JPWO2009072632A1 - Curable composition, optical element coating composition, LED sealing material, and method for producing the same - Google Patents

Abstract

The present invention provides a curable composition, an optical element coating composition, an LED sealing material, and an LED encapsulating material that are capable of obtaining a cured product having excellent ultraviolet resistance and transparency and high hardness. The object is to provide a manufacturing method. The curable composition of the present invention has an organic group containing an epoxy group at the end, and one or two hydroxyl groups are bonded to silicon bonded with the epoxy group-containing organic group, and the epoxy equivalent is 150 g. / Eq. Or more, 2000 g / eq. It is characterized by containing an epoxy group-terminated polydimethylsiloxane and a curing agent that are less than.

Description

  The present invention relates to a curable composition, an optical element coating composition, an LED sealing material, and a method for producing the same.

  A polysiloxane material is a material having excellent durability such as heat resistance and ultraviolet resistance. In such a polysiloxane-based material, in order to ensure thick film properties, in particular, mm-thick film properties required for LED encapsulating materials, etc., it contains a flexible polydimethylsiloxane component that is flexible and can relieve stress Although it is necessary to increase the amount, such a material has a problem in that it has few crosslinking groups (crosslinking points) and is inferior in curability.

  On the other hand, organopolysiloxane having an epoxy group is known as a curable polysiloxane mainly composed of polydimethylsiloxane. This curable polysiloxane can be crosslinked by condensing an alkoxy group remaining in the siloxane skeleton, using an acid anhydride as a crosslinking agent, or ring-opening polymerization of an epoxy group.

  The method of curing the above epoxy-containing polysiloxane with an acid anhydride is generally known, but there is a problem in ultraviolet resistance such as yellowing or burning when the cured product is irradiated with ultraviolet rays of 400 nm or less. was there.

  For example, JP-A-7-126391 discloses an epoxy group and an alkoxy group obtained by reacting an organopolysiloxane having a SiOH group with an alkoxysilane having an epoxy group in the presence of a divalent tin-based compound. Epoxy functional organopolysiloxanes having the following are disclosed: This organopolysiloxane can be cured by ultraviolet irradiation, but an acid generator such as an onium salt is required to open the epoxy group. As described above, when a cured product is formed using an acid generator such as an onium salt, there are various problems such as separation and bleeding of the acid generator due to the compatibility with polydimethylsiloxane and making it opaque. It was. Also in the case of thermosetting, an acid generator such as an onium salt is used to open an epoxy group, but there are problems such as insufficient curability. It is known that a silanol group-containing compound such as triphenylsilanol is blended with an epoxy group-containing polydimethylsiloxane as a silanol component and cured with a metal chelate compound, but it is curable when the amount of the silanol group-containing compound is small. However, when the amount of the silanol group-containing compound added is large, there are various problems such as separation / bleeding and opaqueness, and deterioration of light resistance.

WO2005 / 100445 discloses an epoxy group-containing polyorganosiloxane. This publication describes that a cured product of an epoxy group-containing polysiloxane can be obtained by using a carboxylic acid anhydride and a curing accelerator in combination. This cured product is superior to epoxy resin in ultraviolet resistance, but greatly inferior to silicone.
JP-A-7-126391 International Publication No. 2005/100445

  The present invention provides a curable composition, an optical element coating composition, an LED sealing material, and an LED encapsulating material that are capable of obtaining a cured product having excellent ultraviolet resistance and transparency and high hardness. The object is to provide a manufacturing method.

  As a result of intensive studies to solve the above problems, the present inventors have found that a silanol group-containing epoxy group-terminated polysiloxane obtained by further hydrolyzing a condensate of a silanol group-containing polydimethylsiloxane and an epoxy group-containing alkoxysilane. By using dimethylsiloxane and a specific catalyst, it can be cured without adding an acid generator such as an acid anhydride or onium salt used as an epoxy group curing agent, or a silanol group-containing compound. As a result, the present invention has been completed.

  That is, the curable composition according to the present invention has an epoxy group-terminated polydimethyl group having an epoxy group-containing organic group at the end and one or two hydroxyl groups bonded to silicon to which the organic group is bonded. It contains siloxane and a curing agent.

  The epoxy equivalent of the epoxy group-terminated polydimethylsiloxane was 150 g / eq. Or more, 2000 g / eq. It is preferable that it is less than.

  Moreover, the curable composition which concerns on this invention is polydimethylsiloxane which has a silanol group at the terminal, following formula (1)

(In the formula (1), R ^E represents an organic group containing an epoxy group, R ¹ and R ² each independently represents an unsubstituted or substituted monovalent hydrocarbon group, m is 1 or 2, and n is 2 Or 3 and m + n is 4 or less)
It contains an epoxy group-terminated polydimethylsiloxane obtained by subjecting the epoxy group-containing alkoxysilane represented by the formula to dealcoholization reaction, introducing an epoxy group into polydimethylsiloxane and then hydrolyzing the reaction product, and a curing agent. . In addition, a molar ratio ((number of moles of silanol group-containing polydimethylsiloxane)) in the dealcoholization reaction of the polydimethylsiloxane having a silanol group at the terminal and the epoxy group-containing alkoxysilane represented by the formula (1): (Number of moles of epoxy group-containing alkoxysilane)) is preferably in the range of 1: 0.6 to 1:10. R ^E in the formula (1) is preferably an organic group containing an epoxycycloalkyl group.

  The metal chelate compound is preferably an aluminum chelate.

  The curable composition may further contain silica particles. Moreover, following formula (1)

(In the formula (1), R ^E represents an organic group containing an epoxy group, R ¹ and R ² each independently represents an unsubstituted or substituted monovalent hydrocarbon group, m is 1 or 2, and n is 2 Or 3 and m + n is 4 or less)
And an epoxy group-containing alkoxysilane represented by the following formula (2)

(In Formula (2), R ³ and R ⁴ each independently represents an unsubstituted or substituted monovalent hydrocarbon group, and p is an integer of 0 to 2)
It may further contain a hydrolysis condensate with an alkoxysilane represented by the formula: Furthermore, you may further contain the at least 1 sort (s) of compound selected from the compound which has an oxetane compound, a thiol compound, and an isocyanuric ring structure.

  The optical element coating material according to the present invention comprises the above curable composition.

  The LED sealing material according to the present invention is composed of the curable composition.

  The cured product according to the present invention is obtained by thermally curing the curable polysiloxane composition.

  The epoxy group-terminated polydimethylsiloxane according to the present invention has an epoxy group-containing organic group at the end, and one or two hydroxyl groups are bonded to silicon bonded with the epoxy group-containing organic group. Equivalent is 150 g / eq. Or more, 2000 g / eq. It is characterized by being less than.

