JP2006336010A - Siloxane-based condensate, method for producing the same and polysiloxane composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polysiloxane-based condensate excellent in heat resistance, ultraviolet resistance and light transmission and formable of a thick film and to provide a polysiloxane composition comprising the same. <P>SOLUTION: The siloxane-based condensate is obtained by carrying out a dealcoholization of a difunctional polysiloxane having a specific weight average molecular weight and a polyfunctional siloxane polymer having a specific weight average molecular weight in an organic solvent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a siloxane-based condensate useful as a sealing material for a light-emitting diode element, and a polysiloxane composition containing the condensate.

  A light emitting diode (LED) element is usually covered with a sealing material in order to protect the LED element and change the color. In particular, the white LED element is composed of a blue LED element and a sealing material containing a yellow phosphor formed so as to cover the blue LED element. And as a sealing material of this LED element, the epoxy resin was common conventionally (for example, refer patent documents 1 and 2).

  However, blue LED elements used in white LED elements emit near ultraviolet light as well as blue light, so the epoxy resin encapsulating material turns yellow near the blue LED elements or heat deteriorates due to heat generated by the blue LED elements. There was a problem that. In particular, in applications that require high brightness such as electric lamps, the amount of light emitted from the blue LED element is large, and yellowing and thermal deterioration are likely to occur.

  For this reason, a silicone resin sealing material has been studied as a heat-resistant sealing material that does not cause yellowing due to near ultraviolet rays even in a high luminance environment. However, silicone resin made of dimethylsiloxane has poor adhesion to LED elements and substrates, and has tackiness so that dust and the like are likely to adhere to it. Furthermore, carbon-carbon bonds formed during crosslinking are decomposed by near ultraviolet rays. As a result, the performance as a sealing material may be impaired.

  Patent Documents 3 and 4 disclose a silicone resin composition containing a silicone resin having an alkenyl group bonded to a silicon atom and an organohydrogenpolysiloxane having a Si—H bond. In Patent Documents 3 and 4, this silicone resin composition is crosslinked by a hydrosilylation reaction to form a cured product. However, since the carbon-carbon bond is present in the crosslinked structure of the cured product, it may be decomposed by near ultraviolet rays to impair the performance as a sealing material.

On the other hand, a polysiloxane film formed by hydrolysis and condensation of an alkoxysilane monomer is liable to crack when a thick film is formed, and is unsuitable for an LED sealing material.
JP 2000-281868 A JP 2004-339319 A JP 2004-186168 A JP 2004-221308 A

  The present invention seeks to solve the problems associated with the prior art as described above, and provides a siloxane-based condensate that is excellent in heat resistance, ultraviolet resistance, and light transmittance and can form a thick film, and a method for producing the same. It is intended to provide. Another object of the present invention is to provide a polysiloxane composition containing such a siloxane-based condensate and a filler or phosphor.

As a result of diligent research to solve the above problems, the present inventor cured a siloxane-based condensate obtained by condensing a bifunctional polysiloxane and a polyfunctional siloxane polymer or oligomer by a dealcoholization reaction. The present inventors have found that a cured body (film) excellent in heat resistance, ultraviolet resistance, and light transmittance, particularly a thick film, can be obtained, and the present invention has been completed.

  That is, the siloxane-based condensate according to the present invention has (A1) the following formula (1):

(In the formula, R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and when a plurality of R ¹ and R ² are present, they are the same as each other. Or n is an integer of 5 to 2000)
And a hydroxyl group-containing polysiloxane having a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography in the range of 500 to 100,000,
(B1) The following average composition formula (2)
R ³ _a R ⁴ _b SiO _c (OR ⁵ ) _d (2)
(Wherein R ³ and R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ⁵ is an alkyl group, and R ³ , R ⁴ and R ⁵ are When there are a plurality of them, they may be the same or different from each other, a and b are independently 0 or more and less than 1, a + b is more than 0 and less than 2, c is more than 0 and less than 2, d Is greater than 0 and less than 4 and a + b + c × 2 + d = 4)
And an alkoxy group-containing siloxane polymer having a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography in the range of 1,000 to 100,000,
It can be produced by a dealcoholization reaction in an organic solvent.

  At this time, it is preferable that the polysiloxane (A1) and the siloxane polymer (B1) are mixed and reacted in a range where the weight ratio (A1 / B1) in terms of complete hydrolysis condensate is 1/50 to 50/1. . Moreover, it is also preferable to mix and react polysiloxane (A1) and siloxane polymer (B1) in the range whose molar ratio (A1 / B1) is 1/10 to 10/1.

  Further, the siloxane-based condensate according to the present invention has (A2) the following formula (3):

Wherein R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ⁶ is an alkyl group, R ¹ , R ² and R ⁶ are When there are a plurality of them, they may be the same or different from each other, and n is an integer of 5 to 2000). The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography is 500 to 500. An alkoxy group-containing polysiloxane in the range of 100,000;
(B2) The following average composition formula (4)
R ³ _a R ⁴ _b SiO _c (OH) _d (4)
(In the formula, R ³ and R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and when a plurality of R ³ and R ⁴ are present, they are the same as each other. A and b are each independently 0 or more and less than 1, a + b is more than 0 and less than 2, c is more than 0 and less than 2, d is more than 0 and less than 4, and a + b + c × (2 + d = 4)
And a hydroxyl group-containing siloxane polymer having a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography in the range of 1,000 to 100,000,
It can also be produced by dealcoholization reaction in an organic solvent.

  At this time, the polysiloxane (A2) and the siloxane polymer (B2) are mixed and reacted in a weight ratio (A2 / B2) in terms of complete hydrolysis condensate of 1/50 to 50/1. Good. Moreover, it is also preferable to mix and react polysiloxane (A2) and siloxane polymer (B2) in the range whose molar ratio (A2 / B2) is 1/10 to 10/1.

  Further, the siloxane-based condensate according to the present invention has (A1) the following formula (1):

(In the formula, R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and when a plurality of R ¹ and R ² are present, they are the same as each other. Or n is an integer of 5 to 2000)
And a hydroxyl group-containing polysiloxane having a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography in the range of 500 to 100,000,
(B1 ′) The following average composition formula (2)
R ³ _a R ⁴ _b SiO _c (OR ⁵ ) _d (2)
(Wherein R ³ and R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ⁵ is an alkyl group, and R ³ , R ⁴ and R ⁵ are When there are a plurality of them, they may be the same or different from each other, a and b are independently 0 or more and less than 1, a + b is more than 0 and less than 2, c is more than 0 and less than 2, d Is greater than 0 and less than 4 and a + b + c × 2 + d = 4)
And an alkoxy group-containing siloxane oligomer having a polystyrene-reduced weight average molecular weight in a range of 500 or more and less than 1,000, as measured by gel permeation chromatography,
It can also be produced by mixing in the range of 80/20 to 99/1 by weight ratio (A1 / B1 ′) in terms of complete hydrolysis condensate and subjecting it to a dealcoholization reaction in an organic solvent.

