KR20120114237A - Curable resin composition and cured product thereof - Google Patents

Abstract

An object of this invention is to provide the curable resin composition which gives the hardened | cured material excellent in the optical property, such as corrosiveness, heat-resistant coloring property, or light extraction effect, to a gas in an environment. Curable resin composition of this invention has organopolysiloxane (A), a zinc salt, and / or a zinc complex (C) as an essential component. However, organopolysiloxane (A) satisfy | fills the following conditions.
Organopolysiloxane (A): The epoxy resin which has a glycidyl group and / or an epoxycyclohexyl group at least in the molecule | numerator.

Description

Curable resin composition and its hardened | cured material {CURABLE RESIN COMPOSITION AND CURED PRODUCT THEREOF}

TECHNICAL FIELD This invention relates to curable resin composition and its hardened | cured material suitable for an electric and electronic material use, especially an optical semiconductor use.

Conventionally, an epoxy resin composition has been employed as a sealing material for optical semiconductor elements such as LED products in terms of balance between performance and economy. In particular, glycidyl ether type epoxy resin compositions represented by bisphenol A epoxy resins having excellent balance of heat resistance, transparency and mechanical properties have been widely used.

However, the shortening of the emission wavelength of LED products (mainly 480 nm in LED products emitting blue light) results in that the sealing material is colored on the LED chip under the influence of the short wavelength of light, resulting in lower illumination as an LED product. It is pointed out.

Therefore, the alicyclic epoxy resin represented by 3, 4- epoxycyclohexyl methyl-3 ', 4' epoxy cyclohexyl carboxylate is excellent in transparency compared with the glycidyl ether type epoxy resin composition which has an aromatic ring. Therefore, examination has been made actively as an LED sealing material (patent documents 1 and 2).

In addition, the recent LED products have been further enhanced in the illumination or TV backlight, and accompanied with a lot of heat generation when the LED lights up, so even in the resin composition using the alicyclic epoxy resin, the coloring on the LED chip finally results in LED products. As a result, the illuminance is reduced, leaving a problem in terms of durability (Patent Document 3).

Japanese Patent Laid-Open No. 9-213997 Japanese Patent No. 3618238 WO / 2005-100445 publication Japanese Patent Publication No. 2007-324256 Japanese Patent Publication No. 2000-174347

From the viewpoint of the durability of the said epoxy resin, the examination which uses resin which introduce | transduced the siloxane skeleton (specifically, the skeleton which has a Si-0 bond) represented by silicone resin, silicone modified epoxy resin, etc. as a sealing material is performed (patent document 3). ).

In general, it is known that resins incorporating the siloxane skeleton are more stable to heat and light than epoxy resins. Therefore, when applied to the sealing material of LED products, it is said that durability is superior to epoxy resin from the viewpoint of coloring on an LED chip. However, resins incorporating a siloxane skeleton are inferior in gas permeability compared to epoxy resins. Therefore, when using a silicone resin or a silicone modified epoxy resin as a LED sealing material, coloring on an LED chip does not become a problem, but the problem that the internal structural member deteriorates and coloring occurs. In particular, when used in a living environment, various compounds are suspended, and these compounds penetrate into the interior, which is an opportunity to cause problems. For example, when the said resin is used for lighting use, the silver component plated on the metal lead frame which is a structural member in an LED package by the gas etc. in an environment permeate | transmits the LED sealing material (silver plating is performed in order to raise a reflection factor). ) Have a problem of discoloring or blackening and finally lowering the performance as an LED product (Patent Documents 5 and 6).

In order to solve this gas permeability problem, Patent Literatures 5 and 6 use a method such as coating a metal part covering the gas permeability protective agent with an inorganic material, but there is a problem that the productivity increases due to the increase in the process.

This invention is made | formed in view of the said prior art, and the objective is to provide the curable resin composition which can provide the hardened | cured material which satisfy | fills the product property calculated | required as an electrical / electronic material use, especially an optical semiconductor sealing material, and especially It is providing the curable resin composition which can provide the hardened | cured material excellent in the optical characteristic, such as corrosiveness, heat-resistant coloring property, or the light extraction effect with respect to gas in an environment.

MEANS TO SOLVE THE PROBLEM The present inventors came to complete this invention, as a result of earnestly examining in view of the actual situation mentioned above.

That is,

(One)

Curable resin composition and organopolysiloxane (A) which make organopolysiloxane (A) and a zinc salt and / or a zinc complex (C) an essential component satisfy | fill the following conditions.

Organopolysiloxane (A):

An epoxy resin having at least a glycidyl group and / or an epoxycyclohexyl group in its molecule,

(2)

(1) The zinc salt and / or zinc complex (C) is selected from the group consisting of zinc salts of at least one acid selected from phosphate esters and phosphoric acid and zinc complexes having the acid and the zinc salt as ligands. At least one curable resin composition,

(3)

The zinc salt and / or zinc complex (C) is at least 1 selected from the group consisting of a zinc salt of carboxylic acid having 1 to 30 carbon atoms and a zinc complex having the acid and the zinc salt as ligands (1). Curable resin composition,

(4)

Curable resin composition in any one of (1)-(3) which has a 2 or more carboxyl group and contains the polyhydric carboxylic acid (B) which makes an aliphatic hydrocarbon group main skeleton,

(5)

Curable resin composition as described in (4) whose said polyhydric carboxylic acid (B) is a compound obtained by reaction of C5 or more C2-C6 polyhydric alcohol and saturated aliphatic cyclic anhydride,

(6)

Curable resin composition in any one of (1)-(5) containing acid anhydride,

(7)

Curable resin composition in any one of (1)-(6) containing a hindered amine light stabilizer and / or phosphorus containing antioxidant,

(8)

It is related with the hardened | cured material formed by hardening | curing curable resin composition in any one of said (1)-(7).

(Effects of the Invention)

The curable resin composition of the present invention has excellent optical properties such as corrosion resistance gas resistance, heat resistance colorability, or light extraction effect, and is very suitable as an optical material (LED product, etc.) adhesive and sealing material for optical semiconductors, especially in living environments such as lighting. useful.

Hereinafter, it describes about curable resin composition of this invention.

The epoxy resin composition of this invention has organopolysiloxane (A), a zinc salt, and / or a zinc complex (C) as an essential component.

The organopolysiloxane (A) is at least an epoxy resin having a glycidyl group and / or an epoxycyclohexyl group in its molecule, and generally a trialkoxysilane having a glycidyl group or an epoxycyclohexyl group is used as a raw material. It is obtained by the sol-gel reaction.

Specifically, Japanese Patent Publication No. 2004-256609, Japanese Patent Publication No. 2004-346144, WO 2004/072150, Japanese Patent Publication No. 2006-8747, WO 2006/003990, Japanese Patent Publication Japanese Patent Application Laid-Open No. 2006-104248, WO 2007/135909, Japanese Patent Publication 2004-10849, Japanese Patent Publication 2004-359933, WO 2005/100445, Japanese Patent Publication 2008-174640 And organopolysiloxanes of silsesquioxane type having a three-dimensionally expanded manganese structure as described.

Although it does not specifically limit about the structure of organopolysiloxane, If it is a siloxane compound of a simple three-dimensional mesh structure, since it is too hard, the structure which relaxes hardness is desired. Especially in this invention, the block structure which has the said silsesquioxane structure obtained by a silicon segment and sol-gel reaction in 1 molecule is preferable (henceforth a block-type siloxane compound (A1)).

The block-type siloxane compound (A1) is not a compound having a repeating unit in a straight chain like a conventional block copolymer, but has a mesh-like structure that extends in three dimensions, and the chain silicon segment extends using the silsesquioxane structure as a core. It becomes the structure which couple | bonds with next silsesquioxane structure. This structure is effective in the sense of providing the balance of hardness and flexibility to the hardened | cured material of curable resin composition of this invention.

Block type siloxane compound (A1) can be manufactured using the alkoxysilane compound (a) represented by General formula (1) and silicone oil (b) represented by General formula (2) as a raw material, for example, as follows. Moreover, the alkoxysilane compound (c) represented by General formula (3) can also be used as a raw material as needed. The chain silicone segment of the block siloxane compound (A1) is formed from silicone oil (b), and the three-dimensional manganese silsesquioxane segment is an alkoxysilane (a) (and an alkoxysilane (c) used as necessary). Is formed from. Each raw material is demonstrated in detail below.

The alkoxysilane compound (a) is represented by following formula (1).

XSi (OR ₂ ) ₃ (1)

(In formula (1), X represents the organic group which has a glycidyl group and / or an epoxycyclohexyl group. _{Two or} more R <_2> represents a C1-C10 linear, branched, or cyclic alkyl group, and is the same as each other. May be different)

X in General formula (1) does not have a restriction | limiting in particular if it is an organic group which has glycidyl group and / or an epoxycyclohexyl group. For example, glycidoxy C1-4 alkyl groups, glycidyl groups, (beta)-(3, 4- epoxy cyclohexyl), such as (beta)-glycidoxy ethyl, (gamma)-glycidoxy propyl, and (gamma)-glycidoxy butyl, ) Ethyl group, (gamma)-(3, 4- epoxycyclohexyl) propyl group, (beta)-(3, 4- epoxycycloheptyl) ethyl group, (beta)-(3, 4- epoxycyclohexyl) propyl group, (beta)-(3, 4- C1-C5 alkyl group substituted by the C5-C8 cycloalkyl group which has oxirane groups, such as an epoxy cyclohexyl) butyl group and (beta)-(3, 4- epoxycyclohexyl) pentyl group, is mentioned. Among these, a C1-3 alkyl group substituted with a glycidoxy group, a C1-3 alkyl group substituted with a C5-8 cycloalkyl group having an epoxy group, for example, β-glycidoxyethyl group and γ-glycidoxy A propyl group and β- (3,4-epoxycyclohexyl) ethyl group are preferable, and a β- (3,4-epoxycyclohexyl) ethyl group is particularly preferable.

When an alkoxysilane compound wherein X is a glycidyl group and an alkoxysilane compound where X is an epoxycyclohexyl group is used, the alkoxysilane compound where X is an epoxycyclohexyl group is 80% or more of the total amount of the alkoxysilane compound (a). It is preferable to use.

_{Two or} more R <_2> in General formula (1) represents a C1-C10 linear, branched, or cyclic alkyl group, and may be same or different. 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. These R <_2> has preferable methyl group or ethyl group from a viewpoint of reaction conditions, such as compatibility and reactivity, and especially a methyl group is preferable.

Specific examples of preferred alkoxysilanes (a) include β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltrie. Oxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, etc. are mentioned, Especially β- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane is preferred. These alkoxysilane compounds (a) may be used independently, 2 or more types may be used, and they may be used together with the alkoxysilane (c) mentioned later.