  The epoxy group-terminated polydimethylsiloxane according to the present invention includes a polydimethylsiloxane having a silanol group at the terminal, and the following formula (1):

(In the formula (1), R ^E represents an organic group containing an epoxy group, R ¹ and R ² each independently represents an unsubstituted or substituted monovalent hydrocarbon group, m is 1 or 2, and n is 2 Or 3 and m + n is 4 or less)
It is obtained by subjecting the epoxy group-containing alkoxysilane represented by the formula to dealcoholization reaction and then hydrolyzing the reaction product.

  The epoxy group-terminated polydimethylsiloxane according to the present invention includes a polydimethylsiloxane having a silanol group at the terminal, and the following formula (1):

(In the formula (1), R ^E represents an organic group containing an epoxy group, R ¹ and R ² each independently represents an unsubstituted or substituted monovalent hydrocarbon group, m is 1 or 2, and n is 2 Or 3 and m + n is 4 or less)
The molar ratio ((number of moles of silanol group-containing polydimethylsiloxane) :( number of moles of epoxy group-containing alkoxysilane)) is 1: 0.6 to 1:10. It is obtained by subjecting to a dealcoholization reaction followed by hydrolysis of the reaction product.

  The method for producing an epoxy group-terminated polydimethylsiloxane according to the present invention comprises a polydimethylsiloxane having a silanol group at the terminal, and the following formula (1):

(In the formula (1), R ^E represents an organic group containing an epoxy group, R ¹ and R ² each independently represents an unsubstituted or substituted monovalent hydrocarbon group, m is 1 or 2, and n is 2 Or 3 and m + n is 4 or less)
It is characterized in that the epoxy group-containing alkoxysilane represented by the formula (2) is dealcoholized and then the reaction product is hydrolyzed.

  The method for producing an epoxy group-terminated polydimethylsiloxane according to the present invention comprises a polydimethylsiloxane having a silanol group at the end, and the following formula (1):

(In the formula (1), R ^E represents an organic group containing an epoxy group, R ¹ and R ² each independently represents an unsubstituted or substituted monovalent hydrocarbon group, m is 1 or 2, and n is 2 Or 3 and m + n is 4 or less)
The molar ratio ((number of moles of silanol group-containing polydimethylsiloxane) :( number of moles of epoxy group-containing alkoxysilane)) is 1: 0.6 to 1:10. It is characterized in that it is subjected to a dealcoholization reaction followed by hydrolysis of the reaction product.

In the method for producing the epoxy group-terminated polydimethylsiloxane, R ^E in the formula (1) is preferably an organic group containing an epoxycycloalkyl group.

  According to the present invention, there can be obtained an epoxy group-terminated polydimethylsiloxane and a curable composition, which are excellent in storage stability and curability, and provide a cured product excellent in transparency, light resistance, and heat and moisture resistance. The epoxy group-terminated polydimethylsiloxane can be cured without using an acid generator such as an acid anhydride or an onium salt generally used as a curing agent for an epoxy group, or a silanol group-containing compound. In addition, it is possible to suppress deterioration of the cured product properties due to acid generators such as acid anhydrides and onium salts, and silanol group-containing compounds. Furthermore, since the said curable composition does not generate | occur | produce a defect even when it forms and hardens | cures the thick film of a mm unit, it can be used conveniently as a sealing material for LED.

It is a schematic diagram of a light emitting diode. It is a schematic diagram of the light emitting diode which has a fluorescence part.

Explanation of symbols

50 Light-Emitting Element 51 Sealing Material 52 Fluorescent Portion 53 Binder 54 Phosphor

<Epoxy group-terminated polydimethylsiloxane>
The epoxy group-terminated polydimethylsiloxane according to the present invention has an organic group containing an epoxy group at the end, and one or two hydroxyl groups are bonded to silicon to which the organic group, that is, the epoxy group-containing organic group is bonded. Yes.

  The epoxy equivalent of the epoxy-terminated polydimethylsiloxane according to the present invention is 150 g / eq. Or more, 2000 g / eq. It is preferable that it is less than. A more preferable epoxy equivalent is 200 to 2000, and a particularly preferable epoxy equivalent is 300 to 1500. In the curable polysiloxane composition described later, if this epoxy equivalent is less than 150, cracks may occur during curing, and if this epoxy equivalent is 2000 or more, the cured product hardness may be inferior.

  Such an epoxy group-terminated polydimethylsiloxane can be produced by the following procedure. First, polydimethylsiloxane having a silanol group at the terminal and the following formula (1)

(In the formula (1), R ^E represents an organic group containing an epoxy group, R ¹ and R ² each independently represents an unsubstituted or substituted monovalent hydrocarbon group, m is 1 or 2, and n is 2 Or 3 and m + n is 4 or less)
And an epoxy group-containing alkoxysilane represented by the formula: As a result, polydimethylsiloxane having an epoxy group-containing organic group at the terminal and one or two alkoxy groups bonded to silicon bonded with the epoxy group-containing organic group is formed. Thereafter, the epoxy group-terminated polydimethylsiloxane of the present invention is obtained by hydrolyzing the alkoxy group of the polydimethylsiloxane.

Therefore, the epoxy group-containing organic group in the epoxy group-terminated polydimethylsiloxane of the present invention is derived from R ^E of the above formula (1).

[Silanol-terminated polydimethylsiloxane]
The polydimethylsiloxane having a silanol group at the terminal (hereinafter abbreviated as “silanol group-terminated polydimethylsiloxane”) is a polydimethylsiloxane having at least one, preferably two or more silanol groups at the ends of the main chain and / or side chain. If it is dimethylsiloxane, it will not specifically limit. Such a silanol group-terminated polydimethylsiloxane can be produced, for example, by hydrolyzing and condensing dimethyl dialkoxysilane or dimethyldichlorosilane.

  Examples of the dimethyldialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-i-propoxysilane, and dimethyldi-n-butoxysilane. These dimethyl dialkoxysilanes can be used alone or in combination of two or more.

  The silanol group-terminated polydimethylsiloxane can also be produced by ring-opening condensation of a cyclic organosiloxane. Cyclic organosiloxanes include hexaphenylcyclotrisiloxane, octaphenylcyclotetrasiloxane, tetilavinyltetramethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, pentamethylcyclotetrasiloxane, hexamethylcyclotetrasiloxane, Examples thereof include tetramethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like.

  In addition, as the silanol group-terminated polydimethylsiloxane, commercially available both-end silanol group-containing poly, such as YF-3800, XC96-723 manufactured by Momentive Performance Materials, and FM9915 manufactured by Chisso (or a trade name). Dimethylsiloxane can also be used. The silanol group-terminated polydimethylsiloxane may have a branched structure such as a star shape or a comb shape.

  The silanol group-terminated polydimethylsiloxane has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of preferably 300 to 5,000, more preferably 400 to 4,500, and particularly preferably 400 to 4,000. When a silanol group-terminated polydimethylsiloxane having a weight average molecular weight in the above range is used, an epoxy group-terminated polydimethylsiloxane having a good balance between cured product hardness and thick film formability can be obtained.