  Furthermore, the siloxane-based condensate according to the present invention comprises (A2) the following formula (3)

Wherein R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ⁶ is an alkyl group, R ¹ , R ² and R ⁶ are When there are a plurality of them, they may be the same or different from each other, and n is an integer of 5 to 2000). The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography is 500 to 500. An alkoxy group-containing polysiloxane in the range of 100,000;
(B2 ′) The following average composition formula (4)
R ³ _a R ⁴ _b SiO _c (OH) _d (4)
(In the formula, R ³ and R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and when a plurality of R ³ and R ⁴ are present, they are the same as each other. A and b are each independently 0 or more and less than 1, a + b is more than 0 and less than 2, c is more than 0 and less than 2, d is more than 0 and less than 4, and a + b + c × (2 + d = 4)
And a hydroxyl group-containing siloxane oligomer having a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography in the range of 500 or more and less than 1,000,
It can also be produced by mixing in the range of 80/20 to 99/1 by weight ratio (A2 / B2 ′) in terms of complete hydrolysis condensate and subjecting to dealcoholization reaction in an organic solvent.

  The siloxane-based condensate preferably has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography in the range of 2,000 to 200,000.

The polysiloxane composition according to the present invention contains the siloxane-based condensate and a filler or a phosphor.
A white light-emitting diode element according to the present invention comprises a blue light-emitting diode element or an ultraviolet light-emitting diode element, and a sealing material formed from a polysiloxane composition containing the phosphor so as to cover the light-emitting diode element. It is characterized by that.

  According to the present invention, a cured product excellent in heat resistance, ultraviolet resistance, and light transmittance, particularly a polysiloxane thick film can be obtained. Such a polysiloxane thick film is useful as a sealing material for LED.

First, each component used in the present invention will be described in detail.
[Hydroxyl-containing polysiloxane (A1)]
The hydroxyl group-containing polysiloxane (A1) used in the present invention is a polysiloxane having two hydroxyl groups in one molecule (hereinafter also referred to as “polysiloxane (A1)”), and is represented by the following formula (1). The

In formula (1), R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and when there are a plurality of R ¹ and R ² , they are the same as each other. Or n may be an integer of 5 to 2000.

  This polysiloxane (A1) has a polystyrene-reduced weight average molecular weight of 500 to 100,000, preferably 1,000 to 80,000, more preferably 1,500 to 70,000 as measured by gel permeation chromatography. Is in range. When bifunctional polysiloxane (A1) having a weight average molecular weight in the above range is used, it is possible to achieve both suppression of crack generation and good curability during the formation of a cured product.

Examples of the monovalent unsubstituted hydrocarbon group include an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group, and a tolyl group. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, and octyl group. Examples of the monovalent substituted hydrocarbon group include substituted alkyl groups having 1 to 8 carbon atoms. Examples of the substituent of the substituted alkyl group include halogen, amino group, mercapto group, isocyanate group, glycidyl group, glycidoxy group, ureido group and the like. Moreover, as said monovalent | monohydric substituted hydrocarbon group, following formula (5)
_{^{- (R 7 O) p -}} (R 8 O) q -R 9 (5)
(In Formula (5), R ⁷ and R ⁸ each independently represents an alkylene group having 1 to 5 carbon atoms, R ⁹ represents an alkyl group having 1 to 5 carbon atoms, R ⁷ , R ⁸ and When there are a plurality of R ^{9 s} , they may be the same or different from each other, and p and q are integers having a value of p + q of 2 to 50)
The oxyalkylene group represented by these is mentioned. Examples of such oxyalkylene groups include polyoxyalkylene groups such as polyoxyethylene groups, polyoxypropylene groups, and poly (oxyethylene / oxypropylene) groups.

This polysiloxane (A1) can be produced, for example, by hydrolyzing and condensing dialkoxysilane or dichlorosilane.
Examples of the dialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, Di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane , Di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxy Silane, di-n-cyclohex Such as diethoxymethylsilane silane. These dialkoxysilanes can be used alone or in combination of two or more.

The hydroxyl group-containing siloxane oligomer 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.

  Moreover, as polysiloxane (A1), it is also possible to use commercially available bifunctional organopolysiloxanes such as XC96-723, YF-3800, YF-3905, and YF-3804 (above, trade names) manufactured by GE Toshiba Silicone. it can.

[Alkoxy group-containing polysiloxane (A2)]
The alkoxy group-containing polysiloxane (A2) used in the present invention is a polysiloxane having two alkoxy groups in one molecule (hereinafter also referred to as “polysiloxane (A2)”), which is represented by the following formula (3): expressed.

In formula (3), R ¹ and R ² are defined in the same manner as R ¹ and R ² in formula (1). R ⁶ is an alkyl group, and when a plurality of R ¹ , R ² and R ⁶ are present, they may be the same or different from each other, and n is an integer of 5 to 2000. Moreover, this polysiloxane (A2) may contain a hydroxyl group in a range that does not impair the object of the present invention, specifically, a range that does not inhibit the dealcoholization reaction.

  This polysiloxane (A2) has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of 500 to 100,000, preferably 1,000 to 80,000, more preferably 1,500 to 70,000. Is in range. When bifunctional polysiloxane (A2) having a weight average molecular weight in the above range is used, it is possible to achieve both suppression of crack generation and good curability during the formation of a cured product.

Examples of the alkyl group represented by R ⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Of these alkyl groups, a methyl group and an ethyl group are preferable.

This polysiloxane (A2) can be produced, for example, by hydrolyzing and condensing dialkoxysilane or dichlorosilane.
As said dialkoxysilane, the thing similar to the dialkoxysilane illustrated by the said polysiloxane (A1) can be mentioned, These can be used individually by 1 type or in mixture of 2 or more types.

[Alkoxy group-containing siloxane polymer (B1) and oligomer (B1 ′)]
The alkoxy group-containing siloxane polymer (B1) used in the present invention has the following average composition formula (2)
R ³ _a R ⁴ _b SiO _c (OR ⁵ ) _d (2)
And a siloxane polymer containing an alkoxy group (hereinafter also referred to as “siloxane polymer (B1)”).

In formula (2), R ³ and R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ⁵ is an alkyl group, R ³ , R ⁴ and R ^A plurality of ⁵ may be the same or different from each other, a and b are independently 0 or more and less than 1, a + b is more than 0 and less than 2, and c is more than 0 and less than 2 , D is greater than 0 and less than 4, and a + b + c × 2 + d = 4.

  Of these siloxane polymers (B1), branched or tertiary crosslinked siloxane polymers are preferred. Moreover, this siloxane polymer (B1) may contain a hydroxyl group within a range not impairing the object of the present invention, specifically, within a range not inhibiting the dealcoholization reaction.