Silicone oil (b) is a following formula (2)

(In formula (2), two or more R <_3> represents a C1-C10 alkyl group, a C6-C14 aryl group, and a C2-C10 alkenyl group, and may mutually be same or different. M represents a repeating unit number. The terminal which has a structure represented by) is a linear silicone oil which has a silanol group.

Two or more R <_3> in the formula of General formula (2) represents a C1-C10 alkyl group, a C6-C14 aryl group, and a C2-C10 alkenyl group, and may be same or different.

As a C1-C10 alkyl group, a C1-C10 linear, branched, or cyclic alkyl group is mentioned, for example, a methyl group, an ethyl group, n-propyl group, 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, etc. are mentioned. Among these, in consideration of light resistance and heat resistance, a methyl group, an ethyl group, an n-propyl group, and a cyclohexyl group are preferable.

As a C6-C14 aryl group, a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, etc. are mentioned, for example.

Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl groups, 1-methylvinyl groups, allyl groups, propenyl groups, butenyl groups, pentenyl groups, and alkenyl groups such as hexenyl groups.

R ₃ is preferably a methyl group, a phenyl group, a cyclohexyl group or an n-propyl group from the viewpoint of light resistance and heat resistance, and particularly preferably a methyl group or a phenyl group.

The repeating unit number m of the compound of the formula (2) represents 3 to 200 as an average value, preferably 3 to 100, and more preferably 3 to 50. When m is less than 3, hardened | cured material will become hard too much and low elastic modulus characteristic will fall. When m exceeds 200, since the mechanical characteristic of hardened | cured material tends to deteriorate, it is unpreferable.

It is preferable that the weight average molecular weight (Mw) of silicone oil (b) is the range of 300-18,000 (gel permeation chromatography (GPC) measurement value). Among these, considering the modulus of elasticity at low temperature, those having a molecular weight of 300 to 10,000 are preferable, considering the compatibility at the time of composition, it is even more preferable that it is 300 to 5,000, and particularly preferably 500 to 3,000. If the weight average molecular weight is less than 300, the characteristic of the chain silicon portion of the characteristic segment is difficult to come out, and the characteristics as a block type may be impaired. If the weight average molecular weight exceeds 18,000, it has a strong layer separation structure, and thus the permeability deteriorates for use in optical materials. It becomes difficult to use it. As molecular weight of a silicone oil (b) in this invention, polystyrene conversion and weight average molecular weight (Mw) measured on condition of the following using GPC can be calculated.

Conditions of GPC

Manufacturer: Shimadzu Seisakusho

Column: Guard Column SHODEX GPC LF-G LF-804 (3ea)

Flow rate: 1.0 ml / min.

Column temperature: 40 ℃

Solvent used: THF (tetrahydrofuran)

Detector: Differential Refractive Detector (RI)

The kinematic viscosity of the silicone oil (b) is preferably in the range of 10 to 200 cSt, more preferably 30 to 90 cSt. When it is less than 10 cSt, the viscosity of the block-type siloxane compound (A1) may be too low to be suitable as an optical semiconductor sealant, and when it is higher than 200 cSt, the viscosity of the block-type siloxane compound (A1) is increased to work. It is not preferable because it tends to cause adverse effects on sex.

Specific examples of the silicone oil (b) include the following product names. For example, PRX-413, BY16-873, made by Toray Dou Corning Silicone, X-21-5841, KF-9701, manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd., XC96-723, TSR-160, YR-3370, manufactured by Momentive, YF-3800, XF-3905, YF-3057, YF-3807, YF-3802, YF-3897, YF-3804, XF-3905, 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 the above, from the viewpoint of molecular weight and kinematic viscosity, PRX-413, BY16-873, X-21-5841, KF-9701, XC96-723, YF-3800, YF-3804, DMS-S12, DMS-S14, DMS-S15, DMS-S21 and PDS-1615 are preferred. Among these, X-21-5841, XC96-723, YF-3800, YF-3804, DMS-S14, and PDS-1615 are especially preferable from the viewpoint of molecular weight in order to give the flexibility characteristics of the silicone segment. These silicone oils (b) may be used independently and may be used in combination of 2 or more type.

Next, the alkoxysilane (c) is demonstrated in detail. The alkoxysilane (c) has a structure of the following formula (3).

R ₄ (OR ₅ ) ₃ (3)

(R <_4> in General formula (3) represents a methyl group or a phenyl group. Two or more R <_5> represents a C1-C10 linear, branched, or cyclic alkyl group, and may be same or different.)

Two or more R <_5> in General formula (3) represents a C1-C10 linear, branched or cyclic alkyl group, and may be same or different. 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. It is preferable that these R <_5> is a methyl group or an ethyl group from a viewpoint of reaction conditions, such as compatibility and reactivity.

Preferable specific examples of the alkoxysilane (c) include methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane and the like. Among these, methyl trimethoxysilane and phenyl trimethoxysilane are preferable.

In the present invention, the alkoxysilane (c) adjusts the heat resistance, light resistance, low moisture permeability, low gas permeability, and the like of the cured product in order to improve the compatibility of the block-type siloxane compound (A1) when the composition is used. In order to do that, it can use together with an alkoxysilane (a).

When using an alkoxysilane (c), it is preferable to use an alkoxysilane (c) in the range of 5-70 mol% among the total moles of an alkoxysilane (a) and an alkoxysilane (c), and 5-50 mol% is further used. It is preferable and 10-40 mol% is especially preferable. When it is larger than 70 mol%, since the crosslinking density of hardened | cured material is inferior and mechanical strength falls, it is unpreferable.

As a reaction ratio of an alkoxysilane (a), a silicone oil (b), and an alkoxysilane (c), an alkoxysilane (a) (and the alkoxysilane (c) used as needed) with respect to 1 equivalent of the silanol groups of a silicone oil (b). The alkoxy group in) is preferably 1.5 to 200, preferably 2 to 200, and particularly preferably 2 to 100 as an equivalent value.

When the equivalent value exceeds 200, the hardened | cured material using a block type siloxane compound (A1) will become hard too much, and the target low elasticity rate characteristic will fall.

Hereinafter, the preferable manufacturing method of a block type | mold siloxane compound (A1) is mentioned concretely.

As a manufacturing method of a block type | mold siloxane compound (A1), it is preferable to go through the manufacturing process shown by following (i) and (ii).

Production process (iii): Process of performing de-alcohol condensation of a silanol terminal silicone oil (b) and the alkoxysilane (a) (and the alkoxysilane (c) used as needed) which has an alkoxy group

Manufacturing process (ii): The process of hydrolytic condensation of the alkoxy groups of an alkoxysilane (a) (and the alkoxysilane (c) used as needed) by adding water.

The manufacturing steps (iii) and (ii) may be reacted in any order via the respective steps.

Specifically as a preferable manufacturing method, the following three types of manufacturing methods are mentioned.

<Manufacturing method (a)>

First, as a manufacturing process (i), the dealcohol condensation reaction of the silicone oil (b) which has a silanol group at the terminal, and the alkoxysilane (a) (and the alkoxysilane (c) used as needed) which is a silicon compound which has an alkoxy group is carried out. By alkoxysilane modification of the silicone oil terminal, the process of obtaining the alkoxysilane modified body (d) is performed.

Next, the alkoxysilane (a) (and the alkoxysilane (c) used as needed) which is a silicon compound which has an alkoxy group as manufacturing process (ii), and the alkoxysilane modified body (d) of the silicone oil obtained at the manufacturing process (iii) The method of manufacturing a block type | mold siloxane compound (A1) by going through the process of adding water to a hydrolysis condensation reaction of alkoxy groups.

<Production Method (B)>

First, a silsesquioxane having an alkoxy group in the molecule is subjected to hydrolysis condensation reaction between the alkoxy groups by addition of water of the alkoxysilane (a) (and the alkoxysilane (c) to be used if necessary) as the production step (iii). The process of obtaining (e) is performed.

Subsequently, as a manufacturing step (ii), a block-type siloxane is subjected to a step of de-alcohol condensation reaction of the alkoxy group and the silanol group remaining in the silsesquioxane structure by the reaction of the silicone oil (b) and the silsesquioxane (e). Method for preparing compound (A1).

<Manufacturing method (C)>

First, as a manufacturing process, by dealcohol condensation reaction of the silicone oil (b) which has a silanol group at the terminal, and the alkoxysilane (a) which is a silicon compound which has an alkoxy group (and the alkoxysilane (c) used as needed) By modifying the silicone oil terminal to an alkoxysilane to make an alkoxysilane modified body (d), water is added to the system, and the alkoxysilane (a) (and alkoxysilane to be used if necessary) which remains as a manufacturing process (ii) in one pot. (c)) and the method of manufacturing block type | mold siloxane compound (A1) by performing hydrolytic condensation reaction of the alkoxy groups of an alkoxysilane modified body (d).

In this invention, it is preferable to use the said manufacturing method (c) made to react with a one pot gradually from a viewpoint of shortening of a manufacturing process.

Hereinafter, the manufacturing method (C) will be described more specifically.

In the case of reacting with a single pot, when the production process (iii) is performed in the reverse order to the above production method (c), that is, after the production process (ii), the silsesquioxane oligomer and the silicone oil having an alkoxy group formed in the production process (ii) ( b) is incompatible, and de-alcohol condensation polymerization does not progress in the post-production process, and there is a high possibility of leaving silicone oil. On the other hand, when the manufacturing process (ii) is performed in one pot after the manufacturing process (iii) as in the manufacturing method (c), the compatibility between the silicone oil (b) and the alkoxysilane (a) or alkoxysilane (c) Since it is relatively high, the problem that it is not compatible and reaction does not progress as mentioned above can be avoided. Moreover, since a large amount of unreacted low molecular weight alkoxysilane will exist with respect to a silanol group, it is also preferable from a reactive viewpoint. In the case of one-pot, first, dealcohol condensation of the silicone oil (b) and the alkoxysilane (a) (and the alkoxysilane (c) to be used, if necessary) is carried out in the production process, and the terminal of the silicone oil is alkoxy. The silyl modification is carried out to obtain an alkoxysilane modified body (d). Since no water is added in the production step, hydrolysis and condensation of the alkoxy groups does not occur, and when the alkoxy group is reacted with 3 equivalents or more of alkoxy groups relative to 1 equivalent of a silanol group, the alkoxysilane modified body (d) is represented by the following formula It is considered to exist in the structure shown by (4).

(In formula (4), R <_3> and m show the same meaning as the above, and two or more R <_6> represents the said X or said R <_4> independently, and R <_7> binds the same silicon as -OR <^7> and R <_6>. If this is the case of the X, the R ₆ for combining the R _2, -OR ⁷ on the same silicon wherein R ₄ is, it represents the R ₅ each)

When the alkoxy group is reacted in an amount less than 1 equivalent with respect to 1 equivalent of the silanol group in the production step (v), no alkoxy group is present at the end of the production step (v), and the alkoxy group does not proceed to the production step (ii). Reaction between 1 and 1.5 equivalents causes two or more alkoxy groups in the alkoxysilane (a) (and the alkoxysilane (c) to be used if necessary) to react with the silanol groups of the silicone oil (b), thus completing the production process. The gel becomes excessively high in the gel, causing gelation. 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 a viewpoint of reaction control, 2 equivalent or more is preferable and 3 equivalent or more is more preferable.