[Epoxy group-containing alkoxysilane]
As shown in the above formula (1), the epoxy group-containing alkoxysilane is a silane compound having an organic group containing an epoxy group and two or three alkoxy groups. In the above formula (1), R ^E is an organic group containing an epoxy group, for example, γ-glycidoxypropyl group, 3,4-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 2- (3 , 4-epoxycyclopentyl) ethyl group, 2- (3,4-epoxycyclohexyl) ethyl group and the like, and an epoxy group-containing hydrocarbon group having 5 to 20 carbon atoms. Among these organic groups, an organic group containing an epoxycycloalkyl group is preferable, and an epoxycyclohexylethyl group is more preferable from the viewpoint of stability during a hydrolysis reaction described later. R ¹ and R ² are each independently an unsubstituted or substituted monovalent hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, or an i-butyl group. , Sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like, preferably methyl group and ethyl group.

  Among the epoxy group-containing alkoxysilanes, γ-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are preferred, and in terms of stability during the hydrolysis reaction described later, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is particularly preferred.

[Dealcoholization reaction]
In the above dealcoholization reaction, the mixing molar ratio ((number of moles of silanol group-containing polydimethylsiloxane) :( number of moles of epoxy group-containing alkoxysilane)) of silanol group-terminated polydimethylsiloxane and epoxy group-containing alkoxysilane is 1: The range is from 0.6 to 1:10, preferably from 1: 0.6 to 1: 9, and more preferably from 1: 0.8 to 1: 8. When the mixing molar ratio is in the above range, the dealcoholization reaction proceeds efficiently, and the epoxy group-containing polydimethylsiloxane within the above-mentioned epoxy equivalent range is obtained, and a cured product having excellent heat resistance can be obtained. The number of moles of the silanol group-containing polydimethylsiloxane is a value obtained by dividing the amount of the mixed silanol group-containing polydimethylsiloxane by the weight average molecular weight.

  In addition, the epoxy group-containing alkoxysilane remaining without being introduced into the silanol terminal is removed by a neutralization / water washing step or an organic solvent extraction step, which will be described later, for the purpose of preventing problems that occur when cured in a thick film state. It is preferable. The remaining epoxy group-containing alkoxysilane can also be reduced by reacting an epoxy group-containing alkoxysilane having a silanol content equivalent to the terminal of polydimethylsiloxane.

  The temperature of the dealcoholization reaction is preferably 10 to 100 ° C, more preferably 10 to 80 ° C, and particularly preferably 15 to 70 ° C. The reaction time is preferably 1 to 48 hours, more preferably 1 to 24 hours, and particularly preferably 2 to 12 hours. The dealcoholization reaction may be carried out by charging each component in a reaction vessel at once, or may be carried out while adding the other component intermittently or continuously to one component. The dealcoholization reaction is preferably performed using a catalyst in an organic solvent.

  By the dealcoholization reaction, an epoxy group-containing polydimethylsiloxane having a structure in which an epoxy group-containing alkoxysilane is bonded to the silanol terminal of the silanol group-terminated polydimethylsiloxane is produced. This epoxy group-containing polydimethylsiloxane has an organic group containing an epoxy group at the terminal, and one or two alkoxy groups are bonded to silicon to which the epoxy group-containing organic group is bonded (hereinafter referred to as “this”). The epoxy group-containing polydimethylsiloxane is referred to as “alkoxy group-containing epoxy group-terminated polydimethylsiloxane”).

[Hydrolysis reaction]
By hydrolyzing the alkoxy group-containing epoxy group-terminated polydimethylsiloxane generated by the dealcoholization reaction, one or more silicon groups having an epoxy group-containing organic group bonded to the epoxy group-containing organic group are bonded to the silicon. Polydimethylsiloxane in which two hydroxyl groups are bonded (hereinafter referred to as “silanol group-containing epoxy group-terminated polydimethylsiloxane”) is produced. This hydrolysis reaction is preferably performed using a catalyst in an organic solvent. As the catalyst used at this time, the catalyst used in the dealcoholization reaction may be used continuously, or the same or different kind of catalyst may be newly added. In the present invention, it is not necessary for all the alkoxy groups to be converted to hydroxyl groups, and some alkoxy groups may remain in the state of alkoxy groups. A part of the silanol group of the silanol group-containing epoxy group-terminated polydimethylsiloxane may be condensed.

  The amount of water added in the hydrolysis reaction is usually 10 to 500 parts by weight, preferably 20 to 200 parts by weight, more preferably 30 to 100 parts by weight based on 100 parts by weight of the alkoxy group-containing epoxy group-terminated polydimethylsiloxane. 100 parts by weight. It is preferable that the amount of water added be in the above range because the hydrolysis reaction proceeds sufficiently and the amount of water removed after the reaction is small.

  The temperature of the hydrolysis reaction is preferably 10 to 100 ° C, more preferably 10 to 80 ° C, and particularly preferably 15 to 70 ° C. The reaction time is preferably 0.3 to 48 hours, more preferably 0.4 to 24 hours, and particularly preferably 0.5 to 12 hours.

(Organic solvent)
Examples of the organic solvent used in the dealcoholization reaction and hydrolysis reaction include alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like. Examples of the alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, i-butyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, Examples include ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, and diacetone alcohol. Aromatic hydrocarbons include benzene, toluene, xylene, etc., ethers include tetrahydrofuran, dioxane, etc., and ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and the like. Examples of the esters include ethyl acetate, propyl acetate, butyl acetate, propylene carbonate, methyl lactate, ethyl lactate, normal propyl lactate, isopropyl lactate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and the like. . These organic solvents may be used individually by 1 type, or 2 or more types may be mixed and used for them. Among these organic solvents, in the dealcoholization reaction, from the viewpoint of accelerating the reaction, the reaction may be performed in a solventless system, or an organic solvent other than alcohol, for example, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, etc. is used. It is preferable to do.

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

(catalyst)
Examples of the catalyst used in the dealcoholization reaction or hydrolysis reaction include basic compounds, organotin compounds, and partially hydrolyzed compounds.

(Basic compound)
Examples of the basic compound include ammonia (including ammonia aqueous solution), organic amine compounds, alkali metals such as sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals, alkalis such as sodium methoxide and sodium ethoxide. Examples thereof include metal alkoxides. Of these, ammonia and organic amine compounds are preferred.

  Examples of the organic amine include alkylamine, alkoxyamine, alkanolamine, and arylamine. Alkylamines include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine , Alkylamine having an alkyl group having 1 to 4 carbon atoms such as triethylamine, tripropylamine, tributylamine, N, N-diethylmethylamine, N, N-diisopropylethylamine, and the like.

  Alkoxyamines include methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxybutylamine, butoxymethylamine , Alkoxyamines having 1 to 4 carbon atoms such as butoxyethylamine, butoxypropylamine, and butoxybutylamine.