  This siloxane polymer (B1) has a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of 1,000 to 100,000, preferably 1,000 to 80,000, more preferably 1,500 to 70,000. In the range of 000. When the siloxane polymer (B1) having a weight average molecular weight in the above range is used, it is possible to achieve both suppression of crack generation and good curability during the formation of the cured product.

  Moreover, if the mixing ratio with polysiloxane (A1) is a range described later, the weight average molecular weight in terms of polystyrene represented by the above average composition formula (2) and measured by gel permeation chromatography is 500 or more and 1,000. Less than, preferably 600 or more and 900 or less low molecular weight alkoxy group-containing siloxane oligomer (B1 ′) can be used, and it is possible to achieve both suppression of crack generation and good curability during formation of a cured product.

  This siloxane oligomer (B1 ′) is also preferably a branched or tertiary-crosslinked siloxane oligomer, and may contain a hydroxyl group in a range that does not impair the object of the present invention, specifically, a range that does not inhibit the dealcoholization reaction. Good.

Examples of the substituted or unsubstituted monovalent hydrocarbon group include the same as the substituted or unsubstituted monovalent hydrocarbon group exemplified for the polysiloxane (A1).
Examples of the alkyl group represented by R ⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Of these alkyl groups, a methyl group and an ethyl group are preferable.

  This siloxane polymer (B1) and siloxane oligomer (B1 ') can be produced, for example, by hydrolyzing and condensing polyfunctional alkoxysilane or polyfunctional chlorosilane.

Examples of the polyfunctional alkoxysilane include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxysilane;
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxy Silane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Cypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- Trialkoxysilanes such as (meth) acrylicoxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane;
Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxy Silane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldi Ethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyl Diethoxysilane, diphenyl Silane, dialkoxy silanes such as diphenyl diethoxy silane. These alkoxysilanes can be used individually by 1 type or in mixture of 2 or more types.

  Moreover, in addition to polyfunctional alkoxysilane, monofunctional alkoxysilane can also be used together. Examples of monofunctional alkoxysilanes include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, and triethylethoxysilane. These monofunctional alkoxysilanes are desirably used in an amount of 10% by weight or less, preferably 7% by weight or less, more preferably 5% by weight or less based on the total amount of alkoxysilane used.

  As siloxane polymer (B1) and siloxane oligomer (B1 ′), X40-9220 and X40-9225 (trade name) manufactured by Shin-Etsu Silicone, XR31-B1410, XR31-B0270 and XR31 manufactured by GE Toshiba Silicone are used. Commercially available organosiloxane polymers and siloxane oligomers such as -B2733 and XC96-B0446 (above, trade names) can also be used.

[Hydroxyl-containing siloxane polymer (B2) and oligomer (B2 ′)]
The hydroxyl group-containing siloxane polymer (B2) used in the present invention has the following average composition formula (4) R ³ _a R ⁴ _b SiO _c (OH) _d (4)
A siloxane polymer containing a hydroxyl group (hereinafter also referred to as “siloxane polymer (B2)”).

In formula (4), R ³ and R ⁴ are defined in the same manner as R ³ and R ⁴ in formula (2), and when there are a plurality of R ³ and R ⁴ , they may be the same or different from each other. It may be. a and b are each independently 0 or more and less than 1, a + b is more than 0 and less than 2, c is more than 0 and less than 2, d is more than 0 and less than 4, and a + b + c × 2 + d = 4.

Of such siloxane polymers (B2), branched or tertiary crosslinked siloxane polymers are preferred.
This siloxane polymer (B2) has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of 1,000 to 100,000, preferably 1,000 to 80,000, more preferably 1,500 to 70,000. In the range of 000. When the siloxane polymer (B2) having a weight average molecular weight in the above range is used, it is possible to achieve both suppression of crack generation and good curability during formation of the cured product.

  If the mixing ratio with the polysiloxane (A2) is within the range described later, the weight average molecular weight in terms of polystyrene represented by the above average composition formula (4) and measured by gel permeation chromatography is 500 or more and 1,000. Less than, preferably 600 or more and 900 or less low molecular weight alkoxy group-containing siloxane oligomer (B2 ′) can be used, and it is possible to achieve both suppression of crack generation and good curability during the formation of a cured product.

  The siloxane oligomer (B2 ′) is also preferably a branched or tertiary-crosslinked siloxane oligomer, and may contain a hydroxyl group within a range that does not impair the object of the present invention, specifically, a range that does not inhibit the dealcoholization reaction. Good.

Examples of the substituted or unsubstituted monovalent hydrocarbon group include the same as the substituted or unsubstituted monovalent hydrocarbon group exemplified for the polysiloxane (A1).
This siloxane polymer (B2) and siloxane oligomer (B2 ′) can be produced, for example, by hydrolyzing and condensing polyfunctional alkoxysilane or polyfunctional chlorosilane.

  Examples of the polyfunctional alkoxysilane include the same polyfunctional alkoxysilanes exemplified in the siloxane polymer (B1) and the siloxane oligomer (B1 ′), and these may be used alone or in combination of two or more. Can be used.

  Further, in the siloxane polymer (B2) and the siloxane oligomer (B2 ′), in addition to the polyfunctional alkoxysilane, the monofunctional alkoxysilane exemplified in the siloxane polymer (B1) and the siloxane oligomer (B1 ′) is used in combination. May be. At this time, the monofunctional alkoxysilane is desirably used in an amount of 10% by weight or less, preferably 7% by weight or less, more preferably 5% by weight or less based on the total amount of alkoxysilane used.

<Siloxane-based condensate>
The siloxane-based condensate according to the present invention requires the hydroxyl group-containing polysiloxane (A1) and the alkoxy group-containing siloxane polymer (B1), or the alkoxy group-containing polysiloxane (A2) and the hydroxyl group-containing siloxane polymer (B2). Depending on the condition, it can be produced by dealcoholization reaction in an organic solvent. Further, the hydroxyl group-containing polysiloxane (A1) and the alkoxy group-containing siloxane oligomer (B1 ′), or the alkoxy group-containing polysiloxane (A2) and the hydroxyl group-containing siloxane oligomer (B2 ′) are mixed at a mixing ratio described later. If necessary, it can also be produced by a dealcoholization reaction in an organic solvent. If a siloxane-based condensate prepared by this dealcoholization reaction is used, a uniform cured body (film) can be formed. If the siloxane-based condensate is formed by hydrolysis / condensation without causing a dealcoholization reaction, the polysiloxanes (A1) and (A2) have a low number of functional groups per molecule and a low reactivity. Hydrolysis / condensation reaction of polyfunctional siloxane polymer (B1), polyfunctional siloxane oligomer (B1 ′), polyfunctional siloxane polymer (B2) or polyfunctional siloxane oligomer (B2 ′) with a high number of functional groups It becomes difficult to form a uniform cured body (film). From this viewpoint, when forming a cured body (film), it is preferable to use the siloxane-based condensate prepared in advance.