After completion of the production step (iii), water is added as it is to perform a second stage reaction (manufacturing step (ii)) to hydrolyze and condense the alkoxy groups.

In manufacturing process (ii), reaction of (I)-(III) shown below is occurring.

(I) Condensation reaction of the alkoxy groups of the alkoxysilane (a) (and the alkoxysilane (c) used as needed) which remain in the system.

(II) Condensation reaction of the alkoxy groups of the alkoxysilane modified body (d) obtained in the manufacturing process (i) and the alkoxysilane (a) (and the alkoxysilane (c) used as needed).

(III) Alkoxy groups of the alkoxy groups of the partial condensate of the alkoxysilane modified body (d) obtained in the production process (i) and the alkoxysilane (a) (and the alkoxysilane (c) to be used if necessary) produced in (I) Condensation reaction.

In the manufacturing step (ii), the above reaction occurs in combination, and the formation of the silsesquioxane segment and the condensation of the chain silicon segment derived from the silicone oil are simultaneously performed.

Although preparation of a block type | mold siloxane compound (A1) is performed also without a catalyst, if it is a non-catalyst, it is preferable to carry out reaction in the presence of a catalyst from a viewpoint of shortening reaction time because reaction progresses. As a catalyst which can be used, if it is a compound which shows acidic or basicity, it can be used. Examples of acidic catalysts 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 inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, alkali metal hydroxides such as cesium hydroxide, sodium metal carbonate, potassium carbonate, sodium hydrogen carbonate and alkali metal carbonates such as potassium hydrogen carbonate, ammonia and triethyl. Organic bases, such as an amine, diethylene triamine, n-butylamine, dimethylamino ethanol, triethanolamine, and tetramethylammonium hydrooxide, can be used. Among these, an inorganic base is preferable at the point which is easy to remove a catalyst from a product, and sodium hydroxide and potassium hydroxide are especially preferable. The amount of the catalyst added is usually 0.001 to 7.5% by weight, preferably 0.01 to 5% by weight relative to the total weight of the alkoxysilane (a) (and the alkoxysilane (c) to be used if necessary) in the reaction system.

The addition method of a catalyst is used in the state added directly or dissolved in a soluble solvent etc. Especially, it is preferable to add in the state which melt | dissolved the catalyst in alcohol, such as methanol, ethanol, propanol, butanol, in advance. At this time, adding as an aqueous solution using water or the like unilaterally proceeds the condensation of the alkoxysilane (a) (and the alkoxysilane (c) to be used if necessary) as described above, thereby producing a silsesquioxane oligomer And silicone oil (b) are not commercially available and may be cloudy.

Production of a block type siloxane compound (A1) can be performed in a non-solvent or a solvent. Moreover, a solvent can also be added in the middle of a manufacturing process. There is no restriction | limiting in particular as a solvent in the case of using, if it is a solvent which melt | dissolves an alkoxysilane (a), an alkoxysilane (c), silicone oil (b), and an alkoxysilane modified body (d). As such a solvent, for example, aprotic polar solvents such as dimethylformamide, dimethylacetamide, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclopentanone, ethyl acetate, butyl acetate, ethyl lactate, and Esters such as isopropyl carbonate, alcohols such as methanol, ethanol, propanol and butanol, hydrocarbons such as hexane, cyclohexane, toluene and xylene, and the like can be exemplified. In this invention, reaction in alcohols is preferable from a 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 is usually 0 based on 100 parts by weight of the total weight of the compounds of the alkoxysilane (a) (and the alkoxysilane (c) to be used if necessary) and the silicone oil (b). Use about 900 parts by weight. Although reaction temperature is based also on catalyst amount, it is 20-160 degreeC normally, Preferably it is 40-140 degreeC, Especially preferably, it is 50-150 degreeC. Moreover, reaction time is 1-40 hours normally in each manufacturing process, Preferably it is 5-30 hours.

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

The reaction may be performed by washing only with water, but the reaction is carried out under either of an acidic or basic condition, and after quenching by neutralization, washing with water or adsorbing the catalyst using an adsorbent is followed by filtration. It is preferable to remove the adsorbent by.

Any neutralizing reaction can be used as long as it is an acidic or basic compound. Examples of the compound showing 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 the compound showing basicity include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate, phosphoric acid and sodium dihydrogen phosphate. Inorganic bases such as phosphates such as sodium dihydrogen phosphate, trisodium phosphate, polyphosphate and sodium tripolyphosphate, ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, tetramethyl Organic bases, such as ammonium hydrooxide, can be used. Among these, an inorganic base or an inorganic acid is preferable at the point which is easy to remove from a product, More preferably, it is phosphate etc. which are easier to adjust pH to neutral vicinity.

Examples of the adsorbent include activated clay, activated carbon, zeolite, inorganic and organic synthetic adsorbents, ion exchange resins, and the like, and specific examples thereof include the following products.

As activated clay, for example, activated clay SA35, SA1, T, R-15, E, Nikkanite G-36, G-153, G-168 are manufactured by Toshin Kasei Co., Ltd., Galeonus is manufactured by Mizusawa Kagaku Kogyo Co., Ltd. Mizukaes etc. are mentioned. As activated carbon, CL-H, Y-10S, Y-10SF are manufactured by Ajinomoto Fine Techno Co., Ltd., S, Y, FC, DP, SA1000, K, A, KA, M, CW130BR, CW130AR are manufactured by Futamura Kagaku Co., Ltd. And GM130A. Examples of the zeolite include molecular 3A, 4A, 5A, 13X, and the like, manufactured by Union Showa. As a synthetic adsorbent, for example, Kyowa Kawaku Co., Ltd. is 100, 200, 300, 400, 500, 600, 700, 1000, 2000, or Rohm & Haas Co., Ltd. Amberlyst 15JWET, 15DRY, 16WET, 31WET , A21, Amberlite IRA400JCl, IRA403BLCl, IRA404JCl or Dow Chemical Co., Ltd., Dow X 66, HCR-S, HCR-W2, MAC-3, etc. are mentioned.

The adsorbent can be added to the reaction solution to carry out treatment such as stirring and heating to adsorb the catalyst, followed by filtering the adsorbent and washing the residue with water to remove the catalyst and the adsorbent.

After completion | finish of reaction or after quenching, a product can be refine | purified by the separation and purification means for other pipes of water washing and filtration. As purification means, column chromatography, concentration under reduced pressure, distillation, extraction, etc. are mentioned, for example. These refinement | purification means may be performed independently, and it does not matter even if it combines in plurality.

When reacting using a solvent mixed with water as the reaction solvent, it is preferable to remove the reaction solvent mixed with water by distillation or concentration under reduced pressure after quenching and washing with water using a solvent which can be separated from water.

After washing with water, the block siloxane compound (A1) can be obtained by removing the solvent by concentration under reduced pressure.

The appearance of the block siloxane compound (A1) thus obtained is usually colorless and transparent, and is a liquid having fluidity at 25 ° C. Moreover, as the weight average molecular weight measured by GPC, the thing of 800-20,000 is preferable, It is more preferable that it is 1,000-10,000, It is especially preferable that the thing of 1,500-6,000. If the weight average molecular weight is lower than 800, the heat resistance may be lowered. If the weight average molecular weight is higher than 20,000, the viscosity rises and adversely affects workability. In addition, the molecular weight is the equivalent ratio of the alkoxysilane (a) (and the alkoxysilane (c) used as needed) and the silicone oil (b), the molecular weight of the silicone oil (b), the amount of water added during the reaction, the reaction time, the reaction temperature Adjustable by

The said weight average molecular weight is the weight average molecular weight (Mw) of polystyrene conversion measured under the following conditions using GPC (gel permeation chromatography).

Conditions of GPC

Manufacturer: Shimadzu Seisakusho

Column: Guard Column SHODEX GPC LF-G LF-804 (3ea)

Flow rate: 1.0 ml / min.

Column temperature: 40 ℃

Solvent used: THF (tetrahydrofuran)

Detector: Differential Refractive Detector (RI)

Moreover, it is preferable that the epoxy equivalent (measured by the method of JIS K-7236) of the said block type siloxane compound (A1) is 300-1,600 g / eq, It is more preferable that it is 400-1,000 g / eq, Especially 450 It is preferable that it is? 900 g / eq. When the epoxy equivalent is less than 300 g / eq, the cured product is hard and the modulus of elasticity tends to be too high. When the epoxy equivalent exceeds 1,600 g / eq, the mechanical properties of the cured product tend to be deteriorated, which is not preferable.

It is preferable that the viscosity (E-type viscosity meter, measured at 25 degreeC) of a block type siloxane compound (A1) is 50-20,000 mPa * s, It is more preferable that it is 500-10,000 mPa * s, Especially 800-5,000 mPa * s Is preferably. When the viscosity is less than 50 mPa · s, the viscosity may be too low and unsuitable for use in the optical semiconductor sealing material. When the viscosity is higher than 20,000 mPa · s, the viscosity may be too high and the workability may be inferior.

As for the ratio with respect to the total silicon atom of the silicon atom couple | bonded with three oxygen derived from the silsesquioxane in a block-type siloxane compound (A1), 5-50 mol% is preferable, 8-30 mol% is more preferable Especially, 10-20 mol% is preferable. When the ratio of the silicon atoms bonded to the three oxygens derived from the silsesquioxane to the total silicon atoms is less than 5 mol%, the cured product tends to be too soft as a characteristic of the chain silicon segment, and the surface jaw and scratches There is concern. Moreover, when it exceeds 50 mol%, since hardened | cured material becomes too hard as a characteristic of a silsesquioxane segment, it is unpreferable.

The ratio of the silicon atom which exists can be calculated | required by ¹ H NMR, ²⁹ Si NMR, elemental analysis, etc. of a block type siloxane compound (A1).

Curable resin composition of this invention contains polyhydric carboxylic acid (B) as a preferable component.

Polyhydric carboxylic acid (B) is a compound which has at least 2 or more carboxyl groups, and makes an aliphatic hydrocarbon group main skeleton. In the present invention, the term "polyvalent carboxylic acid" includes not only a polyvalent carboxylic acid having a single structure but also a mixture of a plurality of compounds having different positions or different substituents, that is, a polyvalent carboxylic acid composition. It is called polyhydric carboxylic acid.

As polyhydric carboxylic acid (B), a 2-6 functional carboxylic acid is especially preferable, and the compound obtained by reaction of a C5 or more 2-6 functional polyhydric alcohol and an acid anhydride is more preferable. Moreover, the polycarboxylic acid whose said acid anhydride is saturated aliphatic cyclic acid anhydride is preferable.