  As alkanolamine, methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N-butylmethanolamine, N-methylethanolamine, N-ethyl Ethanolamine, N-propylethanolamine, N-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethylbutanolamine N-propylbutanolamine, N-butylbutanolamine, N, N-dimethylmethanolamine, N, N-diethylmethanolamine, N, N-dipropylmethanolamine N, N-dibutylmethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N, N-dibutylethanolamine, N, N-dimethylpropanolamine, N, N-diethylpropanolamine, N, N-dipropylpropanolamine, N, N-dibutylpropanolamine, N, N-dimethylbutanolamine, N, N-diethylbutanolamine, N, N-dipropylbutanolamine, N, N-dibutylbutanolamine, N-methyldimethanolamine, N-ethyldimethanolamine, N-propyldimethanolamine, N-butyldimethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanol Min, N-butyldiethanolamine, N-methyldipropanolamine, N-ethyldipropanolamine, N-propyldipropanolamine, N-butyldipropanolamine, N-methyldibutanolamine, N-ethyldibutanolamine, N -Propyldibutanolamine, N-butyldibutanolamine, N- (aminomethyl) methanolamine, N- (aminomethyl) ethanolamine, N- (aminomethyl) propanolamine, N- (aminomethyl) butanolamine, N -(Aminoethyl) methanolamine, N- (aminoethyl) ethanolamine, N- (aminoethyl) propanolamine, N- (aminoethyl) butanolamine, N- (aminopropyl) methanolamine, N- (aminopropyl) Ethanor Ruamine, N- (aminopropyl) propanolamine, N- (aminopropyl) butanolamine, N- (aminobutyl) methanolamine, N- (aminobutyl) ethanolamine, N- (aminobutyl) propanolamine, N- ( Examples thereof include alkanolamines having an alkyl group having 1 to 4 carbon atoms such as (aminobutyl) butanolamine.

  Examples of the arylamine include aniline and N-methylaniline. Further, as organic amines other than the above, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide; tetramethylethylenediamine, tetraethylethylenediamine Tetraalkylethylenediamine such as tetrapropylethylenediamine and tetrabutylethylenediamine; methylaminomethylamine, methylaminoethylamine, methylaminopropylamine, methylaminobutylamine, ethylaminomethylamine, ethylaminoethylamine, ethylaminopropylamine, ethylaminobutylamine, Propylaminomethylamine, propylamino Alkylaminoalkylamines such as tilamine, propylaminopropylamine, propylaminobutylamine, butylaminomethylamine, butylaminoethylamine, butylaminopropylamine, butylaminobutylamine; pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, morpholine, methyl Also included are morpholine, diazabicycloocrane, diazabicyclononane, diazabicycloundecene, bis (dimethylamino) naphthalene and the like.

  Such basic compounds may be used alone or in combination of two or more. Of these, triethylamine, pyrrolidine, tetramethylammonium hydroxide, pyridine, diazabicyclononane and diazabicycloundecene are particularly preferable, and diazabicyclononane and diazabicycloundecene are most preferable.

(Organic tin compounds)
Examples of the organotin compound include tetravalent tin organometallic compounds in which one or two alkyl groups having 1 to 10 carbon atoms are bonded to one tin atom. Specifically, for example,

Carboxylic acid type organotin compounds such as;

Mercaptide-type organotin compounds such as

Sulfide-type organotin compounds such as;

Chloride-type organotin compounds such as: organotin oxides such as (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO, and these organotin oxides and silicates, dimethyl maleate, diethyl maleate, phthalic acid Reaction products with ester compounds such as dioctyl; and the like.

  Among basic compounds, organotin compounds and partially hydrolyzed compounds, both in the dealcoholization reaction and the hydrolysis reaction, in terms of their reactivity and the stability of the epoxy group, and the cured product under high humidity From the viewpoint of stability, basic compounds are preferred.

  In the dealcoholization reaction, the catalyst is usually 0.01 to 50 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight in total of the silanol group-terminated polydimethylsiloxane and the epoxy group-containing alkoxysilane. More preferably, 0.5 to 20 parts by weight are added.

  In the hydrolysis reaction, the catalyst is usually 0.01 to 50 parts by weight, preferably 0.1 to 30 parts by weight, with respect to 100 parts by weight in total of the silanol group-terminated polydimethylsiloxane and the epoxy group-containing alkoxysilane. More preferably, 0.5 to 20 parts by weight are added.

  In addition, when the hydrolysis reaction is subsequently performed after the dealcoholization reaction, the catalyst used in the dealcoholization reaction may be used as it is as a hydrolysis catalyst, or the same or different catalyst may be newly added. May be.

  From the viewpoint of the storage stability of the silanol group-containing epoxy group-terminated polydimethylsiloxane obtained above, it is preferable to carry out water washing as a decatalyzing step after the hydrolysis reaction. In particular, when a basic compound is used as a catalyst, it is more preferable to perform water washing after neutralization with an acidic compound after the reaction.

  Examples of the acidic compound used for neutralization include organic acids and inorganic acids. Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, maleic anhydride, methylmalonic acid, adipic acid, Sebacic acid, gallic acid, butyric acid, meritic acid, arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfone Examples include acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, methanesulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

  The amount of the acidic compound used is usually 0.5 to 2 N, preferably 0.8 to 1.5 N, more preferably 0.9 to 1 N of the basic compound used in the dealcoholization reaction and hydrolysis reaction. 1.3. The acidic compound is preferably a water-soluble acidic compound from the viewpoint that it can be easily extracted into the aqueous layer at the time of washing with water. When used by dissolving in water, the acidic compound is usually added in an amount of 0.5 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 2 to 10 parts by weight with respect to 100 parts by weight of water.

  After neutralization, the mixture is sufficiently stirred and allowed to stand, and after confirming phase separation between the aqueous phase and the organic solvent phase, the lower layer moisture is removed. The water used for the water washing after neutralization is usually 10 to 500 parts by weight, preferably 20 to 300 parts, more preferably 100 parts by weight in total of silanol group-terminated polydimethylsiloxane and epoxy group-containing alkoxysilane. 30 to 200 parts.

  Washing with water is performed by adding water and stirring sufficiently, and then allowing to stand, and after confirming phase separation between the aqueous phase and the organic solvent phase, removing the lower layer moisture. The number of washings is preferably 1 or more times, more preferably 2 or more times.

  Moreover, you may extract with an organic solvent for the purpose of the removal of an impurity after water washing. As the organic solvent necessary for extraction, the above organic solvents can be used. The kind of organic solvent and its compounding quantity can be selected suitably.

<Curable polysiloxane composition>
The curable polysiloxane composition according to the present invention contains the silanol group-containing epoxy group-terminated polysiloxane and a curing agent. A metal chelate compound is preferable as the curing agent. This composition is cured by heating. This is presumably because hydrogen ions are dissociated from the silanol groups by the action of the metal chelate compound, and the epoxy groups are opened by these hydrogen ions to form a crosslinked structure.