  In the dealcoholization reaction, the polysiloxane (A1) and the siloxane polymer (B1) have a weight ratio (A1 / B1) in terms of a complete hydrolysis condensate, preferably 1/50 to 50/1, more preferably 1. / 40 to 40/1, particularly preferably 1/25 to 25/1, or the molar ratio (A1 / B1) is preferably 1/10 to 10/1, more preferably 1/10 to 7/1. In particular, it is desirable to mix and react at 1/5 to 5/1. The weight ratio (A2 / B2) of the polysiloxane (A2) and the siloxane polymer (B2) in terms of complete hydrolysis condensate is preferably 1/50 to 50/1, more preferably 1/40 to 40. / 1, particularly preferably 1/25 to 25/1, or the molar ratio (A1 / B1) is preferably 1/10 to 10/1, more preferably 1/10 to 7/1, particularly preferably It is desirable to react by mixing at 1/5 to 5/1. In addition, let the said molar ratio be ratio of the value (number of moles) which divided the preparation weight of each component by the weight average molecular weight.

  On the other hand, when the polysiloxane (A1) and the siloxane oligomer (B1 ′) are reacted, the weight ratio (A1 / B1 ′) in terms of the complete hydrolysis condensate is 80 / 20˜ 99/1, preferably 80/20 to 98/2, and more preferably 82/18 to 96/4. Further, when the polysiloxane (A2) and the siloxane oligomer (B2 ′) are reacted, the weight ratio (A2 / B2 ′) in terms of complete hydrolysis condensate is 80 / 20˜ 99/1, preferably 80/20 to 98/2, and more preferably 82/18 to 96/4.

  When polysiloxane (A1) or (A2) and siloxane polymer (B1) or siloxane oligomer (B1 ′) or siloxane polymer (B2) or siloxane oligomer (B2 ′) are mixed and reacted in the above ratio, a hydroxyl group is contained. No siloxane-based condensate having a very low content and excellent storage stability can be easily obtained. In particular, it is preferable to use a combination of polysiloxane (A1) and siloxane polymer (B1) from the viewpoint of ensuring long-term storage stability.

  Further, the cured product according to the present invention has a weight ratio or a molar ratio within the above range, and a structure derived from polysiloxane (A1) and a structure derived from siloxane polymer (B1) or siloxane oligomer (B1 ′), or polysiloxane (A2). ) -Derived structure and a siloxane polymer (B2) or siloxane oligomer (B2 ′)-derived structure. Such a cured body is excellent in curability and thick film performance.

Examples of the organic solvent include alcohols, aromatic hydrocarbons, ethers, ketones, esters, and the like. Examples of the alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, i-butyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, Examples include ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, and diacetone alcohol. Also, 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. Of these organic solvents, organic solvents other than alcohols such as methyl ethyl ketone, methyl isobutyl ketone, toluene, and xylene are preferable from the viewpoint of promoting the dealcoholization reaction. Moreover, it is preferable to use these organic solvents in the state which gave the dehydration process previously and removed the water | moisture content.

The organic solvent can be used as appropriate when controlling the dealcoholization reaction or adjusting the concentration or viscosity of the final product or the thickness of the cured product.
The amount of the organic solvent used can be appropriately determined according to the purpose. For example, the concentration of the obtained siloxane-based condensate is preferably 5 to 100% by weight in terms of complete hydrolysis condensate. The amount is preferably 7 to 95% by weight, particularly preferably 10 to 90% by weight.

The temperature of the dealcoholization reaction is preferably 30 to 150 ° C, more preferably 40 to 120 ° C, and particularly preferably 50 to 100 ° C.
Moreover, when performing the said dealcoholization reaction, it is preferable to use the catalyst which accelerates | stimulates this reaction. Examples of the catalyst used in the dealcoholization reaction include acidic compounds, alkaline compounds, salt compounds, amine compounds, organometallic compounds and / or partial hydrolysates thereof (hereinafter referred to as organometallic compounds and / or partial hydrolysates thereof. And “organometallic compounds”).

Examples of the acidic compound include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl titanic acid, p-toluenesulfonic acid, and phthalic acid, and among these, acetic acid is preferable.
Examples of the alkaline compound include sodium hydroxide and potassium hydroxide. Of these, sodium hydroxide is preferable.

Examples of the salt compound include naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and alkali metal salts such as carbonic acid.
Examples of the amine compounds include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, m-phenylenediamine, p-phenylenediamine, ethanolamine, triethylamine, 3-aminopropyl trimethoxy. Silane, 3-aminopropyl-triethoxysilane, 3- (2-aminoethyl) -aminopropyl-trimethoxysilane, 3- (2-aminoethyl) -aminopropyl-triethoxysilane, 3- (2-aminoethyl) ) -Aminopropyl / methyl / dimethoxysilane, 3-anilinopropyl / trimethoxysilane, alkylamine salts, and quaternary ammonium salts such as tetramethylammonium hydroxide. Various modified amines used as a curing agent for epoxy resins can also be used. Of these, 3-aminopropyl / trimethoxysilane, 3-aminopropyl / triethoxysilane, and 3- (2-aminoethyl) -aminopropyl / trimethoxysilane are preferable.

Examples of the organometallic compounds include the following formula (6):
M (OR ¹⁰ ) _r (R ¹¹ COCHCOR ¹² ) _s (6)
(In the formula, M represents at least one metal atom selected from the group consisting of zirconium, titanium, aluminum and sodium, and R ¹⁰ and R ¹¹ each independently represents a methyl group, an ethyl group, or n-propyl. A monovalent carbon having 1 to 6 carbon atoms such as a group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, phenyl group, etc. R ¹² represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, or methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy. Represents an alkoxyl group having 1 to 16 carbon atoms such as a group, t-butoxy group, lauryloxy group, stearyloxy group, and r and s are each independently 0 to 4
And satisfies the relationship (r + s) = (M valence))
(Hereinafter referred to as “organometallic compound (6)”),
A tetravalent tin organometallic compound in which one or two alkyl groups having 1 to 10 carbon atoms are bonded to one tin atom (hereinafter referred to as “organotin compound”), or
These partial hydrolysates are exemplified.

  Further, as organometallic compounds, tetraalkoxytitanium such as tetramethoxytitanium, tetraethoxytitanium, tetra-i-propoxytitanium, tetra-n-butoxytitanium; methyltrimethoxysilane, ethyltriethoxysilane, n-propyltri Methoxysilane, i-propyltriethoxysilane, n-hexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane Trialkoxysilanes such as 3-isocyanatopropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-ureidopropyltrimethoxysilane; dimethyldiethoxy Lan, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, diphenyl Titanium alcoholates such as dialkoxysilanes such as dimethoxysilane and condensates thereof can be used.