Although it will not specifically limit, if it is a compound which has an alcoholic hydroxyl group as a 2-6 functional polyhydric alcohol, 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, tricyclodecane dimethanol, norbornenediol, etc. Triols such as diols, glycerin, trimethylol ethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol and ditrimethylolpropane, dipentaerythritol, and the like. Hexaol etc. are mentioned.

Particularly preferred polyhydric alcohols are alcohols having 5 or more carbon atoms, in particular 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 2, 4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentylglycol, tricyclodecane dimethanol, norbornenediol and the like are preferable, and 2-ethyl-2-butyl- Polyhydric alcohol which has branched structure or cyclic structure, such as 1, 3- propanediol, neopentyl glycol, 2, 4- diethyl pentanediol, 1, 4- cyclohexane dimethanol, tricyclodecane dimethanol, norbornene diol This is more preferable.

Examples of the acid anhydrides include methyltetrahydrophthalic anhydride, methylnadic acid anhydride, nadic acid 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, etc. Methylhexahydro phthalic anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4- anhydride are especially preferable.

Although conditions for addition reaction are not specifically specified, One of the specific reaction conditions includes a method in which an acid anhydride and a polyhydric alcohol are reacted and heated at 40 to 150 ° C under a catalyst-free and solvent-free condition, and withdrawn after the reaction is completed. However, the reaction conditions are not limited.

As a polycarboxylic acid obtained in this way, following formula (5)

(In the formula, a plurality of Q represents at least one of a hydrogen atom, a methyl group and a carboxyl group. P is a chain, branched or cyclic aliphatic group derived from the polyhydric alcohol. M is the number of functional groups of the polyhydric alcohol (alcohol group Number), preferably an integer of 2 to 6).

It is preferable that curable resin composition of this invention contains an acid anhydride. Specific examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydro phthalic anhydride, methyltetrahydro phthalic anhydride, methylnadic anhydride, nadic acid, hexahydro phthalic anhydride, and methyl hexa Hydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicar Acid anhydrides, such as an acid anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4- anhydride, are mentioned.

In particular methyltetrahydro phthalic anhydride, methylnadic acid anhydride, nadic acid anhydride, hexahydro phthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dica Preference is given to lenic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride.

In addition, in the said acid anhydride, following formula (6)

Hexahydro phthalic anhydride represented by (wherein Z represents at least one of a hydrogen atom, a methyl group and a carboxyl group), methylhexahydro phthalic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4- Anhydrides are preferred, and methylhexahydrophthalic anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride are particularly preferred.

When the curable resin composition of this invention contains an acid anhydride, the usage-amount is determined by the ratio with polyhydric carboxylic acid (B), and the range of the following formula is preferable.

W1 / (W1 + W2) = 0.05? 0.65

(W1 is a compounding weight part of polyhydric carboxylic acid (B), W2 represents the compounding weight part of an acid anhydride)

In the above description, the range of W1 / (W1 + W2) is more preferably 0.05 to 0.65, still more preferably 0.10 to 0.65, and particularly preferably 0.3 to 0.6. When it is less than 0.05, the tendency for volatilization of an acid anhydride to increase at the time of hardening is strong, and it is unpreferable. If it exceeds 0.65, the viscosity becomes high and handling becomes difficult. In the case of not containing an acid anhydride (except when there is a small amount remaining), the shape of the polyvalent carboxylic acid (B) is a problem because it becomes a solid or near solid state or crystal at room temperature.

When using a polyhydric carboxylic acid (B) and an acid anhydride together, the method of preparing in excess acid anhydride at the time of preparation of a polyhydric carboxylic acid (B), and also preparing the mixture of polyhydric carboxylic acid (B) and an acid anhydride It is preferable at the point of simplicity of operation.

Curable resin composition of this invention contains a zinc salt and / or a zinc complex (C) as an essential component. Zinc salt and / or zinc complex (C) contributes as a hardening accelerator of an epoxy resin and a hardening | curing agent in this invention.

The zinc salt and / or zinc complex (C) is not particularly limited as long as it is a salt and / or a complex containing zinc ions as a center element, but it is a carboxylic acid, a phosphate ester having an alkyl group having 1 to 30 carbon atoms as a counter ion and / or ligand, and It is preferred to have at least one acid selected from phosphoric acid. In this invention, zinc carboxylate and phosphate ester zinc are especially preferable, and zinc carboxylate is especially preferable from a compatibility point.

Examples of the alkyl group include methyl, isopropyl, butyl, 2-ethylhexyl, octyl, isodecyl, isostearyl, decanyl, cetyl and undecylene.

As a carboxylic acid zinc body, at least 1 sort (s) chosen from the group which consists of a zinc salt of C1-C30 carboxylic acid, a C1-C30 carboxylic acid, and the zinc complex which has the said zinc salt as a ligand can be used. As a carboxylic acid zinc body, the said C1-C30 carboxylic acid is preferably an alkyl group which has functional groups, such as alkyl or olefin which has a linear branched structure, More preferably, it is C3-C30 carbon number, Especially, the thing of 5-20 carbon atoms is preferable. These are preferable from the viewpoint of compatibility, and are not preferable because they have poor compatibility with resins when the carbon number is too large (more than 30 carbon atoms) or when there is no structure such as a branched structure or a functional group such as olefin.

Specifically, zinc 2-ethylhexyl acid, zinc isostearate, zinc undecylenate, etc. are mentioned.

As the phosphate ester, at least one member selected from the group consisting of zinc salts of phosphate esters, phosphate esters and zinc complexes having the zinc salts as ligands can be used. The phosphate ester may also contain phosphoric acid derived from the phosphate ester as a counter ion and / or a ligand.

Particularly preferred phosphoric acid esters in the present invention are zinc salts and / or zinc complexes of phosphoric acid esters (monoalkyl esters, dialkyl esters, trialkyl esters or mixtures thereof), and contain a plurality of phosphoric acid esters. It does not matter. Specifically, the molar ratio of the monoalkyl ester, the dialkyl ester, and the trialkyl ester among the phosphate esters contained in the phosphate ester (replaced by the purity of gas chromatography. However, since trimethylsilylation needs to be performed, In the step of trimethylsilylation treatment, the amount of monoalkyl ester produced is preferably 50 area% or more.

Such zinc salt and / or zinc complex of zinc phosphate ester can be obtained, for example, by reacting phosphate ester with zinc carbonate, zinc hydroxide or the like (Patent Document EP699708).

As phosphoric acid ester, 2-ethylhexyl phosphoric acid, stearyl phosphoric acid, etc. are preferable.

As a detail of the zinc salt and / or zinc complex of such phosphate ester, 1.2-2.3 are preferable and, as for the ratio (P / Zn) of a phosphorus atom and a zinc atom, 1.3-2.0 are more preferable. Especially preferably, it is 1.4-1.9. That is, in a particularly preferred form, the phosphoric acid ester (or phosphoric acid derived from the phosphate ester) is 2.0 moles or less with respect to 1 mole of zinc ions, and a structure in which several molecules are related by ionic bonds (or coordination bonds) rather than simple ionic structures. It is preferable to have a. As such a zinc salt and / or a zinc complex, it can also be obtained by the method of Unexamined-Japanese-Patent No. 2003-51495, for example.

Commercially available products such as Zn-St, Zn-St 602, Zn-St NZ, ZS-3, ZS-6, ZS-8, ZS-8, ZS-7, ZS-10, ZS -5, ZS-14, ZS-16 (manufactured by Nitto Kasei), XK-614 (King Industry Co., Ltd.), 18% Octope Zn, 12% Octope Zn, 8% Octope Zn (Hope Seiyaku), Phosphoric Acid Examples of the ester and / or zinc phosphate include LBT-2000B (manufactured by SC Organic Kagaku) and XC-9206 (manufactured by King Industries).

In the curable resin composition of the present invention, the ratio of the organopolysiloxane (A) and the zinc salt and / or the zinc complex (C) is a zinc salt and / or zinc complex (C) relative to the organopolysiloxane (A). 0.01 to 8% by weight, more preferably 0.05 to 5% by weight, and also 0.1 to 4% by weight. Moreover, Especially preferably, it is 0.1-2 weight%.

When using curable resin composition of this invention for an optical material, especially an optical semiconductor sealing agent, it is preferable to contain a hindered amine compound as an optical stabilizer and a phosphorus compound as antioxidant as an especially preferable component. In this invention, it is especially preferable to contain a hindered amine compound, and it is preferable to contain a phosphorus compound as needed.

Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate and tetrakis (2,2 , 6,6-tetramethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6, Mixed esters of 6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane , Decane diacid bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidine-4- I) carbonate, 2,2,6,6, -tetramethyl-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) propy Nyloxy] -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] butylmalonate, decanoic acid bis [2,2,6 , 6-tetramethyl-1 (octyloxy) -4-piperidinyl] ester, reaction product of 1,1-dimethylethylhydroperoxide with 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-diaza Decane-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-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl -4-piperidyl) imino]], dimethyl succinate and 4-hydride Polymer of 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] henic acid-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] henic acid-21-one, 2,2,4,4-tetramethyl-21-oxa -3,20-diazacyclo- [5,1,11,2] -henicoic acid-20-propanoic acid dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) -methylene ] -Bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol, 1,3- Hindered amine compounds, such as benzenedicarboxyamide and N, N'-bis (2,2,6,6- tetramethyl-4- piperidinyl), etc. are mentioned.

The commercial item shown below can be used as an amine compound which is the said light stabilizer.

For example, TINUVIN765, TINUVIN770DF, TINUVIN144, TINUVIN123, TINUVIN622LD, TINUVIN152, CHIMASSORB944, Adeka made by Chiba Specialty Chemicals, LA-52, LA-57, LA-62, LA-63P, LA-77Y, LA-81 , LA-82, LA-87 and the like.

In the curable resin composition of this invention, the usage-amount of an optical stabilizer is 0.005 to 5 weight%, More preferably, it is 0.01 to 4 weight% and 0.1 to 2 weight% with respect to organopolysiloxane (A).

Although it does not specifically limit as said phosphorus compound, For example, 1,1, 3- tris (2-methyl-4- ditridecyl phosphite-5-tert- butylphenyl) butane, distearyl pentaerythritol diphosphite, bis ( 2,4-di-tert-butylphenyl) pentaerythritoldiphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritoldiphosphite, phenylbisphenol Apentaerythritoldiphosphite, dicyclohexylpentaerythritol Diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite , 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'-methylene (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-ethylidenebis (4-methyl-6-tert-butylphenyl) (2- tert-butyl-4-methylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butyl Phenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di -tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, 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-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di- tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-pe Phosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, Trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl monoorthoquixenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate and the like.

A commercial item can also be used for the said phosphorus compound.