  Examples of metal chelate compounds include tri-n-butoxy ethyl acetoacetate zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, n-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (n-propyl acetoacetate). ) Zirconium chelate compounds such as zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; di-i-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (acetylacetate) ) Titanium chelate compounds such as titanium, di-i-propoxy bis (acetylacetone) titanium; di-i-propoxy-ethyl acetoacetate aluminum, di-i-prop Xyl acetylacetonate aluminum, i-propoxy bis (ethylacetoacetate) aluminum, i-propoxy bis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetate Examples thereof include aluminum chelate compounds such as nat-bis (ethylacetoacetate) aluminum, and among these, aluminum chelate compounds are preferred from the viewpoints of curability and heat and humidity resistance of the resulting cured product.

  The amount of the metal chelate compound added is usually 0.001 to 1 part by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the silanol group-containing epoxy group-terminated polysiloxane, 0.05 to 0 0.5 part by weight is more preferable, and 0.08 to 0.2 is particularly preferable. When the addition amount of the metal chelate compound is within the above range, the balance between the liquid stability after mixing the metal chelate compound and the curability is excellent.

  The curable polysiloxane composition of the present invention further includes silica particles, an epoxy group-containing polysiloxane other than the silanol group-containing epoxy group-terminated polysiloxane, an oxetane compound, a thiol compound, a compound having an isocyanuric ring structure, an alkoxysilane, The hydrolyzate or condensate thereof may be included. When silica particles are blended, it can also be used in the form of a powder or a solvent-based sol or colloid dispersed in a polar solvent such as isopropyl alcohol or a nonpolar solvent such as toluene. In the case of a solvent-based sol or colloid, the solvent may be distilled off after compounding. In order to improve the dispersibility of the silica particles, a surface treatment may be performed.

  The primary particle diameter of these silica particles is usually 0.0001 to 1 μm, more preferably 0.001 to 0.5 μm, and particularly preferably 0.002 to 0.2 μm. In the case of a silica particle solvent-based sol or colloid, the solid content concentration is usually more than 0% by weight and 50% by weight or less, preferably 0.01% by weight or more and 40% by weight or less.

  In the present invention, as surface-treated untreated powdered silica, # 150, # 200, # 300 manufactured by Nippon Aerosil Co., Ltd., and as hydrophobized powdered silica, R972, R974, R976, RX200 manufactured by Nippon Aerosil Co., Ltd. , RX300, RY200S, RY300, R106, SS50A manufactured by Tosoh Corporation, Fuji Silicia's Silo Hovic 100, and the like.

  Examples of the solvent-dispersed colloidal silica include alcohol-based solvent-dispersed colloidal silica such as isopropyl alcohol manufactured by Nissan Chemical Industries, ketone-based solvent-dispersed colloidal silica such as methylisobutyl, and nonpolar solvent-dispersed colloidal silica such as toluene. It is done. The silica particles may be added at the time of preparing the curable polysiloxane, or may be added after adjusting the curable polysiloxane.

  When the inorganic filler (D) is used in combination, the amount used is usually more than 0% by weight and 80% by weight or less, preferably 5% by weight or more, in terms of solid content, relative to the solid content of the polysiloxane (A). 50% by weight or less.

  As the epoxy group-containing polysiloxane other than the silanol group-containing epoxy group-terminated polysiloxane, the epoxy group-containing alkoxysilane represented by the above formula (1) and the following formula (2)

(In Formula (2), R ³ and R ⁴ each independently represents an unsubstituted or substituted monovalent hydrocarbon group, and p is an integer of 0 to 2)
And hydrolyzed condensates with alkoxysilanes, and epoxy group-containing polydimethylsiloxanes that do not contain silanol groups.

  Specific examples of the alkoxysilane represented by the above formula (2) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxysilane. Tetraalkoxysilanes (p = 0 in formula (2)); methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n -Octtilt Remeki Silane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3, 3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2- Hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypro Rutriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, Trialkoxysilanes such as 3- (meth) acrylicoxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, and 3-ureidopropyltriethoxysilane (p = 1 in formula (2)); dimethyldimethoxysilane, dimethyl Diethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldi Ethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyl Diethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n- Dialkoxysilanes such as cyclohexyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane (p = 2 in formula (2));

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

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

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

  Moreover, as an alkoxysilane, its hydrolyzate, or its condensate, the alkoxysilane represented by Formula (2) mentioned above, its hydrolyzate, or its condensate is mentioned. Examples of the condensate of formula (2) include a single condensate of alkoxysilanes exemplified above and a condensate of two or more alkoxysilanes, such as tetramethoxysilane oligomer, tetraethoxysilane oligomer, methyltrimethoxysilane oligomer, methyltrimethoxysilane. Examples include condensates of methoxysilane and dimethyldimethoxysilane. When an alkoxysilane condensate is used, Mw is preferably 3000 or less from the viewpoint of compatibility with the silanol group-containing epoxy group-terminated polydimethylsiloxane.

  These silica particles, epoxy group-containing polysiloxanes other than the silanol group-containing epoxy group-terminated polysiloxanes, or oxetane compounds, thiol compounds, compounds having an isocyanuric ring structure, alkoxysilanes and hydrolysates or condensates thereof are The silanol group-containing epoxy group-terminated polysiloxane may be added during synthesis, or may be added when a cured product is obtained. In order to improve the compatibility with the silanol group-containing epoxy group-terminated polysiloxane, it is more preferable to add at the time of synthesis.

<Hardened body>
Since the curable polysiloxane composition of the present invention does not contain an acid generator such as an onium salt, a cured product having excellent transparency can be formed. In particular, since the content of the linear polydimethylsiloxane component is large, the stress can be relaxed and the film thickness can be secured, the cured product can be suitably used as an LED sealing material.

[Composition for light emitting device coating]
FIG. 1 is a schematic diagram of an LED. The light emitting element portion 50 is sealed around with a sealing material 51. As shown in FIG. 2, the light emitting element portion 50 may include a fluorescent portion 52 containing a binder 53 and a phosphor 54. In addition, the phosphor may be dispersed in the sealing material 51. The cured body of the curable composition according to the present invention can be suitably used as a member for coating a light emitting element, such as an LED sealing material and a fluorescent part binder.

[Light emitting device]
A light-emitting device can be obtained by coating the curable composition of the present invention on a light-emitting element such as an LED element and curing it. As the LED element, a blue LED element, a white LED element, an ultraviolet LED element, or the like can be used. Furthermore, the fluorescent substance can be contained in the cured body, and the light emitted from the LED element can be converted. In the present invention, the term “coating” is a concept that includes both the case where the composition is applied and cured on the surface of the light emitting element and the case where the light emitting element is sealed in a cured body made of the composition of the present invention. Show.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. In the examples and comparative examples, “parts” and “%” indicate “parts by weight” and “% by weight” unless otherwise specified. In addition, various measurements in Examples and Comparative Examples were performed by the following methods.

