a cast after casting or a transfer molding machine, and further cured by heating. The curing temperature and time are 80 to 200 ° C. and 2 to 10 hours. As a curing method, curing can be performed at a high temperature at a stretch, but it is preferable to increase the temperature stepwise to advance the curing reaction. Specifically, initial curing is performed between 80 and 150 ° C., and post-curing is performed between 100 and 200 ° C. As the curing stage, the temperature is preferably divided into 2 to 8 stages, more preferably 2 to 4 stages.

  Further, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. to obtain a curable resin composition varnish, which contains glass fiber, -Making the cured product of the epoxy resin composition of the present invention by hot press molding a prepreg obtained by impregnating a base material such as bon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating. Can do. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the epoxy resin composition of the present invention and the solvent. Moreover, the epoxy resin hardened | cured material which contains a carbon fiber by a RTM system with a liquid composition can also be obtained.

Moreover, the epoxy resin composition of this invention can also be used as a film type sealing composition. When obtaining such a film-type resin composition, the curable resin composition of the present invention is coated on the release film with the varnish, the solvent is removed under heating, and a B-stage adhesive is formed. Get. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like, and a batch film sealing of an optical semiconductor.
Next, the case where the epoxy resin composition of the present invention is used as an optical semiconductor sealing material or die bonding material will be described in detail.

  When the epoxy resin composition of the present invention is used as a sealing material or die bond material for an optical semiconductor such as a high-intensity white LED, an addition of an epoxy resin, a curing agent, a coupling agent, an antioxidant, a light stabilizer, etc. An epoxy resin composition is prepared by thoroughly mixing the materials, and is used as a sealing material or as both a die bond material and a sealing material. As a mixing method, a kneader, a three-roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill or the like is used to mix at room temperature or warm.

  Optical semiconductor elements such as high-intensity white LEDs are generally GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN laminated on a substrate of sapphire, spinel, SiC, Si, ZnO or the like. Such a semiconductor chip is bonded to a lead frame, a heat sink, or a package using an adhesive (die bond material). There is also a type in which a wire such as a gold wire is connected to pass an electric current. The semiconductor chip is sealed with a sealing material such as an epoxy resin in order to protect it from heat and moisture and play a role of a lens. The epoxy resin composition of the present invention can be used as this sealing material or die bond material. From the viewpoint of the process, it is advantageous to use the epoxy resin composition of the present invention for both the die bond material and the sealing material.

  As a method of adhering a semiconductor chip to a substrate using the epoxy resin composition of the present invention, the epoxy resin composition of the present invention is applied by a dispenser, potting, or screen printing, and then the semiconductor chip is placed and heat-cured. Yes, the semiconductor chip can be bonded. For the heating, methods such as hot air circulation, infrared rays and high frequency can be used.

  The heating condition is preferably about 80 to 230 ° C. and about 1 minute to 24 hours, for example. For the purpose of reducing internal stress generated during heat curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.

As a molding method of the sealing material, as described above, an injection method in which the sealing material is injected into the mold frame in which the substrate on which the semiconductor chip is fixed is inserted and then heat-cured and molded, and the sealing material is formed on the mold. A compression molding method or the like in which a semiconductor chip fixed on a substrate is immersed therein and heat-cured and then released from a mold is used.
Examples of the injection method include dispenser, transfer molding, injection molding and the like.
For the heating, methods such as hot air circulation, infrared rays and high frequency can be used. For example, the heating condition is preferably 80 to 230 ° C. and about 1 minute to 24 hours. For the purpose of reducing internal stress generated during heat curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.

  Furthermore, general applications in which a curable resin such as an epoxy resin is used include adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (printed boards, electric wires). In addition to the encapsulating material, the encapsulating material, a cyanate resin composition for the substrate, an acrylic ester resin as a curing agent for the resist, an additive to other resins, and the like.

  Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

  As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip For example, underfill for QFP, BGA, CSP, etc., and sealing (including reinforcing underfill) can be used.