For example, as adekaze, adecastabPEP-4C, adecastabPEP-8, adecastabPEP-24G, adecastabPEP-36, adecastab HP-10, adecastab 2112, adecas Tab 260, Adecastab 522A, Adecastab 1178, Adecastab 1500, Adecastab C, Adecastab 135A, Adecastab 3010, Adekastab TTP.

In the curable resin composition of this invention, the usage-amount of a phosphorus compound is 0.005 to 5 weight%, More preferably, it is 0.01 to 4 weight% and 0.1 to 2 weight% with respect to organopolysiloxane (A).

The curable resin composition of this invention makes an organopolysiloxane (A) an epoxy resin and a zinc salt and / or a zinc complex (C) an essential component, and a polyhydric carboxylic acid (B), an acid anhydride, and an additive as a hardening | curing agent. Although hindered amine light stabilizer and phosphorus containing antioxidant are further contained as a preferable arbitrary component, these can also be used together with another epoxy resin, a hardening | curing agent, and various additives.

In the epoxy resin component, when organopolysiloxane (A) is used in combination with other epoxy resins, the proportion of the organopolysiloxane (A) in the total epoxy resin is preferably 60% by weight or more, particularly preferably 70% by weight or more.

As epoxy resins other than what can be used together with organopolysiloxane (A), a novolak-type epoxy resin, a bisphenol-A epoxy resin, a biphenyl type epoxy resin, a triphenylmethane type epoxy resin, a phenol aralkyl type epoxy resin, etc. are mentioned. Can be. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpendiphenol, 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, dihydroxybenzene, dihydroxynaphthalene etc.), formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxy Benzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (cromethyl) -1,1'-biphenyl, 4,4'-bis ( Polycondensates such as methoxymethyl) -1,1'-biphenyl, 1,4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, and modified substances thereof and tetrabromobisphenol A Such as halogenated bisphenols and alcohols Solid or liquid epoxy resins, such as a glycidyl ether derivative, an alicyclic epoxy resin, a glycidyl amine epoxy resin, and a glycidyl ester epoxy resin derived from, are not limited to these. These may be used independently and may be used together 2 or more types.

In particular, the curable resin composition of this invention makes it the main objective to use for optical uses. When used for an optical use, combined use with an alicyclic epoxy resin is preferable. In the case of an alicyclic epoxy resin, the compound which has an epoxy cyclohexane structure in a frame | skeleton is preferable, and the epoxy resin obtained by the oxidation reaction of the compound which has a cyclohexene structure is especially preferable.

As these epoxy resins, the esterification reaction of cyclohexene carboxylic acid and alcohols, or the esterification reaction of cyclohexene methanol and carboxylic acids (Tetrahedron vol. 36 p. 2409 (1980), Tetrahedron Letter p. 4475 (1980), etc.). ) Or a thishenco reaction of cyclohexene aldehyde (method disclosed in Japanese Patent Laid-Open No. 2003-170059, Japanese Patent Laid-Open No. 2004-262871, etc.), or a transesterification reaction of cyclohexene carboxylic acid ester (Japanese Patent Laid-Open) And the method of oxidizing the compound which can be produced by the method described in 2006-052187 and the like.

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, and 1,6-hexane Diols such as diol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1.3-propanediol, neopentylglycol, tricyclodecanedimethanol, norbornenediol, glycerin, trimethyl Triols such as rolled ethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol and ditrimethylolpropane, and the like. Examples of the carboxylic acids include oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, cyclohexanedicarboxylic acid, and the like, but are not limited thereto.

Moreover, the epoxy resin which epoxidized the acetal compound obtained by the acetal reaction of a cyclohexene aldehyde derivative and an alcohol body by an oxidation reaction is mentioned as another epoxy resin.

As a specific example of these epoxy resins, ERL-4221, UVR-6105, ERL-4299 (all brand name, all are manufactured by Dow Chemical), Celoxide 2021P, Eporide GT401, EHPE3150, EHPE3150CE (all brand names, all are Daicel Kagaku Kogyo Co., Ltd. products) ) And dicyclopentadiene diepoxide, and the like, but are not limited thereto (Reference: General Epoxy Resin Base Piece I p76-85).

These may be used independently and may be used together 2 or more types.

Although it does not specifically limit as a hardening | curing agent component in this invention, It is preferable to use a polyhydric carboxylic acid compound (B) individually or in combination with an acid anhydride, It is also possible to use these and other hardening agents in combination. When used in combination, the proportion of the total weight of the polyhydric carboxylic acid compound (B) and the acid anhydride in the total curing agent is preferably 30% by weight or more, particularly preferably 40% by weight or more.

As a hardening | curing agent which can be used together, an amine compound, an acid anhydride type compound, an amide type compound, a phenol type compound, a carboxylic acid type compound, etc. are mentioned, for example. Specific examples of the curing agent that can be used include amines and polyamide compounds (diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, dimers of linolenic acid and ethylenediamine Polyamide resins synthesized from the like), and reactants (acid phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydro phthalic anhydride, methyltetrahydro phthalic anhydride, methyl anhydride) Dixic acid, nadic acid anhydride, hexahydro phthalic anhydride, methylhexahydro phthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2 Acid anhydrides, such as heptane-2, 3- dicarboxylic anhydride and cyclohexane- 1,3, 4- tricarboxylic acid-3, 4- anhydride, and silicone type | system | groups, such as carbinol modified silicone Oligosaccharides), polyhydric phenols (bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpendiphenol, 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, dihydroxybenzene, dihydroxynaphthalene, etc.), formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde , o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4, Polycondensates such as 4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene, 1,4'-bis (methoxymethyl) benzene, and modifications thereof Halogenation ratios, such as water and tetrabromobisphenol A Sphenols, condensates of terpenes and phenols), others (imidazole, trifluoroborane-amine complexes, guanidine derivatives, and the like); and the like, but are not limited thereto. These may be used independently and may use 2 or more types.

In the curable resin composition of this invention, the compounding ratio of an epoxy resin component and a hardening | curing agent component uses a hardening | curing agent in the ratio which is 0.7-1.2 equivalent, Especially preferably, it is 0.75-1.1 equivalent with respect to 1 equivalent of epoxy groups of an epoxy resin component. It is desirable to.

When less than 0.7 equivalent with respect to 1 equivalent of epoxy groups or when exceeding 1.2 equivalent, hardening becomes incomplete and there exists a possibility that favorable hardened | cured material property may not be obtained.

In the curable resin composition of this invention, since the zinc salt and / or zinc complex (C) which are an essential component show the function as a curing catalyst as it is, it does not need to add a curing catalyst separately, but it can also use another curing catalyst together. As curing accelerators that can be used, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 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'-methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2'-unde Silimidazole (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: 3 adduct of 2-methylimidazole isocyanuric acid, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyano Various imidazoles of ethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole and those Polyazoles, polyhydric carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, oxalic acid, salts, amides such as dicyandiamide, 1,8-diaza Diaza compounds, such as bicyclo (5.4.0) undecene-7, and salts, such as those of tetraphenylborate and phenol novolak, salts of the said polyhydric carboxylic acid or phosphinic acid, tetrabutylammonium bromide, cetyltrimethylammonium Ammonium salts such as bromide and trioctylmethylammonium bromide, phosphines such as triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, phosphonium compounds, 2,4, Phenols such as 6-trisaminomethylphenol, metal compounds such as amine adducts, octylic acid tin, and the like, and microcapsule-type curing using these curing accelerators as microcapsules And accelerators. Which of these hardening accelerators is used is suitably selected by the characteristic calculated | required by the obtained transparent resin composition called transparency and hardening rate working conditions, for example. A hardening accelerator is normally used in 0.001-15 weight part with respect to 100 weight part of epoxy resin components.

The curable resin composition of this invention can add the various additives and auxiliary materials enumerated below.

Curable resin composition of this invention can also be made to contain a phosphorus containing compound as a flame retardance provision component. As a phosphorus containing compound, a reactive type or an additive type may be sufficient. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tricylelenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, and 1,3-phenylene bis (dike Phosphoric acid esters such as silenyl phosphate), 1,4-phenylene bis (dixylenyl phosphate), and 4,4'-biphenyl (dixylenyl phosphate); 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide Phosphanes, such as these; Although phosphorus containing epoxy compounds obtained by making an epoxy resin react with the active hydrogen of the said phosphanes, red phosphorus, etc. are mentioned, Phosphoric acid ester, a phosphane, or a phosphorus containing epoxy compound is preferable, and 1, 3- phenylene bis (dixylenyl Phosphate), 1,4-phenylenebis (dixylenylphosphate), 4,4'-biphenyl (dixylenylphosphate) or phosphorus-containing epoxy compounds are particularly preferred. As for content of a phosphorus containing compound, phosphorus containing compound / epoxy resin = 0.1-0.6 (weight ratio) are preferable. If it is less than 0.1, the flame retardancy is insufficient, and if it is more than 0.6, there is a risk of adversely affecting the hygroscopicity and dielectric properties of the cured product.

Moreover, binder resin can also be mix | blended with curable resin composition of this invention as needed. Examples of the binder resins include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenolic resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. It is not limited to. It is preferable that the compounding quantity of binder resin is the range which does not impair flame retardance and heat resistance of hardened | cured material, and is 0.05-50 weight part normally with respect to 100 weight part of epoxy resin components and a hardening | curing agent component, Preferably 0.05-20 weight part is used as needed. do.

An inorganic filler can be added to curable resin composition of this invention as needed. As the inorganic filler, powders such as crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, steatite, spinel, titania, talc or spheronized particles Although beads etc. are mentioned, It is not limited to these. In addition, these inorganic fillers may be used independently and may use 2 or more types. The content of these inorganic fillers which occupies 0 to 95 weight% in curable resin composition of this invention is used. The curable resin composition of the present invention can be added a silane coupling agent, stearic acid, palmitic acid, release agents such as zinc stearate, calcium stearate, various compounding agents such as pigments, and various thermosetting resins.

When using the curable resin composition of this invention for an optical material, especially an optical semiconductor sealing agent, it is possible to supplement a mechanical strength etc., without compromising transparency by using a nano order level filler as a particle diameter of the said inorganic filler used. . As a target for nano order level, it is preferable to use the filler of 500 nm or less of average particle diameter, especially 200 nm or less of average particle diameter from a viewpoint of transparency.

When using curable resin composition of this invention for an optical material, especially an optical semiconductor sealing agent, fluorescent substance can be added as needed. The phosphor has a function of absorbing a part of the blue light generated from the blue LED element, and emitting white light by emitting wavelength-converted yellow light. The phosphor is previously dispersed in the curable resin composition, and then 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, aluminate of rare earth elements, thiogallate, orthosilicate, etc. are illustrated. More specifically, there can be a phosphor such as YAG phosphors, TAG phosphor, orthosilicate phosphor, thiogallate phosphor, sulfide _{phosphor, 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. As the particle size of such a phosphor, one having a particle size known in the art is used, but the average particle size is preferably 1 to 250 µm, particularly 2 to 50 µm. When using such fluorescent substance, the addition amount is 1-80 weight part with respect to 100 weight part of organic components, such as organopolysiloxane (A), Preferably it is 5-60 weight part.