(1) GPC measurement The weight average molecular weight of siloxane was measured by gel permeation chromatography under the following conditions, and was shown as a polystyrene equivalent value. Apparatus: HLC-8120C (manufactured by Tosoh Corp.) Column: TSK-gel Multipore H _XL- M (manufactured by Tosoh Corp.) Eluent: THF, flow rate 0.5 mL / min, load 5.0%, 100 μL
(2) Storage stability The obtained silanol group-containing epoxy group-terminated polydimethylsiloxane was sealed in a polyethylene container at room temperature for 1 month, and the presence or absence of gelation was visually determined. About the thing which is not gelatinized, the viscosity was measured at 25 degreeC with the BM type | mold viscosity meter by Tokyo Keiki Co., Ltd., and the following reference | standard evaluated. A: Viscosity change rate before and after storage is 20% or less B: Viscosity change rate before and after storage exceeds 20% (3) Curability The obtained composition was applied on quartz glass so that the dry film thickness was 1 mm. Thereafter, it was dried and cured at 100 ° C. for 1 hour, and then dried and cured at 150 ° C. for 5 hours to produce a cured product. The curability of this cured product was evaluated according to the following criteria.
A: No fluidity, no tack B: No fluidity, but slight tack C: Fluidity D: No fluidity, no tack, but cracks occurred (4) Transparency obtained The composition was coated on quartz glass so that the dry film thickness was 1 mm, and then dried and cured at 100 ° C. for 1 hour, and then dried and cured at 150 ° C. for 5 hours to prepare a cured product. About this hardening body, the spectral transmittance of wavelength 400-700nm was measured with the ultraviolet visible spectrophotometer, and the following reference | standard evaluated.
A: Light transmittance exceeds 90% B: Light transmittance is 70 to 90%
C: Light transmittance is less than 70% (5) Light resistance The obtained composition was applied on quartz glass so that the dry film thickness was 1 mm, then dried and cured at 100 ° C. for 1 hour, and then at 150 ° C. A cured product was produced by drying and curing for 5 hours. The cured product was irradiated with ultraviolet rays having an illuminance of 5000 mW / cm ² for 500 hours using a spot UV irradiation device (USHIO Corp .: SP-VII) in which light having a wavelength of 350 nm or less was cut. The appearance of the cured product after ultraviolet irradiation was visually observed and evaluated according to the following criteria.
A: No change B: Yellowed C: Black scorched (6) Hardness The obtained composition was dried and cured at 100 ° C. for 1 hour, and then dried and cured at 150 ° C. for 5 hours to prepare a cured product. The hardness of the cured product obtained in accordance with JIS K6253 was measured.

(7) Moisture and heat resistance Approximately 2 g of the obtained composition was accurately weighed in an aluminum dish, dried and cured at 100 ° C. for 1 hour, and then dried and cured at 150 ° C. for 5 hours to prepare a cured product. This cured product was stored for 14 days under conditions of a temperature of 85 ° C. and a humidity of 85% RH, and the weight retention rate was calculated from the weight before and after storage, and evaluated according to the following criteria.
A: 99% or more B: 95% or more to less than 99% C: less than 95% (8) Epoxy equivalent Based on JIS C2105, the epoxy equivalent of the obtained silanol group-containing epoxy group-terminated polydimethylsiloxane was measured.
[Example 1]
<Dealcoholization reaction>
Mw = 700 silanol-terminated polydimethylsiloxane (manufactured by Momentive Performance Materials, trade name: XC96-723), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as epoxy group-containing alkoxysilane 85 parts (silanol group-terminated polydimethylsiloxane: epoxy group-containing alkoxysilane (molar ratio) = 1: 3.4), 13 parts of diazabicyclononane as a catalyst, and 77 parts of toluene as a solvent were mixed, and 5 parts at 25 ° C. The alcohol was allowed to react for a time.
<Hydrolysis reaction>
To this reaction product, 240 parts of methyl isobutyl ketone, 120 parts of methanol and 120 parts of water were added and subjected to a hydrolysis reaction at 25 ° C. for 2 hours. A sum reaction was performed. Thereafter, the aqueous layer was separated and the organic phase was washed with 120 parts of water. After performing this washing operation three times, the solvent was distilled off to obtain polydimethylsiloxane (1) having terminal epoxy groups and silanol groups of Mw = 800 (hereinafter referred to as “silanol group-containing epoxy group-terminated polydimethylsiloxane (1 ) "). The storage stability and epoxy equivalent of this silanol group-containing epoxy group-terminated polydimethylsiloxane (1) were evaluated by the above methods. The results are shown in Table 1.

Further, 2 parts of a 5 wt% toluene solution of tris (acetylacetonato) aluminum as a curing agent was added to 100 parts of this silanol group-containing epoxy group-terminated polydimethylsiloxane (1) and sufficiently stirred to obtain a curable polysiloxane composition. Was prepared. About this composition, sclerosis | hardenability, transparency, light resistance, hardness, and heat-and-moisture resistance were evaluated by the said method. The results are shown in Table 1.
[Example 2]
<Dealcoholization reaction>
A dealcoholization reaction was carried out in the same manner as in Example 1 except that 13 parts of diazabicycloundecene was used as a catalyst instead of diazabicyclononane, and toluene as a solvent was not used.
<Hydrolysis reaction>
To this reaction product, 350 parts of methyl isobutyl ketone, 120 parts of methanol and 120 parts of water were added and subjected to a hydrolysis reaction at 25 ° C. for 2 hours. A neutralization reaction was performed. Thereafter, in the same manner as in Example 1, polydimethylsiloxane (2) having a terminal epoxy group and a silanol group having Mw = 800 (hereinafter referred to as “silanol group-containing epoxy group-terminated polydimethylsiloxane (2)”) was obtained. The storage stability and epoxy equivalent of this silanol group-containing epoxy group-terminated polydimethylsiloxane (2) were evaluated by the above methods. The results are shown in Table 1.

In addition, 100 parts of this silanol group-containing epoxy group-terminated polydimethylsiloxane (2) was added with 2 parts of a 5% by weight isopropyl alcohol solution of tris (ethylacetoacetate) aluminum as a curing agent and stirred sufficiently to produce a curable polysiloxane composition. A product was prepared. About this composition, sclerosis | hardenability, transparency, light resistance, hardness, and heat-and-moisture resistance were evaluated by the said method. The results are shown in Table 1.
[Example 3]
Instead of silanol group-terminated polydimethylsiloxane XC96-723 with Mw = 700, 120 parts of silanol group-terminated polydimethylsiloxane with Mw = 4,000 (product name: YF3800, manufactured by Momentive Performance Materials, Inc.) were used. Similar to Example 2, except that 32 parts of (3,4-epoxycyclohexyl) ethyltrimethoxysilane (silanol group-terminated polydimethylsiloxane: epoxy group-containing alkoxysilane (molar ratio) = 1: 4.4) were used. Thus, a dealcoholization reaction and a hydrolysis reaction were performed to obtain a polydimethylsiloxane (3) having a terminal epoxy group and a silanol group (hereinafter referred to as “silanol group-containing epoxy group-terminated polydimethylsiloxane (3)”). . The Mw of this silanol group-containing epoxy group-terminated polydimethylsiloxane (3) was 4,100. The storage stability and epoxy equivalent of this silanol group-containing epoxy group-terminated polydimethylsiloxane (3) were evaluated by the above methods. The results are shown in Table 1.