  The cured product obtained in the present invention can be used for various applications including optical component materials. The optical material refers to general materials used for applications that allow light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material. More specifically, in addition to LED sealing materials such as lamp type and SMD type, the following may be mentioned. It is a peripheral material for liquid crystal display devices such as a substrate material, a light guide plate, a prism sheet, a deflection plate, a retardation plate, a viewing angle correction film, an adhesive, and a film for a liquid crystal such as a polarizer protective film in the liquid crystal display field. In addition, color PDP (plasma display) sealing materials, antireflection films, optical correction films, housing materials, front glass protective films, front glass replacement materials, adhesives, and LED displays that are expected as next-generation flat panel displays LED molding materials, LED sealing materials, front glass protective films, front glass substitute materials, adhesives, and substrate materials for plasma addressed liquid crystal (PALC) displays, light guide plates, prism sheets, deflection plates , Phase difference plate, viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass substitute material, adhesive, and various in field emission display (FED) Film substrate Front glass protective films, front glass substitute material, an adhesive. In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Pickup lenses, protective films, sealing materials, adhesives and the like.

  In the optical equipment field, they are still camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor sections. It is also a photographic lens and viewfinder for video cameras. Projection lenses for projection televisions, protective films, sealing materials, adhesives, and the like. These include lens materials, sealing materials, adhesives, and films for optical sensing devices. In the field of optical components, they are fiber materials, lenses, waveguides, element sealing materials, adhesives and the like around optical switches in optical communication systems. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. For optical passive components and optical circuit components, there are lenses, waveguides, LED sealing materials, CCD sealing materials, adhesives, and the like. These are substrate materials, fiber materials, device sealing materials, adhesives, etc. around an optoelectronic integrated circuit (OEIC). In the field of optical fiber, it is an optical fiber for lighting, light guides for decorative displays, sensors for industrial use, displays / signs, etc., and for communication infrastructure and home digital equipment connection. As the semiconductor integrated circuit peripheral material, it is a resist material for microlithography for LSI and VLSI material. In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Rusted steel plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, glass replacements. In addition, it is a multilayer glass for railway vehicles. Further, they are toughness imparting agents for aircraft structural materials, engine peripheral members, protective / bundling wireness, and corrosion-resistant coatings. In the construction field, it is interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house covering film. Next-generation optical / electronic functional organic materials include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, elements Sealing material, adhesive and the like.

  As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip For example, underfill for sealing, and sealing (reinforcing underfill) when mounting IC packages such as BGA and CSP.

  Other uses of optical materials include general uses in which epoxy resin compositions are used. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials In addition to the sealant (including printed circuit boards and wire coatings), additives to other resins and the like can be mentioned. Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples. The present invention is not limited to these synthesis examples and examples. In addition, each physical property value in an Example was measured with the following method.
(1) Molecular weight: Polystyrene conversion and weight average molecular weight measured under the following conditions were calculated by the GPC method.
Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)
(2) Epoxy equivalent: measured by the method described in JIS K-7236.
(3) Viscosity: Measured at 25 ° C. using an E-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd.

Synthesis example 1
As production step (i), 106 parts of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 234 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1700 (measured GPC value) (silanol equivalent 850, using GPC) 18 parts of 0.5% potassium hydroxide (KOH) methanol solution was charged into the reaction vessel, the bath temperature was set to 75 ° C., and the temperature was raised. After raising the temperature, the reaction was carried out under reflux for 8 hours.
As a manufacturing process (ii), after adding 305 parts of methanol, 86.4 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and reacted at 75 ° C. under reflux for 8 hours. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. 380 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. Subsequently, 300 parts of organopolysiloxane compounds (A-1) which have a reactive functional group were obtained by removing a solvent at 100 degreeC under pressure reduction of an organic phase. The epoxy equivalent of the obtained compound was 729 g / eq, the weight average molecular weight was 2200, and the appearance was colorless and transparent.