When the curable resin composition of the present invention is used in an optical material, especially an optical semiconductor encapsulant, thixotropic imparting agents including fine silica powder (also called aerosil or aerosol) can be added for the purpose of preventing sedimentation upon curing of various phosphors. have. As such a fine silica powder, for example, Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R972, Aerosil R974, Aerosil R202, Aerosil R812, Aerosil R812S, Aerosil R805, RY200 And RX200 (manufactured by Nippon Aerosil Co., Ltd.).

Curable resin composition of this invention can contain a phenol type compound as antioxidant.

It does not specifically limit as a phenol compound, For example, 2, 6- di-tert- butyl- 4-methyl phenol, 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, pentaerythryl-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, triethyleneglycol-bis [3- (3-t-butyl-5- Methyl-4-hydroxyphenyl) propionate], 2,2'-butylidenebis (4,6-di-tert-butylphenol), 4,4'- Thilidenebis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6- tert-butylphenol), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenolacrylate, 2- [1- (2-hydroxy- 3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenylacrylate, 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-pentyl Phenol, 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-pentylphenylacrylate, 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 phenol type compound.

For example, IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, IRGANOX245, IRGANOX259, IRGANOX295, IRGANOX3114, IRGANOX1098, IRGANOX1520L, AdekastacaoAO, AdekastaaAOAO, made by Chiba Specialty Chemicals AO-40, Adecastabe AO-50, Adecastabe AO-60, Adecastabe AO-70, Adecastabe AO-80, Adecastabe AO-90, Adecastabe AO-330, Sumitomo Kagaku High School Examples include Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP, and the like.

In addition, a commercially available additive can be used as a coloring inhibitor of resin. For example, TINUVIN328, TINUVIN234, TINUVIN326, TINUVIN120, TINUVIN477, TINUVIN479, CHIMASSORB2020FDL, CHIMASSORB119FL, etc. are mentioned as Chiba Specialty Chemicals.

Although it does not specifically limit as the compounding quantity when adding the said phenol type compound, It can add in the quantity which occupies 0.005-5.0 weight% in curable resin composition of this invention.

Curable resin composition of this invention is obtained by mixing each component uniformly. Moreover, curable resin composition of this invention can be easily made into the hardened | cured material by the method similar to the method known conventionally.

Curable resin composition of this invention is sufficient until it becomes uniform, for example using an extruder, a kneader, a roll, or a planetary mixer, an epoxy resin component, a hardening | curing agent component, a zinc salt, and / or a zinc complex (C) as needed. It can obtain by mixing. When the obtained curable resin composition is a liquid, it can be made into a hardened | cured material by making it potable, casting, impregnating a base material, pouring curable resin composition into a metal mold, and hardening by heating. On the other hand, when curable resin composition is solid, it can shape into hardened | cured material by shape | molding using a casting mold, a transfer molding machine, etc. after melt | dissolution, and further hardening by heating.

In addition to the optional components, a curing accelerator, an amine compound, a phosphorus containing compound, a phenol compound, a binder resin, an inorganic filler, or the like may be added and mixed in the above mixing step. As hardening temperature and time, it is 2 to 10 hours at 80-200 degreeC. As a hardening method, although it can also harden | cure at high temperature at once, it is preferable to heat up in steps and to advance hardening reaction. Specifically, initial curing is performed at 80 to 150 ° C, and post curing is performed at 100 ° C to 200 ° C. As a step of hardening, it is preferable to divide into 2-8 steps and to heat up, More preferably, it is 2-4 steps.

In addition, the curable 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, and the like as a curable resin composition varnish. It can be set as the hardened | cured material of the curable resin composition of this invention by hot-press-molding the prepreg obtained by impregnating and heat-drying the base material, such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, and paper. The solvent at this time is 10 to 70 weight% normally in the mixture of curable resin composition of this invention and the said solvent, The quantity which preferably occupies 15 to 70 weight% is used. Moreover, the epoxy resin hardened | cured material containing carbon fiber can also be obtained as a liquid composition by Resin Transfer Molding (RTM) system.

Moreover, curable resin composition of this invention can also be used as a composition for film type sealing. As a method of obtaining such a film sealing composition, the method of first performing curable resin composition of this invention as said curable resin composition varnish, apply | coating this on a peeling film, removing a solvent under heating, and performing B stage, Thereby, the composition for film type sealing can be obtained as a sheet-like adhesive agent. This sheet-like adhesive agent can be used as package film sealing of the interlayer insulation layer and optical semiconductor in a multilayer board | substrate.

Next, the case where the epoxy resin composition of this invention is used as a sealing material or die-bonding material of an optical semiconductor is demonstrated in detail.

When using curable resin composition of this invention as a sealing material or die-bonding material of optical semiconductors, such as a high brightness white LED, curable resin composition is prepared by fully mixing additives, such as an epoxy resin, a hardening | curing agent, a coupling agent, antioxidant, and a light stabilizer. . As a mixing method, you may mix at room temperature or warm using a kneader, three rolls, a universal mixer, a planetary mixer, a homo mixer, a homodisper, a bead mill, etc. Curable resin composition obtained can be used for both a sealing material or a die-bonding material, and a sealing material.

Optical semiconductor devices such as high-brightness white LEDs generally include semiconductor chips such as GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN, etc., stacked on substrates such as sapphire, spinel, SiC, Si, and ZnO. It is made by adhering to a lead frame, a heat sink, and a package using an adhesive agent (die bond material). There is also a type in which wires such as gold wires are connected in order to flow an electric current. On the other hand, the semiconductor chip is sealed around it with sealing materials, such as an epoxy resin. The sealing material is used to protect the semiconductor chip from heat and moisture and to serve as a lens function.

Curable resin composition of this invention can be used as this sealing material and die-bonding material. It is preferable to use curable resin composition of this invention for both a die bond material and a sealing material from a process top.

As a method of adhering a semiconductor chip to a substrate using the curable resin composition of the present invention, the curable resin composition of the present invention is applied onto a substrate by a dispenser, potting or screen printing, and then the semiconductor chip is placed on the curable resin composition and heated. The method of hardening is mentioned. In this way, the semiconductor chip can be adhered to the substrate. For heating, methods such as hot air circulation type, infrared ray, and high frequency can be used.

As for heating conditions, 1 minute-about 24 hours are preferable at 80-230 degreeC. For the purpose of reducing the internal stress generated at the time of heat curing, for example, after preliminary curing at 80 to 120 ° C for 30 minutes to 5 hours, it can be post-cured at 120 to 180 ° C for 30 minutes to 10 hours.

As a method of forming a sealing material, as described above, an injection method of molding by heating and curing the sealing material after injecting the sealing material into a mold frame into which a semiconductor chip is fixed, and injecting the sealing material onto the mold in advance, and fixing it thereon The compression molding method etc. which mold-release from a metal mold | die after carrying out heat-hardening by immersing the semiconductor chip which were used are used.

As an injection method, a dispenser, transfer molding, injection molding, etc. are mentioned.

Heating can be performed by hot air circulation, infrared, high frequency, or the like.

As for heating conditions, 1 minute-about 24 hours are preferable at 80-230 degreeC. For the purpose of reducing the internal stress generated at the time of heat curing, for example, after precuring at 80 to 120 ° C for 30 minutes to 5 hours, it can be post-cured at 120 to 180 ° C for 30 minutes to 10 hours.

The use of curable resin composition of this invention is applicable to the general use which curable resin, such as an epoxy resin, is used, without being limited only to the said use. For example, adhesives, paints, coatings, molding materials (including sheets, films, FRP, etc.), insulating materials (including printed boards, wire coatings, etc.), sealing materials, sealing materials, cyanate resin compositions and resists for substrates Additives to other resin, such as acrylic ester resin, etc. are mentioned as a hardening | curing agent for.

Examples of the adhesive include adhesives for electronic materials, in addition to civil engineering, construction, automobile, general office, and medical adhesives. Among these adhesives for electronic materials, interlayer adhesives of multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcement underfills, anisotropic conductive films (ACF), anisotropic conductive pastes (ACP), and the like. Mounting adhesives and the like.

As the sealant, potting such as condenser, transistor, diode, light emitting diode, IC, LSI, immersion, transfer mold sealing, potting seal such as COB, COF, TAB for IC, LSI, underfill such as flip chip, QFP And sealing (including reinforcing underfill) when mounting IC packages such as BGA and CSP.

The hardened | cured material obtained by this invention can be used for various uses including an optical component material. An optical material shows the general material used for the use which makes light, such as visible light, an infrared ray, an ultraviolet-ray, an X-ray, a laser, pass through the material. More specifically, the following are mentioned besides LED sealing materials, such as a lamp type and a SMD type. Liquid crystal display peripheral materials, such as a board | substrate material, a light guide plate, a prism sheet, a deflection plate, a retardation plate, a viewing angle correction film, an adhesive agent, and a polarizer protective film in the liquid crystal display field | area. In addition, LEDs used in sealing materials, antireflection films, optical correction films, housing materials, front glass protective films, front glass replacement materials, adhesives, and LED display devices, which are expected to be the next-generation flat panel displays. Mold material, LED sealing material, protective film of front glass, front glass substitute material, adhesive, substrate material in plasma address liquid crystal (PALC) display, light guide plate, prism sheet, deflection plate, retardation plate, viewing angle correction film, Adhesive film, polarizer protective film, protective film of front glass in organic EL (electroluminescent) display, front glass substitute material, adhesive, and various film substrates in front emission display (FED), front glass Protective film, front glass replacement material, adhesive. In the field of optical recording, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical card, pickup lens , Protective films, sealants, adhesives and the like.

In the field of optical instruments, it is a material for still camera lenses, a finder prism, a target prism, a finder cover, and a light receiving sensor unit. It is also a shooting lens and finder for video cameras. Moreover, it is a projection lens of a projection TV, a protective film, a sealing material, an adhesive agent, etc. Optical sensing device lens materials, sealing materials, adhesives, films and the like. In the field of optical components, fiber materials, lenses, waveguides, sealing materials for devices, adhesives, and the like around optical switches in optical communication systems. Optical fiber materials, ferrules, sealants, adhesives and the like around optical connectors. Optical passive components and optical circuit components include lenses, waveguides, LED sealants, CCD sealants, adhesives, and the like. A substrate material, a fiber material, a sealing material for an element, an adhesive, and the like around an optoelectronic integrated circuit (OEIC). In the optical fiber field, sensors for industrial use such as lighting and light guides for decorative displays, and displays and markers are also optical fibers for communication infrastructures and digital devices in homes. In semiconductor integrated circuit peripheral materials, it is a resist material for microlithography for LSI and ultra LSI materials. In the field of automobiles and transports, automotive lamp reflectors, bearing retainers, gear parts, corrosion resistant coatings, switch parts, headlamps, engine parts, electrical components, various interior and exterior products, drive engines, brake oil tanks, automotive antirust steel plates, Interior panels, interior materials, protective and binding wire harnesses, fuel hoses, automotive lamps and glass replacements. Moreover, it is the multilayer glass for railroad cars. In addition, toughness-imparting agents, structural members of engines, wire harnesses for protection and binding, and corrosion-resistant coatings of structural materials of aircrafts. In the field of construction, the materials are interior and processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. In agriculture, it is a house coating film. Next-generation opto-electronic functional organic materials include organic EL element peripheral materials, organic port reflective elements, optical amplification elements that are photo-optical conversion devices, photo-computation elements, substrate materials around organic solar cells, fiber materials, and sealing materials for elements. , Adhesives and the like.