The silanol group-containing epoxy group-terminated polydimethylsiloxane (3) was evaluated in the same manner as in Example 2 for curability, transparency, light resistance, hardness, and moist heat resistance. The results are shown in Table 1.
[Example 4]
Example 3 except that 1 part of a 10% by weight methyl ethyl ketone solution of di-i-propoxy bis (acetylacetonato) titanium was used instead of a 5% by weight isopropyl alcohol solution of tris (ethylacetoacetate) aluminum as the curing agent. In the same manner, a curable polysiloxane composition was prepared. About this composition, sclerosis | hardenability, transparency, light resistance, hardness, and heat-and-moisture resistance were evaluated by the said method. The results are shown in Table 1.
[Example 5]
Example 3 except that 1 part of a 10% by weight methylethylketone solution of di-n-butoxy bis (acetylacetonate) zirconium was used in place of the 5% by weight isopropyl alcohol solution of tris (ethylacetoacetate) aluminum as the curing agent. In the same manner, a curable polysiloxane composition was prepared. About this composition, sclerosis | hardenability, transparency, light resistance, hardness, and heat-and-moisture resistance were evaluated by the said method. The results are shown in Table 1.
[Example 6]
Example 3 except that Mw = 4,000 silanol group-terminated polydimethylsiloxane (trade name: FM9915) manufactured by Chisso Corporation was used in place of YF3800 as the silanol group-terminated polydimethylsiloxane having Mw = 4,000. A polydimethylsiloxane (6) having a Mw = 4,100 terminal epoxy group and a silanol group (hereinafter referred to as “silanol group-containing epoxy group-terminated polydimethylsiloxane (6)”). ) The storage stability and epoxy equivalent of this silanol group-containing epoxy group-terminated polydimethylsiloxane (6) were evaluated by the above methods. The results are shown in Table 1.

  Further, 2 parts of a 5 wt% isopropyl alcohol solution of tris (ethylacetoacetate) aluminum as a curing agent was added to 100 parts of this silanol group-containing epoxy group-terminated polydimethylsiloxane (6), and the mixture was sufficiently stirred to produce a curable polysiloxane composition. A product was prepared. About this composition, sclerosis | hardenability, transparency, light resistance, hardness, and heat-and-moisture resistance were evaluated by the said method. The results are shown in Table 1.

[Comparative Example 1]
Mw = 700 silanol-terminated polydimethylsiloxane (manufactured by Momentive Performance Materials, trade name: XC96-723), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as epoxy group-containing alkoxysilane 85 parts (silanol group-terminated polydimethylsiloxane: epoxy group-containing alkoxysilane (molar ratio) = 1: 3.4), 13 parts diazabicyclononane as a catalyst, 77 parts toluene, 240 parts methyl isobutyl ketone, methanol After 120 parts and 120 parts of water were added and subjected to a hydrolysis reaction at 25 ° C. for 6 hours, 170 parts of a 6% oxalic acid aqueous solution was added and a neutralization reaction was performed at room temperature for 1 hour. Thereafter, the aqueous layer was separated and the organic phase was washed with 120 parts of water. After performing this washing operation three times, the solvent was distilled off to obtain polysiloxane (C1) (hereinafter referred to as “polysiloxane (C1)”) having Mw = 600. The storage stability of this polysiloxane (C1) was evaluated by the above method. The results are shown in Table 2.

  Further, the curability of this polysiloxane (C1) was evaluated in the same manner as in Example 2. The results are shown in Table 2.

[Comparative Example 2]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as an epoxy group-containing alkoxysilane, 60 parts of dimethyldimethoxysilane (polydimethylsiloxane monomer) Corresponding) 40 parts, 500 parts of methyl isobutyl ketone (MIBK) and 10 parts of diazabicyclononane were added and mixed at room temperature. Next, 100 parts of water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, 108 parts of a 6% aqueous oxalic acid solution was added and neutralized at room temperature for 1 hour. Thereafter, the aqueous layer was separated and the organic phase was washed with 100 parts of water. After performing this washing operation three times, the solvent was distilled off to obtain an epoxy group-containing polysiloxane (C2) (hereinafter referred to as “epoxy group-containing polysiloxane (C2)”) having Mw = 2000. The storage stability and epoxy equivalent of this epoxy group-containing polysiloxane (C2) were evaluated by the above method. The results are shown in Table 2.

  The epoxy group-containing polysiloxane (C2) was evaluated for curability in the same manner as in Example 2. The results are shown in Table 2.

[Comparative Example 3]
Instead of polydimethylsiloxane (1) having a terminal epoxy group and a silanol group, an epoxy group-terminated polydimethylsiloxane having no silanol group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-169B, epoxy equivalent 1700) A polysiloxane composition was prepared in the same manner as in Example 1 except that 100 parts of was used. About this composition, sclerosis | hardenability was evaluated by the said method. The results are shown in Table 2.

[Comparative Example 4]
70 parts of silanol group-terminated polydimethylsiloxane (XC96-723) and 85 parts of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (silanol group-terminated polydimethylsiloxane: epoxy group-containing alkoxysilane (molar ratio) = 1) : 3.4). To 100 parts of this mixture, 2 parts of a 5 wt% isopropyl alcohol solution of tris (ethylacetoacetate) aluminum was added and stirred sufficiently to prepare a polysiloxane composition. About this composition, sclerosis | hardenability was evaluated by the said method. The results are shown in Table 2.

[Comparative Example 5]
After the dealcoholization reaction in the same manner as in Example 3, the solvent was distilled off to obtain polydimethylsiloxane (C3) having a terminal epoxy group having Mw = 4,100 and an alkoxy group (hereinafter referred to as “alkoxy group-containing epoxy group”). Terminal polydimethylsiloxane (C3) ”was obtained. The storage stability of this alkoxy group-containing epoxy group-terminated polydimethylsiloxane (C3) was evaluated by the above method. The results are shown in Table 2.

  Further, 2 parts of a 2 wt% isopropyl alcohol solution of tris (ethylacetoacetate) aluminum as a curing agent was added to 100 parts of this alkoxy group-containing epoxy group-terminated polydimethylsiloxane (C3), and the mixture was sufficiently stirred to prepare a polysiloxane composition. Prepared. About this composition, sclerosis | hardenability was evaluated by the said method. The results are shown in Table 2.