Synthesis example 2
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen while 20 parts of tricyclodecane dimethanol, methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH or less, acid anhydride) 100 parts of product (referred to as product (C-1)) was added, reacted at 40 ° C. for 3 hours and then heated and stirred at 70 ° C. for 1 hour to confirm the disappearance of tricyclodecane dimethanol (1 area% or less) by GPC did. ) 120 parts of a curing agent composition (H-1) containing a polycarboxylic acid (B-1) and an acid anhydride (C-1) were obtained. The resulting colorless liquid resin had a GPC purity of 55 area% for polycarboxylic acid (B-1; the following formula (7)) and 45 area% for methylhexahydrophthalic anhydride. The functional group equivalent was 201 g / eq. Met.

Synthesis example 3
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen, while 15 parts of tricyclodecane dimethanol, 70 parts of acid anhydride (C-1), cyclohexane-1,2,4-tricarboxylic acid- Add 15 parts of 1,2-anhydride (H-TMAn manufactured by Mitsubishi Gas Chemical Co., Ltd., hereinafter referred to as acid anhydride (C-2)), react at 40 ° C. for 3 hours, and then heat and stir at 70 ° C. for 1 hour. (Disappearance of tricyclodecane dimethanol (1 area% or less) was confirmed by GPC.), A curing agent composition containing a polycarboxylic acid (B-2) and an acid anhydride (C-2) (H -2) was obtained 100 parts. The obtained colorless liquid resin has a GPC purity of 37% by area of polycarboxylic acid (B-2; the following formula (8)), 11% of acid anhydride (C-2), and acid anhydride. (C-1) was 52 area%. The functional group equivalent was 171 g / eq. Met.

Synthesis example 4
A flask equipped with a stirrer, reflux condenser, and stirrer is purged with nitrogen while 20 parts of 1,4-cyclohexanedimethanol, methylhexahydrophthalic anhydride and hexahydrophthalic anhydride (Shin Nippon Rika Co., Ltd.) ), Ricacid MH-700 (hereinafter referred to as “anhydride C-3”) 100 parts was added, reacted at 40 ° C. for 3 hours, and then heated and stirred at 70 ° C. for 1 hour (1,4-cyclohexane by GPC). Disappearance of dimethanol (1 area% or less) was confirmed.), 120 parts of a curing agent composition (H-3) containing polycarboxylic acid (B-3) and acid anhydride (C-3) was obtained. It was. The obtained colorless liquid resin had a GPC purity of 57 area% for the polycarboxylic acid (B-3; the following formula (9)) and 43 area% for the acid anhydride (C-3). The functional group equivalent was 200 g / eq. Met.

Synthesis example 5
To a flask equipped with a stirrer, a reflux condenser and a stirrer, 20 parts of 1,6-hexanediol and 100 parts of acid anhydride (C-3) were added while purging with nitrogen. By heating and stirring at 1 ° C. for 1 hour (disappearance of 1,6-hexanediol (1 area% or less) was confirmed by GPC), polyvalent carboxylic acid (B-4) and acid anhydride (C— 120 parts of curing agent composition (H-4) containing 3) was obtained. It was the obtained colorless liquid resin, and the purity by GPC was 65 area% for polycarboxylic acid (B-4; the following formula (11)) and 35 area% for acid anhydride (C-3). The functional group equivalent was 200 g / eq. Met.

Synthesis Example 6
To a flask equipped with a stirrer, reflux condenser, and stirrer, 20 parts of 2,4-diethylpentanediol and 100 parts of acid anhydride (C-3) were added while purging with nitrogen, and reacted at 40 ° C. for 3 hours. By heating and stirring at 70 ° C. for 1 hour (disappearance of 2,4-diethylpentanediol (1 area% or less) was confirmed by GPC), polycarboxylic acid (B-5) and acid anhydride ( 120 parts of a curing agent composition (H-5) containing C-3) was obtained. It was the obtained colorless liquid resin, and the purity by GPC was 50 area% for polyvalent carboxylic acid (B-5; the following formula (12)) and 50 area% for acid anhydride (C-3). The functional group equivalent was 201 g / eq. Met.