Examples of the organometallic compound (6) include tetra-n-butoxyzirconium, tri-n-butoxyethylacetoacetatezirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate). Organic zirconium compounds such as acetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium;
Organic titanium compounds such as tetra-i-propoxy titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (acetylacetate) titanium, di-i-propoxy bis (acetylacetone) titanium ;
Tri-i-propoxyaluminum, di-i-propoxyethyl acetoacetate aluminum, di-i-propoxy acetylacetonate aluminum, i-propoxy bis (ethylacetoacetate) aluminum, i-propoxy bis (acetylacetonate) ) Organoaluminum compounds such as aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethylacetoacetate) aluminum;
Examples include sodium alkoxide such as sodium methoxide.

  As an organic tin compound, 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;
Reaction of organotin oxides such as (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO, and ester compounds such as silicates, dimethyl maleate, diethyl maleate and dioctyl phthalate Product;
Etc.

  Of these catalysts, alkoxytitanium, alkoxysilconium, alkoxyaluminum, chelates thereof, and partial hydrolysates thereof, and sodium alkoxide are preferable, and tri-n-butoxyethyl acetoacetate zirconium is more preferable. Di-i-propoxy bis (acetylacetonate) titanium, di-i-propoxy ethyl acetoacetate aluminum, tris (ethyl acetoacetate) aluminum, partial hydrolysates thereof, and sodium methoxide are used.

  While using the said catalyst when adjusting the condensate of this invention, when manufacturing a hardening body from the condensate of this invention, you may add again as needed. As a catalyst to be added when producing a cured product, alkoxyaluminum, this chelated product and partially hydrolyzed product, and an organotin compound are particularly preferable.

  The siloxane-based condensate produced by the above method comprises a block (A) derived from polysiloxane (A1) or (A2), a siloxane polymer (B1) or a siloxane oligomer (B1 ′) or (B2) or a siloxane oligomer. And a block (B) derived from (B2 ′). Specifically, it is considered that a block structure in which the block (B) is bonded to both ends of the block (A) is formed. Further, it is preferable that another block (A) is bonded to the block (B) to form a structure in which the block (B) is crosslinked with the block (A). Such a block-structured siloxane-based condensate is excellent in adhesion and flexibility to a substrate or the like, and easily forms a thick film with a film thickness of preferably 10 μm or more, more preferably 20 μm or more, and particularly preferably 100 μm or more. can do. Further, no cracks are generated during drying and curing (for example, 150 ° C., 1 hour), and a cured body (film) excellent in light transmittance can be formed.

  Unreacted polysiloxane, siloxane polymer, or siloxane oligomer may remain in the siloxane-based condensate produced by the above method. In particular, when polysiloxane containing a hydroxyl group remains, the storage stability may be lowered, or the hydroxyl group-containing polysiloxane may be separated during curing to form a uniform cured body (film). For this reason, in the present invention, it is preferable to add a polyfunctional alkoxysilane after the dealcoholization reaction to react the unreacted hydroxyl group with this alkoxysilane to reduce the residual amount of hydroxyl group. The addition amount of the polyfunctional alkoxysilane is, for example, preferably 0.01 to 50 parts by weight, more preferably 0.1 to 30 parts by weight, particularly preferably 100 parts by weight of the obtained siloxane-based condensate. 0.2 to 15 parts by weight.

  Examples of the polyfunctional alkoxysilane may include the same polyfunctional alkoxysilanes exemplified for the siloxane polymer (B1) and the siloxane oligomer (B1 ′). These may be used alone or in combination of two or more. Can be used in combination.

  The siloxane-based condensate has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of 2,000 to 200,000, preferably 3,000 to 150,000, more preferably 4,000 to 100,000. It is preferable that it exists in the range. When the weight average molecular weight is in the above range, a film having the following characteristics, particularly a thick film, can be easily formed.

The siloxane-based condensate according to the present invention does not have a carbon-carbon bond in the crosslinked structure, and is excellent in ultraviolet resistance and heat resistance. For example, the cured product of the siloxane-based condensate is 5000 mW.
/ M ² , yellowing (yellowing) is not caused by UV irradiation for 200 hours, and at 150 ° C., 10
There is no thermal degradation even after heating for 00 hours.

  In addition, this cured product has a light transmittance of 90% or more, preferably 93% or more, more preferably 95% or more at a thickness of 10 μm at a wavelength of 350 to 700 nm. Due to this characteristic, light emitted from the blue LED or the ultraviolet LED element can be extracted without being attenuated.

  The siloxane-based condensate is preferably used in the form of a solution mixed with an organic solvent. The organic solvent used at this time can mention the same organic solvent used when forming a siloxane-type condensate.

<Polysiloxane composition>
The polysiloxane composition according to the present invention contains the siloxane-based condensate and additives such as fillers and phosphors. By adding a filler, the strength of the formed cured body (film) can be improved. Moreover, it can use for the sealing material of an LED element by adding fluorescent substance.

  The filler is not particularly limited as long as it does not impair the properties of the siloxane-based condensate, specifically ultraviolet resistance, heat resistance, transparency, etc. For example, glass fiber, inorganic compound powder, sol , Colloids and are formulated according to the desired properties of the coating.

  In the polysiloxane composition containing the siloxane-based condensate and the glass fiber, when ensuring transparency, the difference in refractive index between the siloxane-based condensate and the glass fiber is preferably 0.01 or less.

As the inorganic _{compound, SiO 2, Al 2 O 3} , AlGaAs, Al (OH) 3, Sb 2
O ₅ , Si ₃ N ₄ , Sn—In ₂ O ₃ , Sb—In ₂ O ₃ , MgF, CeF ₃ , CeO ₂ , 3Al ₂ O ₃ .2SiO ₂ , BeO, SiC, AlN, Fe, Co, Co— FeO _x , CrO ₂ , Fe ₄ N, BaTiO ₃ , BaO—Al ₂ O ₃ —SiO ₂ , Ba ferrite, SmCO ₅ , YCO ₅
, CeCO ₅ , PrCO ₅ , Sm ₂ CO ₁₇ , Nd ₂ Fe ₁₄ B, Al ₄ O ₃ , α-Si, SiN ₄
, CoO, Sb—SnO ₂ , Sb ₂ O ₅ , MnO ₂ , MnB, Co ₃ O ₄ , Co ₃ B, LiTa
O ₃ , MgO, MgAl ₂ O ₄ , BeAl ₂ O ₄ , ZrSiO ₄ , ZnSb, PbTe, GeSi, FeSi ₂ , CrSi ₂ , CoSi ₂ , MnSi _1.73 , Mg ₂ Si, β-B, BaC, BP, TiB ₂ , ZrB ₂ , HfB ₂ , Ru ₂ Si ₃ , TiO ₃ , PbTiO ₃ , Al ₂ TiO ₅ ,
_{Zn 2 SiO 4, Zr 2 SiO} 4, 2MgO 2 -Al 2 O 3 -5SiO 2, Nb 2 O 5, Li 2 O-
Al ₂ O ₃ -4SiO _2, Mg ferrite, Ni ferrite, Ni-Zn ferrite, Li
Examples thereof include ferrite and Sr ferrite. These inorganic compounds can be used alone or in admixture of two or more.