Other uses of the optical material include general uses in which the curable resin composition is used, and examples thereof include adhesives, paints, coatings, molding materials (including sheets, films, and FRP), and insulating materials (printed boards, electric wires). Coating, etc.), and additives to other resins, etc., in addition to the sealant.

Example

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated further in detail by the synthesis example and the Example. In addition, this invention is not limited to these synthesis examples and an Example. In addition, in the following synthesis examples and examples, "part" means a weight part and "%" means weight%, respectively. In addition, each physical property value in an Example was measured with the following method.

(1) Molecular weight: The polystyrene conversion and the weight average molecular weight measured under the following conditions were computed by the gel permeation chromatography (GPC) method.

Conditions of GPC

Manufacturer: Shimadzu Seisakusho

Column: Guard Column SHODEX GPC LF-G LF-804 (3ea)

Flow rate: 1.0 ml / min.

Column temperature: 40 ℃

Solvent used: THF (tetrahydrofuran)

Detector: Differential Refractive Detector (RI)

(2) Epoxy equivalent: It measures by the method of JISK-7236.

(3) Viscosity: It measures at 25 degreeC using the Toki Sangyo Co., Ltd. E-type viscosity meter (TV-20).

Synthesis Example 1

106 parts of (beta)-(3,4 epoxycyclohexyl) ethyltrimethoxysilane and 234 parts of silanol terminal methylphenyl silicone oil of the weight average molecular weight 1700 (GPC measurement) as a manufacturing process (Cyrolol equivalent of 850, GPC) It calculated as half of the weight average molecular weight measured using, 18 parts of 0.5% potassium hydroxide (KOH) methanol solutions (0.09 parts as KOH number) were put into the reaction container, and the bath temperature was set to 75 degreeC, and it heated up. After heating, the mixture was reacted under reflux for 8 hours.

After adding 305 parts of methanol as a manufacturing process (ii), 86.4 parts of 50% distilled-water methanol solutions were dripped over 60 minutes, and it was made to react at 75 degreeC under reflux for 8 hours. After completion of the reaction, methanol was distilled off at 80 ° C. after neutralization with an aqueous 5% sodium dihydrogen phosphate solution. 380 parts of methyl isobutyl ketones (MIBK) were added, and water washing was repeated 3 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 718 g / eq, the weight average molecular weight was 2200, and the appearance was colorless and transparent.

Synthesis Example 2

20 parts of tricyclodecane dimethanol, methylhexahydrophthalic anhydride (Shin Nihon Rika) Co., Ltd. product, lycaside MH, the following acid anhydride (H), performing nitrogen purge to the flask provided with the stirrer, the reflux condenser, and the stirring apparatus. 100 parts were added, and the reaction was carried out at 40 ° C. for 3 hours, followed by heating and stirring at 70 ° C. for 1 hour (the loss of tricyclodecane dimethanol (1 area% or less) was confirmed by GPC). 120 parts of hardening agent compositions (T-1) containing a carboxylic acid (B-1) and an acid anhydride (H-1) were obtained. The obtained hardening | curing agent composition (T-1) is a colorless liquid resin, The purity by GPC is 55 area% of polyhydric carboxylic acid (B-1; following formula (7)) and 45 area of acid anhydride (H-1). It was%. In addition, the functional group equivalent was 201 g / eq. In addition, the viscosity in 25 degreeC was 18900 mPa * s (E-type viscosity meter).

Synthesis Example 3

20 parts of 2,4-diethylpentanediol and 100 parts of acid anhydrides (H-1) were added, carrying out nitrogen purge to the flask provided with the stirrer, the reflux condenser, and the stirring apparatus, and 70 degreeC after reaction at 40 degreeC for 3 hours. The polyvalent carboxylic acid (B-2) and the acid anhydride (H-1) were removed by heating and stirring for 1 hour (GPC confirmed loss of 2,4-diethylpentanediol (1 area% or less)). 120 parts of hardening agent compositions (T-2) containing were obtained. The obtained curing agent composition (T-2) was a colorless liquid resin, and the purity by GPC was 50 area% of polyhydric carboxylic acid (B-2; formula 8) and 50 area% of acid anhydride (H-1). . In addition, the functional group equivalent was 201 g / eq. In addition, the viscosity in 25 degreeC was 16200 mPa * s (E-type viscosity meter).

Synthesis Example 4

As a manufacturing process, 296 parts of (beta)-(3,4 epoxycyclohexyl) ethyltrimethoxysilane and 505 parts (yranol equivalent of 850, GPC) of a silanol terminal methylphenyl silicone oil of the weight average molecular weight 1700 (GPC measurement value) It calculated as half of the weight average molecular weight measured and used, and 40 parts of 0.5% potassium hydroxide (KOH) methanol solutions (0.2 parts as KOH number) were put into the reaction container, and the bath temperature was set to 75 degreeC, and it heated up. After heating, the mixture was reacted under reflux for 8 hours.

After adding 510 parts of methanol as a manufacturing process (ii), 130 parts of 50% distilled-water methanol solutions were dripped over 60 minutes, and it was made to react at 75 degreeC under reflux for 8 hours. After completion of the reaction, methanol was distilled off at 80 ° C. after neutralization with an aqueous 5% sodium dihydrogen phosphate solution. 704 parts of methyl isobutyl ketones (MIBK) were added, and water washing was repeated 3 times. Subsequently, 697 parts of organopolysiloxane compound (A-2) which has a reactive functional group were obtained by removing a solvent at 100 degreeC under pressure reduction of an organic phase. Epoxy equivalent of the obtained compound was 598 g / eq, the weight average molecular weight was 2370, and the external appearance was colorless and transparent.

Synthesis Example 5

12 parts of tricyclodecane dimethanol, 18 parts of 2,4-diethyl-1,5-pentanediol, methylhexahydrophthalic anhydride (Shin Nihon), performing nitrogen purge to the flask provided with the stirrer, the reflux condenser, and the stirring apparatus. RICCA Co., Ltd. product, ricaside MH (equivalent to acid anhydride (H-1)) 155 parts, 1,3,4-cyclohexane tricarboxylic acid-3,4- anhydride (Mitsubishi Gas Kagaku Co., Ltd.) First, 15 parts of H-TMAn, hereinafter referred to as acid anhydride (H-2) were added, and the mixture was heated and stirred at 70 ° C for 1 hour after reaction at 40 ° C for 3 hours (loss of raw material alcohol by GPC (one area). % Or less)) 200 parts of hardening agent compositions (T-3) containing polyhydric carboxylic acid (B-1) (B-2) and acid anhydride (H-1) (H-2) were obtained. The obtained curing agent composition (T-3) is a colorless liquid resin, and purity by GPC is 52 area% of polyhydric carboxylic acids (B-1, B-2) and acid anhydrides (H-1, H-2). 48 area%. In addition, the functional group equivalent was 190 g / eq. In addition, the viscosity in 25 degreeC was 15500 mPa * s (E-type viscosity meter).

Synthesis Example 6

44 parts of (beta)-(3,4 epoxycyclohexyl) ethyl trimethoxysilane and 153 parts (yranol equivalent of 850, GPC) of a silanol terminal methylphenyl silicone oil of a weight average molecular weight 1700 (GPC measurement) as a manufacturing process (vi) It calculated | required as half of the weight average molecular weight measured using, and 11.2 parts (0.56 parts as KOH number) of 0.5% potassium hydroxide (KOH) methanol solution were put into the reaction container, and the bath temperature was set to 75 degreeC, and it heated up. After heating, the mixture was reacted under reflux for 8 hours.

After adding 157 parts of methanol as a manufacturing process (ii), 19.3 parts of 50% distilled-water methanol solutions were dripped over 60 minutes, and it reacted at 75 degreeC under reflux for 8 hours. After completion of the reaction, methanol was distilled off at 80 ° C. after neutralization with an aqueous 5% sodium dihydrogen phosphate solution. 177 parts of methyl isobutyl ketones (MIBK) were added, and water washing was repeated 3 times. Subsequently, 178 parts of organopolysiloxane compounds (A-3) 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 1020 g / eq, the weight average molecular weight was 2100, and the appearance was colorless and transparent.

Examples 1, 2, 3, 4, Comparative Examples 1, 2, 3

Organopolysiloxane compound (A-1) obtained by the synthesis example 1 as an epoxy resin, the hardening | curing agent composition (T-1) obtained by the synthesis examples 2 and 3 as a hardening | curing agent, (T-2) (organopolysiloxane (A) and hardening | curing agent composition The ratio of (T-1) and (T-2) is 1: 1 in functional group equivalents, 2-ethylhexane ester of phosphoric acid as phosphoric acid salt and / or zinc complex (phosphate: monoester: diester: triester) Sieve 3.5: 68.2: 26.5: 1.8 However, since the trimethylsilylation treatment is performed, the sensitivity is not accurate and is not an accurate weight ratio. Hereinafter, a zinc complex of zinc salt and / or zinc complex (C-1) (phosphorus: Zinc = 1.7: 1 measured by ICP emission spectroscopy, according to JIS K 0166) Propylene glycol solution (manufactured according to Japanese Patent Publication No. 2003-51495, hereinafter referred to as (C-1)), 4 as a curing accelerator A class phosphonium salt (it is called Nippon Kagaku Co., Ltd. hishicholine PX4MP, hereinafter a catalyst (I-1)), bis (as an additive 2,2,6,6-tetramethyl-4-piperidyl) sepacate (TINUVIN770DF manufactured by Chiba Japan, hereinafter referred to as (L-1)) and 4,4'-butylidene bis (3- Using methyl-6-tert-butylphenyl-di-tridecylphosphite) (ADEKASTAB 260 manufactured by ADEKA, hereinafter referred to as (M-1)), and blended in the compounding ratio (parts by weight) shown in Table 1 below. Defoaming was performed for 20 minutes, and the curable resin composition for this invention or comparison was obtained.

The obtained curable resin composition was shape | molded gradually to the metal mold | die for test pieces, the casting material was hardened on condition of 150 degreeC * 1 hour after the precure of 120 degreeC * 3 hours, and the hardened | cured material for various tests was obtained. About the obtained hardened | cured material, the following hardness and the tests of the heat durability transmittance test were evaluated on the conditions described below. The results are shown in Table 1 together.