[Comparative Example 6]
Instead of silanol group-containing epoxy group-terminated polydimethylsiloxane (1), 100 parts of epoxy group-terminated polydimethylsiloxane having no silanol group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-169B, epoxy equivalent 1700) A polysiloxane composition was prepared in the same manner as in Example 1 except that 7 parts of an acid anhydride (trade name: MH-700G, manufactured by Shin Nippon Rika Co., Ltd.) was used as a curing agent. About this composition, sclerosis | hardenability was evaluated by the said method. The results are shown in Table 2.

[Comparative Example 7]
Instead of silanol group-containing epoxy group-terminated polydimethylsiloxane (1), 100 parts of epoxy group-terminated polydimethylsiloxane having no silanol group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-169B, epoxy equivalent 1700) A polysiloxane composition was prepared in the same manner as in Example 1 except that it was used. The polysiloxane composition was mixed with 3 parts of triphenylsilanol as a silanol component and stirred well, and the curability of this composition was evaluated by the above method. The results are shown in Table 2.

[Comparative Example 8]
Instead of silanol group-containing epoxy group-terminated polydimethylsiloxane (1), 100 parts of epoxy group-terminated polydimethylsiloxane having no silanol group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-169B, epoxy equivalent 1700) A polysiloxane composition was prepared in the same manner as in Example 1 except that it was used. After adding 20 parts of triphenylsilanol as a silanol component to this polysiloxane composition and stirring well, the composition was evaluated for curability, transparency, light resistance, hardness, and moist heat resistance by the above methods. The results are shown in Table 2.

Claims (18)

  It has an organic group containing an epoxy group at the end, and one or two hydroxyl groups are bonded to silicon to which the organic group is bonded, and the epoxy equivalent is 150 g / eq. Or more, 2000 g / eq. A curable composition comprising an epoxy group-terminated polydimethylsiloxane and a curing agent which are less than A polydimethylsiloxane having a silanol group at the terminal and the following formula (1):

(In the formula (1), R ^E is an organic group containing an epoxy group, R ^1, R ² represents a monovalent hydrocarbon radical unsubstituted or substituted independently, m is 1 or 2, n is 2 Or 3 and m + n is 4 or less)
A curable composition comprising an epoxy group-terminated polydimethylsiloxane obtained by dealcoholizing an epoxy group-containing alkoxysilane represented by the following formula and then hydrolyzing the reaction product, and a curing agent. . A polydimethylsiloxane having a silanol group at the terminal and the following formula (1):

(In the formula (1), R ^E represents an organic group containing an epoxy group, R ¹ and R ² each independently represents an unsubstituted or substituted monovalent hydrocarbon group, m is 1 or 2, and n is 2 Or 3 and m + n is 4 or less)
The molar ratio ((number of moles of silanol group-containing polydimethylsiloxane) :( number of moles of epoxy group-containing alkoxysilane)) is 1: 0.6 to 1:10. A curable composition comprising an epoxy-terminated polydimethylsiloxane obtained by dealcoholization reaction and then hydrolyzing the reaction product, and a curing agent. 5. The curable composition according to claim 3, wherein R ^E in the formula (1) is an organic group containing an epoxycycloalkyl group.   The curable composition according to claim 1, wherein the curing agent is a metal chelate compound.   The curable composition according to claim 5, wherein the metal chelate compound is an aluminum chelate.   The curable composition according to claim 1, further comprising silica particles. Following formula (1)

(In the formula (1), R ^E represents an organic group containing an epoxy group, R ¹ and R ² each independently represents an unsubstituted or substituted monovalent hydrocarbon group, m is 1 or 2, and n is 2 Or 3 and m + n is 4 or less)
And an epoxy group-containing alkoxysilane represented by the following formula (2)

(In Formula (2), R ³ and R ⁴ each independently represents an unsubstituted or substituted monovalent hydrocarbon group, and p is an integer of 0 to 2)
The curable composition according to claim 1, further comprising a hydrolysis condensate with an alkoxysilane represented by the formula:   The curable composition according to claim 1, further comprising at least one compound selected from an oxetane compound, a thiol compound, and a compound having an isocyanuric ring structure.   An optical element coating material comprising the curable composition according to claim 1.   LED sealing material which consists of a curable composition in any one of Claims 1-9.   Hardened | cured material obtained by thermosetting the curable composition in any one of Claims 1-9.   One or two hydroxyl groups are bonded to silicon having an organic group containing an epoxy group at the end, and bonded to the epoxy group-containing organic group, and an epoxy equivalent of 150 g / eq. Or more, 2000 g / eq. An epoxy group-terminated polydimethylsiloxane, characterized by being less than. A polydimethylsiloxane having a silanol group at the terminal and the following formula (1):

(In the formula (1), R ^E represents an organic group containing an epoxy group, R ¹ and R ² each independently represents an unsubstituted or substituted monovalent hydrocarbon group, m is 1 or 2, and n is 2 Or 3 and m + n is 4 or less)
An epoxy group-terminated polydimethylsiloxane obtained by dealcoholization reaction with an epoxy group-containing alkoxysilane represented by the following formula and then hydrolyzing the reaction product. A polydimethylsiloxane having a silanol group at the terminal and the following formula (1):

(In the formula (1), R ^E represents an organic group containing an epoxy group, R ¹ and R ² each independently represents an unsubstituted or substituted monovalent hydrocarbon group, m is 1 or 2, and n is 2 Or 3 and m + n is 4 or less)
The molar ratio ((number of moles of silanol group-containing polydimethylsiloxane) :( number of moles of epoxy group-containing alkoxysilane)) is 1: 0.6 to 1:10. An epoxy-terminated polydimethylsiloxane obtained by subjecting to a dealcoholization reaction and then hydrolyzing the reaction product. A polydimethylsiloxane having a silanol group at the terminal and the following formula (1):

(In the formula (1), R ^E represents an organic group containing an epoxy group, R ¹ and R ² each independently represents an unsubstituted or substituted monovalent hydrocarbon group, m is 1 or 2, and n is 2 Or 3 and m + n is 4 or less)
3. The method for producing an epoxy group-terminated polydimethylsiloxane according to claim 1, wherein the reaction product is hydrolyzed with a dealcoholization reaction with an epoxy group-containing alkoxysilane represented by the formula: A polydimethylsiloxane having a silanol group at the terminal and the following formula (1):

(In the formula (1), R ^E represents an organic group containing an epoxy group, R ¹ and R ² each independently represents an unsubstituted or substituted monovalent hydrocarbon group, m is 1 or 2, and n is 2 Or 3 and m + n is 4 or less)
The molar ratio ((number of moles of silanol group-containing polydimethylsiloxane) :( number of moles of epoxy group-containing alkoxysilane)) is 1: 0.6 to 1:10. The method for producing an epoxy group-terminated polydimethylsiloxane according to claim 1, wherein the reaction product is subjected to a dealcoholization reaction and then the reaction product is hydrolyzed. 14. The method for producing an epoxy group-terminated polydimethylsiloxane according to claim 12, wherein R ^E in the formula (1) is an organic group containing an epoxycycloalkyl group.

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