  As described above, the filler is used in the form of powder, an aqueous sol or colloid dispersed in water, or a solvent sol or colloid dispersed in a polar solvent such as isopropyl alcohol or a nonpolar solvent such as toluene. can do. In the case of a solvent-based sol or colloid, depending on the dispersibility of the inorganic compound, it may be further diluted with water or a solvent, or may be used after surface treatment to improve the dispersibility.

The average particle size of these fillers is usually 0.005 to 1 μm, more preferably 0.01 to 0.5 μm, and particularly preferably 0.01 to 0.2 μm.
When the filler is a water-based sol or colloid, or a 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. is there.

  In the present invention, colloidal silica or aluminum oxide is particularly preferably used as the filler. Examples of the colloidal silica include organic solvent-based colloidal silica such as methanol-dispersed colloidal silica, isopropanol-dispersed colloidal silica, methyl isobutyl ketone-dispersed colloidal silica, and toluene-dispersed colloidal silica. Examples of colloidal aluminum oxide include water-dispersed aluminum oxide.

  The amount of the filler used is usually more than 0% by weight and 90% by weight or less, preferably 5% by weight or more and 80% by weight or less, in terms of solid content, with respect to the total solid content of the polysiloxane composition. When the usage-amount of a filler exceeds the said upper limit, storage stability and film forming property may be inferior.

  Moreover, as said fluorescent substance, conventionally well-known fluorescent substances, such as a red fluorescent substance, a green fluorescent substance, a blue fluorescent substance, a yellow fluorescent substance, can be used, for example. In particular, when a yellow phosphor is added as a phosphor, it can be applied to a sealing material for a white LED element using a blue LED element as a light emitting element, and when an ultraviolet absorbing white phosphor is added as a phosphor, a light emitting element As a sealing material for white LED elements using ultraviolet LED elements. At this time, the encapsulant may be formed using only the polysiloxane composition, but the encapsulant in the vicinity of the light-emitting element is formed from the polysiloxane composition, and the remaining part is a conventionally known epoxy resin. You may form from a sealing material. Thus, when at least the sealing material in the vicinity of the light emitting element is formed from the polysiloxane composition, the sealing material is a near ultraviolet ray (wavelength 400 to 550 nm) emitted from the blue LED element or an ultraviolet ray emitted from the ultraviolet LED element. (Wavelength of 350 to 400 nm), and does not deteriorate due to heat, and exhibits excellent durability even in a high luminance environment.

  The polysiloxane composition usually contains an organic solvent and is used in the form of a solution. Specifically, the liquid polysiloxane composition is applied onto a substrate or the like, and the siloxane-based condensate is cured by removing the solvent by drying to obtain a cured body (film), preferably the film thickness. A cured body (thick film) can be formed. The drying conditions are appropriately set depending on the performance of the dryer to be used. For example, the drying temperature is preferably 70 to 250 ° C., more preferably 100 to 230 ° C., and the drying time is preferably 0.1 to 24 hours. More preferably, it is 0.2 to 3 hours. Moreover, you may implement multistage drying which changes drying temperature in multistage.

[Example]
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 shown as a polystyrene conversion value measured under the following conditions by gel permeation chromatography.
Apparatus: HLC-8120C (manufactured by Tosoh Corporation)
Column: TSK-gel Multipore H _XL- M (manufactured by Tosoh Corporation)
Eluent: THF, flow rate 0.5 mL / min, load 5.0%, 100 μL
(2) Storage stability The obtained condensate was sealed in a polyethylene container at room temperature for 1 month, and the presence or absence of gelation was judged visually. About the thing which is not gelatinized, the viscosity was measured 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) Transparency To 100 parts by weight of the obtained condensate, i-butyl alcohol of dioctyltin dimaleate ester After adding 15 parts of a solution (solid content concentration of about 10%) and stirring sufficiently, it was applied on quartz glass so that the dry film thickness was 10 μm, then dried and cured at 100 ° C. for 1 hour, and then at 200 ° C. A cured product was produced by drying and curing for 1 hour. About this hardening body, the spectral transmittance of wavelength 350-700nm 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% (4) Light resistance 15 parts of i-butyl alcohol solution of dioctyltin dimaleate ester (solid content concentration of about 10%) is sufficiently added to 100 parts by weight of the obtained condensate. Then, it was coated on quartz glass so that the dry film thickness was 10 μm. Subsequently, it dried and hardened at 100 degreeC for 1 hour, and also dried and hardened at 200 degreeC for 1 hour, and produced the hardening body. The cured product was irradiated with ultraviolet light having an illuminance of 5000 mW / cm ² using a spot UV irradiation device (USHIO Corporation: SP-V) in which light having a wavelength of 350 nm or less was cut to approximate the emission wavelength of the ultraviolet LED element. 200
Irradiated for hours. The appearance of the cured product after ultraviolet irradiation was visually observed and evaluated according to the following criteria.
A: No change B: Slightly discolored C: Yellowish (5) Heat resistance To 100 parts by weight of the obtained condensate, an i-butyl alcohol solution of dioctyltin dimaleate ester (solid content concentration of about 10%) was added. After adding 15 parts and stirring sufficiently, it apply | coated on quartz glass so that a dry film thickness might be set to 10 micrometers. Subsequently, it dried and hardened at 100 degreeC for 1 hour, and also dried and hardened at 200 degreeC for 1 hour, and produced the hardening body. The appearance of the cured body after visually storing this cured body at 150 ° C. for 1000 hours was visually observed and evaluated according to the following criteria.
(Color change) A: No change
B: Slightly discolored
C: Yellowish (crack) A: No change
B: Small amount generated
C: Generated on the entire surface

  50 parts of a silanol-terminated polydimethylsiloxane having a Mw = 3500 as a hydroxyl group-containing polysiloxane (A1) (trade name: YF-3800, manufactured by GE Toshiba Silicone Co., Ltd.), and an alkoxy having a Mw = 2,000 as an alkoxy group-containing siloxane polymer (B1) 50 parts of terminal silicon polymer (trade name: X40-9225, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.6 part of sodium methoxide diluted with propylene bricol monopropyl ether 500 times as a condensation catalyst, and methyl isobutyl ketone 66 as a solvent Part was added and a dealcoholization reaction was carried out at 60 ° C. for 4 hours. Subsequently, 6 parts of γ-glycidoxypropyltrimethoxysilane was added, and a silanol group capping reaction was performed at 60 ° C. for 2 hours to obtain a solution containing a siloxane-based condensate having a solid content concentration of about 55% by weight. The weight average molecular weight of the obtained siloxane-based condensate was 5,000.