(Hardness)

Shore A

It measured based on JISK7215 "the durometer hardness test method of plastic."

(Thermal durability transmittance test)

Heat test conditions: 96 hours in 150 ℃ oven

Test piece size: Thickness 1mm

Evaluation conditions: The transmittance | permeability of 400 nm was measured with the spectrophotometer, and the change rate (retention rate) was computed.

(LED lighting test)

Moreover, after performing curable resin composition obtained by the Example and the comparative example for 20 minutes by vacuum defoaming, it filled in the syringe and cast on the surface mount type LED which mounted the light emitting element which has light emission wavelength 465nm using the precision ejection apparatus. Thereafter, the LED for lighting test is obtained by curing under predetermined curing conditions (2 hours at 110 ° C and 3 hours at 150 ° C). The lighting test performed the lighting test at 60 mA (30 mA of constant current drive specified electric current) which is double of a specified electric current, and measured initial stage roughness.

Examples 5 and 6, Comparative Example 4

The organopolysiloxane compound (A-2) obtained by the synthesis example 2 as an epoxy resin, and the hardener composition (T-1) (organopolysiloxane (A) and the hardening | curing agent composition (T-1) which were obtained by the synthesis example 2 as a hardening | curing agent are 1: 0.8) as functional group equivalent, zinc salt and / or a zinc complex (C-1), a catalyst (I-1), and an additive (L-1) (M-1) shown as following Table 2 as a hardening accelerator It mix | blended in a compounding ratio (weight part), defoamed for 20 minutes, and obtained curable resin composition for this invention or a comparison.

The obtained curable resin composition was shape | molded gradually to the metal mold | die for test pieces, the casting material was hardened on condition of 150 degreeC * 1 hour after the precure of 120 degreeC * 3 hours, and the hardened | cured material for various tests was obtained. About the obtained hardened | cured material, the following heat resistance test, hardness, and the test of the transmittance | permeability test were evaluated on the conditions described below. The results are shown in Table 2 together.

(Heat resistance test)

Measuring conditions

Dynamic Viscoelasticity Meter: Made in TA-instruments, DMA-2980

Measuring temperature range: -30 ℃ to 280 ℃

Temperature rise rate: 2 ℃ / min

Test piece size: The thing cut out to 5 mm x 50 mm was used (thickness about 800 micrometers).

Analysis condition

Tg: The peak point of Tan-δ in the DMA measurement was defined as Tg.

30 degreeC elastic modulus: The elasticity modulus at 30 degreeC was measured.

(Hardness test)

Shore A

It measured based on JISK7215 "the durometer hardness test method of plastic."

Transmittance test

Test piece size: Thickness 1mm

Evaluation condition: The transmittance | permeability of 400 nm was measured with the spectrophotometer.

In addition, an outer diameter of 5 mm x 5 mm surface-mount LED package (inner diameter 4.4 mm, outer wall height 1.25 mm), which was filled with a syringe using the obtained curable resin composition and mounted with a chip having a center emission wave of 465 nm using a precision ejection device, was used. ). The castings were put into a heating furnace and cured at 120 ° C for 1 hour and at 150 ° C for 3 hours to prepare an LED package. The LED package was left to stand in the corrosive gas on condition of the following, and the change of the color of the silver-plated lead frame part inside the sealing was observed (corrosion gas permeability test). The result was combined with Table 2 and shown.

Corrosion Gas Permeability Test

Measuring conditions

Corrosive gas: 20% aqueous ammonium sulfide solution (discolors black when sulfur component reacts with silver)

Contact method: The container of the ammonium sulfide aqueous solution and the said LED package were mixed in the glass bottle, and the cover of the bulb glass bottle was covered, and the volatilized ammonium sulfide gas and the LED package were contacted and exposed in a sealed condition.

Determination of Corrosion: The time when the lead frame inside the LED package was discolored black (called blackening) was observed, and the longer the discoloration time was, the better the corrosion resistance gas was. Observation was withdrawn after 1 hour, 2 hours, 3 hours, and 4 hours, and it confirmed that evaluation did not change color | variation, (circle) and a brownish-brown thing were made into x and a completely blackened thing × x.

According to Examples 1-4 and Comparative Examples 1-3, the curable resin composition of this invention is excellent in heat-coloring property (heat-resistant transmittance test), and gives the hardened | cured material which is excellent in the extraction efficiency of light (LED lighting test), and an optical characteristic is It can be seen that it is excellent.

From Examples 5, 6 and Comparative Example 4, the curable resin composition of the present invention provides a cured product having excellent gas permeability (corrosion gas permeability test), and is used in fields requiring optical properties such as semiconductor chips or LEDs that are weak to external environments. It is clear that it is useful.

Examples 7-12, Comparative Examples 5-9

The organopolysiloxane compound (A-1) obtained by the synthesis examples 1, 4, 6 as an epoxy resin (A-1), (A-2), (A-3) and the hardening | curing agent composition (T-1) obtained by the synthesis examples 2 and 3 as a hardening | curing agent. (T-2) (The ratio of the organopolysiloxane (A) and the curing agent composition (T-1) or (T-2) is 1: 0.8 in functional group equivalents), acid anhydride (H-1) (organopolysiloxane ( The ratio of A) to acid anhydride (H-1) is 1: 0.8 in functional group equivalents, zinc 2-ethylhexanoate (C-2) and zinc undecylenate (C-3) as zinc salts and / or zinc complexes. Zinc 2-ethylhexanoate (Kimidazole compound-containing King Industries XK-614, hereinafter referred to as (C-4)), and a quaternary phosphonium salt (Nippon Kagaku Kogyo Co., Ltd.) as a curing accelerator, Bis (2,2,6,6-tetramethyl-4-piperi) as an additive, an imidazole compound (hereinafter referred to as Shikoku Kasei 2E4MZ, hereinafter catalyst (I-3)), and an additive Deal) Sepacate (TINUVIN770DF made in Chiba Japan, hereinafter referred to as (L-1) C) by the following Table 3, blended in the blending ratio (parts by weight) shown in the 4 and obtain a curable resin composition for the present invention or a comparative subjected to degassing using a 20 minutes.

The obtained curable resin composition was shape | molded gradually to the metal mold | die for test pieces, the casting material was hardened on condition of 140 degreeC * 5 hours after the precure of 110 degreeC * 3 hours, and the hardened | cured material for various tests was obtained. About the obtained hardened | cured material, the corrosive gas permeability test (as for test methods etc., it carried out similarly to the above except having made observation after 1 hour, 2 hours, 3 hours, 6 hours, and 10 hours later) was performed. The results are shown together in Tables 3 and 4 below.

Example 13, 14

The organopolysiloxane compound (A-3) obtained by the synthesis example 6 as an epoxy resin, and the hardening agent composition (T-3) (organopolysiloxane (A) and the hardening | curing agent composition (T-3) which were obtained by the synthesis example 5 as a hardening | curing agent are 1: 0.8), zinc salt and / or zinc complex (C-1), (C-2) as a functional group equivalent, a hindered amine compound as an additive (referred to as Adekace LA-81, hereinafter referred to as (L-2)) , Using a phosphorus compound (made by Adeca 260, hereinafter referred to as (L-3)) at a blending ratio (weight part) shown in Table 5 below, degassing was performed for 20 minutes to obtain a curable resin composition of the present invention.

Corrosion Gas Permeability Test

The obtained curable resin composition was shape | molded gradually to the metal mold | die for test pieces, the casting material was hardened on condition of 150 degreeC * 3 hours after the precure of 120 degreeC * 1 hour, and the hardened | cured material for various tests was obtained. About the obtained hardened | cured material, the corrosive gas permeability test (as mentioned above regarding test methods etc.) was done. The results are shown in Table 5 together.

(LED lighting test)

The obtained curable resin composition was filled in the syringe, and it casted to the surface-mount type LED (SMD type 5 mm diameter regulation current 20 mA) which mounted the light emitting element which has a light emission wavelength of 465 nm using the precision discharge apparatus. Then, the LED for lighting test is obtained by hardening | curing by predetermined | prescribed hardening conditions (1 hour at 120 degreeC, and 3 hours at 150 degreeC). The lighting test performed the lighting test in the 230 mA current exceeding 20 mA which is a specified electric current. Detailed conditions are shown below. As a measurement item, illuminance before and after lighting for 40 hours was measured using the integrating sphere, and the retention of illuminance of the test LED was calculated. The results are shown in Table 5.

Lighting detailed condition

Emission wavelength: center emission wavelength, 465 nm

Driving method: constant current method, 230 ㎃ (light emitting device specified current is 20 ㎃)

Driving environment: Light at 25 ° C in 65% moist heat

Evaluation: The illuminance after 20 hours and 40 hours and its roughness retention rate were measured, respectively.

Although this invention was demonstrated in detail with reference to the specific aspect, it is clear for those skilled in the art for various changes and correction to be possible, without leaving | separating the mind and range of this invention.

In addition, this application is based on the JP Patent application (Japanese Patent Application 2009-271469) of an application on November 30, 2009, The whole is taken in into the reference. In addition, all references cited herein are accepted in their entirety.

Claims (8)

As curable resin composition which makes organopolysiloxane (A) and a zinc salt and / or a chlorine complex (C) an essential component:
However, said organopolysiloxane (A) satisfy | fills the following conditions, The curable resin composition characterized by the above-mentioned.
Organopolysiloxane (A): The epoxy resin which has a glycidyl group and / or an epoxycyclohexyl group at least in the molecule | numerator. The method of claim 1,
The zinc salt and / or chlorine complex (C) is at least one selected from the group consisting of zinc salts of at least one acid selected from phosphate esters and phosphoric acid, and chlorine complexes having the acid and the zinc salt as ligands. Curable resin composition characterized by the above-mentioned. The method of claim 1,
The zinc salt and / or chlorine complex (C) is at least one member selected from the group consisting of zinc salts of carboxylic acids having 1 to 30 carbon atoms, and zinc complexes having the acid and the zinc salt as ligands. Curable resin composition. The method according to any one of claims 1 to 3,
Curable resin composition which has a 2 or more carboxyl group and contains the polyhydric carboxylic acid (B) which makes an aliphatic hydrocarbon group main skeleton. The method of claim 4, wherein
The said polyhydric carboxylic acid (B) is a compound obtained by reaction of a C5 or more 2- and 6-functional polyhydric alcohol and saturated aliphatic cyclic anhydride, The curable resin composition characterized by the above-mentioned. 6. The method according to any one of claims 1 to 5,
Curable resin composition containing an acid anhydride. 7. The method according to any one of claims 1 to 6,
Curable resin composition containing a hindered amine light stabilizer and / or phosphorus containing antioxidant. Hardened | cured material formed by hardening | curing curable resin composition of any one of Claims 1-7.