Examples 1, 2, 3, 4, 5, Comparative Example 1
The organopolysiloxane compound (A-1) obtained in Synthesis Example 1 as an epoxy resin, and the curing agent composition (H-1) obtained in Synthesis Examples 2, 3, 4, 5, and 6 as curing agents for Examples. ), (H-2), (H-3), (H-4) (H-5), a curing accelerator for a comparative example, an acid anhydride (C-3) is used, and a curing accelerator is used as a curing accelerator. (Nippon Kagaku Kogyo Hishicolin PX4MP, hereinafter referred to as catalyst I-1) was used and blended at the blending ratio (parts by weight) shown in Table 1 below, defoamed for 20 minutes, and the present invention or comparative epoxy A resin composition was obtained.

(Corrosion gas permeability test)
Using the obtained curable resin composition, filling into a syringe and using a precision discharge device, an outer diameter 5 mm square surface-mount LED package (with an inner diameter of 4.4 mm and an outer wall height of 1) on which a chip having a central emission wave of 465 nm is mounted. .25 mm). The cast product was put into a heating furnace and cured at 120 ° C. for 1 hour, further at 150 ° C. for 3 hours, and an LED package was prepared. The LED package was left in a corrosive gas under the following conditions, and the color change of the silver-plated lead frame part inside the seal was observed. The results are shown in Table 1.

Measurement conditions Corrosion gas: 20% aqueous solution of ammonium sulfide (discolors black when sulfur component reacts with silver)
Contact method: A container of an ammonium sulfide aqueous solution and the LED package were mixed in a wide-mouth glass bottle, and the wide-mouth glass bottle was covered to bring the volatilized ammonium sulfide gas into contact with the LED package in a sealed state.
Judgment of corrosion: The time when the lead frame inside the LED package was discolored black (referred to as blackening) was observed, and it was determined that the longer the discoloration time, the better the corrosion gas resistance.
Observation was taken out after 10 minutes, 30 minutes, 1 hour, 2 hours and confirmed. Evaluation was ○ for undiscolored products, × for brown-brown materials, and XX for completely blackened materials. It was written.

  From the above results, the epoxy resin composition of the present invention (a composition containing an organopolysiloxane compound and a polyvalent carboxylic acid) is compared to the epoxy resin composition of a comparative example (containing a siloxane compound and an acid anhydride), It becomes clear that the silver plating of the lead frame is not discolored, and has excellent corrosion gas resistance.

Claims (4)

An epoxy resin composition comprising organopolysiloxane (A) and polyvalent carboxylic acid (B) as essential components,
Organopolysiloxane (A):
At least, an epoxy resin having a grayed glycidyl group and / or an epoxycyclohexyl group in the molecule, represented by an alkoxysilane compound represented by the following general formula (1) (a) and the following general formula (2) Block type siloxane compound produced by hydrolyzing and condensing alkoxy groups after reacting silicone oil (b), or an alkoxysilane compound (a) represented by the following general formula (1) and the following general formula A block produced by reacting a silicone oil (b) represented by the formula (2) with an alkoxysilane compound (c) represented by the following general formula (3) and then hydrolyzing and condensing the alkoxy groups. Type siloxane compound.

(In the general formula (1), X is R ₂ that. Plurality of an organic group having a grayed glycidyl group and / or an epoxycyclohexyl group is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms And may be the same as or different from each other.)

(In the general formula (2), a plurality of R _{3 s} represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms. M represents the number of repeating units.)

(R ₄ in the general formula (3) represents a methyl group or a phenyl group. A plurality of R _{5 s} represent a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms and are identical to each other. Or different.)
Polyvalent carboxylic acid (B):
A polyvalent carboxylic acid having at least two or more carboxyl groups and having an aliphatic hydrocarbon group as a main skeleton. The epoxy resin composition according to claim 1, comprising an acid anhydride (C). The polyhydric carboxylic acid is a compound obtained by a reaction of a C6-C6 di- or polyfunctional polyhydric alcohol and a saturated aliphatic cyclic acid anhydride. The epoxy resin composition described in 1. Hardened | cured material formed by hardening | curing the epoxy fat composition of Claim 3.