  When this siloxane-based condensate was evaluated according to the above method, the storage stability was A, the transparency was A, the weather resistance was A, the heat resistance-color change was A, and the heat resistance-crack was A.

  As hydroxyl group-containing polysiloxane (A1), 23 parts of silanol-terminated polydimethylsiloxane (manufactured by GE Toshiba Silicone, trade name: YF-3800) having Mw = 3500, and alkoxy having Mw = 10,000 as alkoxy group-containing siloxane polymer (B1) 49 parts of terminal silicone polymer (trade name: XR31-B0270, manufactured by GE Toshiba Silicone), and 0.2 part of i-propyl alcohol solution of di-i-propoxy-ethylacetoacetate aluminum (concentration 75% by weight) as a condensation catalyst Was added and reacted at 60 ° C. for 4 hours. Next, 3 parts of γ-glycidoxypropyltrimethoxysilane was added, and after capping reaction of silanol groups at 60 ° C. for 2 hours, 40 parts of methyl isobutyl ketone was added to obtain a siloxane having a solid content concentration of about 55% by weight. A solution containing the system condensate was obtained. The weight average molecular weight of the obtained siloxane-based condensate was 25,000.

  When this siloxane-based condensate was evaluated according to the above method, the storage stability was A, the transparency was A, the weather resistance was A, the heat resistance-color change was A, and the heat resistance-crack was A.

  In a reactor equipped with a stirrer and a reflux condenser, 93 parts by weight of hydroxy-terminated polydimethylsiloxane having a Mw = 20,000 (manufactured by GE Toshiba Silicone Co., Ltd., trade name: XF-3905) as a hydroxyl group-containing polysiloxane (A1) And 7 parts by weight of an alkoxy-terminated polysiloxane having an Mw = 800 (manufactured by GE Toshiba Silicone Co., Ltd., trade name: XC96-B0446) as an alkoxy group-containing siloxane oligomer (B1 ′), 42 parts by weight of toluene, and di-i -0.2 parts by weight of a 75% isopropyl alcohol dilute solution of propoxyethyl acetoacetate aluminum was mixed and subjected to a dealcoholization reaction at 70 ° C for 3 hours with stirring. 53 parts by weight of methyl isobutyl ketone and 53 parts by weight of toluene were added to the obtained reaction solution to obtain a solution containing a siloxane-based condensate having a solid content concentration of 40% by weight. The weight average molecular weight of the obtained siloxane-based condensate was 23,000.

When this siloxane-based condensate was evaluated according to the above method, the storage stability was A, the transparency was A, the weather resistance was A, the heat resistance-color change was A, and the heat resistance-crack was A.
[Comparative Example 1]
Example except that 50 parts of alkoxy-terminated silicon oligomer with Mw = 800 was used in place of alkoxy-terminated silicon polymer with Mw = 2,000 (trade name: X40-9225 manufactured by Shin-Etsu Chemical Co., Ltd.) as the alkoxy group-containing siloxane polymer. In the same manner as in Example 1, a siloxane-based condensate was prepared. The obtained siloxane-based condensate was applied on quartz glass so that the dry film thickness was 10 μm, and then dried and cured at 100 ° C. for 1 hour, and then dried and cured at 200 ° C. for 1 hour to produce a cured product. A crack occurred.

[Comparative Example 2]
Example except that Mw = 200,000 silanol-terminated polydimethylsiloxane was used instead of silanol-terminated polydimethylsiloxane having Mw = 3500 (trade name: YF-3800, manufactured by GE Toshiba Silicone) as the hydroxyl group-containing polysiloxane. In the same manner as in Example 2, a siloxane-based condensate was prepared. The resulting siloxane-based condensate was cloudy and phase separated after standing for 1 day.

[Comparative Example 3]
After 100 parts of hydrogenated bisphenol A glycidyl ether (Japan Epoxy Resin, Epicoat YX8000) and 90 parts of methylhexahydrophthalic anhydride (MH700) were sufficiently stirred and mixed, this mixture was adjusted to a dry film thickness of 10 μm. After coating on quartz glass, it was dried and cured at 100 ° C. for 1 hour, and then dried and cured at 150 ° C. for 2 hours to produce a cured body. When the obtained cured product was evaluated according to the above method, the transparency was A, the transparency was B, the light resistance was C, the heat resistance-color change was B, and the heat resistance-crack was A.

Claims (16)

(A1) The following formula (1)

(In the formula, R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and when a plurality of R ¹ and R ² are present, they are the same as each other. Or n is an integer of 5 to 2000)
And a hydroxyl group-containing polysiloxane having a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography in the range of 500 to 100,000,
(B1) The following average composition formula (2)
R ³ _a R ⁴ _b SiO _c (OR ⁵ ) _d (2)
(Wherein R ³ and R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ⁵ is an alkyl group, and R ³ , R ⁴ and R ⁵ are When there are a plurality of them, they may be the same or different from each other, a and b are independently 0 or more and less than 1, a + b is more than 0 and less than 2, c is more than 0 and less than 2, d Is greater than 0 and less than 4 and a + b + c × 2 + d = 4)
And an alkoxy group-containing siloxane polymer having a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography in the range of 1,000 to 100,000,
A process for producing a siloxane-based condensate, characterized by carrying out a dealcoholization reaction in an organic solvent.   The polysiloxane (A1) and the siloxane polymer (B1) are mixed and reacted in a weight ratio (A1 / B1) in terms of a complete hydrolysis condensate within a range of 1/50 to 50/1. Item 2. A method for producing a siloxane-based condensate according to Item 1.   The siloxane system according to claim 1, wherein the polysiloxane (A1) and the siloxane polymer (B1) are mixed and reacted in a molar ratio (A1 / B1) in the range of 1/10 to 10/1. A method for producing a condensate. (A2) The following formula (3)

Wherein R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ⁶ is an alkyl group, R ¹ , R ² and R ⁶ are When there are a plurality of them, they may be the same or different from each other, and n is an integer of 5 to 2000). The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography is 500 to 500. An alkoxy group-containing polysiloxane in the range of 100,000;
(B2) The following average composition formula (4)
R ³ _a R ⁴ _b SiO _c (OH) _d (4)
(In the formula, R ³ and R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and when a plurality of R ³ and R ⁴ are present, they are the same as each other. A and b are each independently 0 or more and less than 1, a + b is more than 0 and less than 2, c is more than 0 and less than 2, d is more than 0 and less than 4, and a + b + c × (2 + d = 4)
And a hydroxyl group-containing siloxane polymer having a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography in the range of 1,000 to 100,000,
A process for producing a siloxane-based condensate, characterized by carrying out a dealcoholization reaction in an organic solvent.   The polysiloxane (A2) and the siloxane polymer (B2) are mixed and reacted in a weight ratio (A2 / B2) in terms of a complete hydrolysis condensate within a range of 1/50 to 50/1. Item 5. A process for producing a siloxane-based condensate according to Item 4.   5. The siloxane system according to claim 4, wherein the polysiloxane (A2) and the siloxane polymer (B2) are mixed and reacted in a molar ratio (A2 / B2) in the range of 1/10 to 10/1. A method for producing a condensate. (A1) The following formula (1)

(In the formula, R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and when a plurality of R ¹ and R ² are present, they are the same as each other. Or n is an integer of 5 to 2000)
And a hydroxyl group-containing polysiloxane having a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography in the range of 500 to 100,000,
(B1 ′) The following average composition formula (2)
R ³ _a R ⁴ _b SiO _c (OR ⁵ ) _d (2)
(Wherein R ³ and R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ⁵ is an alkyl group, and R ³ , R ⁴ and R ⁵ are When there are a plurality of them, they may be the same or different from each other, a and b are independently 0 or more and less than 1, a + b is more than 0 and less than 2, c is more than 0 and less than 2, d Is greater than 0 and less than 4 and a + b + c × 2 + d = 4)
And an alkoxy group-containing siloxane oligomer having a polystyrene-reduced weight average molecular weight in a range of 500 or more and less than 1,000, as measured by gel permeation chromatography,
A method for producing a siloxane-based condensate, characterized in that a completely hydrolyzed condensate weight ratio (A1 / B1 ′) is mixed within a range of 80/20 to 99/1 and subjected to a dealcoholization reaction in an organic solvent. (A2) The following formula (3)

Wherein R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ⁶ is an alkyl group, R ¹ , R ² and R ⁶ are When there are a plurality of them, they may be the same or different from each other, and n is an integer of 5 to 2000). The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography is 500 to 500. An alkoxy group-containing polysiloxane in the range of 100,000;
(B2 ′) The following average composition formula (4)
R ³ _a R ⁴ _b SiO _c (OH) _d (4)
(In the formula, R ³ and R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and when a plurality of R ³ and R ⁴ are present, they are the same as each other. A and b are each independently 0 or more and less than 1, a + b is more than 0 and less than 2, c is more than 0 and less than 2, d is more than 0 and less than 4, and a + b + c × (2 + d = 4)
And a hydroxyl group-containing siloxane oligomer having a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography in the range of 500 or more and less than 1,000,
A method for producing a siloxane-based condensate, characterized in that a completely hydrolyzed condensate weight ratio (A2 / B2 ') is mixed within a range of 80/20 to 99/1 and subjected to a dealcoholization reaction in an organic solvent. (A1) The following formula (1)

(In the formula, R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and when a plurality of R ¹ and R ² are present, they are the same as each other. Or n is an integer of 5 to 2000)
And a hydroxyl group-containing polysiloxane having a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography in the range of 500 to 100,000,
(B1) The following average composition formula (2)
R ³ _a R ⁴ _b SiO _c (OR ⁵ ) _d (2)
(Wherein R ³ and R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ⁵ is an alkyl group, and R ³ , R ⁴ and R ⁵ are When there are a plurality of them, they may be the same or different from each other, a and b are independently 0 or more and less than 1, a + b is more than 0 and less than 2, c is more than 0 and less than 2, d Is greater than 0 and less than 4 and a + b + c × 2 + d = 4)
And an alkoxy group-containing siloxane polymer having a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography in the range of 1,000 to 100,000,
A siloxane-based condensate obtained by dealcoholization reaction in an organic solvent. (A2) The following formula (3)

Wherein R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ⁶ is an alkyl group, R ¹ , R ² and R ⁶ are When there are a plurality of them, they may be the same or different from each other, and n is an integer of 5 to 2000). The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography is 500 to 500. An alkoxy group-containing polysiloxane in the range of 100,000;
(B2) The following average composition formula (4)
R ³ _a R ⁴ _b SiO _c (OH) _d (4)
(In the formula, R ³ and R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and when a plurality of R ³ and R ⁴ are present, they are the same as each other. A and b are each independently 0 or more and less than 1, a + b is more than 0 and less than 2, c is more than 0 and less than 2, d is more than 0 and less than 4, and a + b + c × (2 + d = 4)
And a hydroxyl group-containing siloxane polymer having a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography in the range of 1,000 to 100,000,
A siloxane-based condensate obtained by dealcoholization reaction in an organic solvent. (A1) The following formula (1)

(In the formula, R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and when a plurality of R ¹ and R ² are present, they are the same as each other. Or n is an integer of 5 to 2000)
And a hydroxyl group-containing polysiloxane having a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography in the range of 500 to 100,000,
(B1 ′) The following average composition formula (2)
R ³ _a R ⁴ _b SiO _c (OR ⁵ ) _d (2)
(Wherein R ³ and R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ⁵ is an alkyl group, and R ³ , R ⁴ and R ⁵ are When there are a plurality of them, they may be the same or different from each other, a and b are independently 0 or more and less than 1, a + b is more than 0 and less than 2, c is more than 0 and less than 2, d Is greater than 0 and less than 4 and a + b + c × 2 + d = 4)
And an alkoxy group-containing siloxane oligomer having a polystyrene-reduced weight average molecular weight in a range of 500 or more and less than 1,000, as measured by gel permeation chromatography,
A siloxane-based condensate obtained by mixing in a range of 80/20 to 99/1 by weight ratio (A1 / B1 ′) in terms of complete hydrolysis condensate and subjecting it to a dealcoholization reaction in an organic solvent. (A2) The following formula (3)

Wherein R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ⁶ is an alkyl group, R ¹ , R ² and R ⁶ are When there are a plurality of them, they may be the same or different from each other, and n is an integer of 5 to 2000). The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography is 500 to 500. An alkoxy group-containing polysiloxane in the range of 100,000;
(B2 ′) The following average composition formula (4)
R ³ _a R ⁴ _b SiO _c (OH) _d (4)
(In the formula, R ³ and R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and when a plurality of R ³ and R ⁴ are present, they are the same as each other. A and b are each independently 0 or more and less than 1, a + b is more than 0 and less than 2, c is more than 0 and less than 2, d is more than 0 and less than 4, and a + b + c × (2 + d = 4)
And a hydroxyl group-containing siloxane oligomer having a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography in the range of 500 or more and less than 1,000,
A siloxane-based condensate obtained by mixing in a range of 80/20 to 99/1 by weight ratio (A2 / B2 ′) in terms of complete hydrolysis condensate and subjecting it to a dealcoholization reaction in an organic solvent.   The siloxane-based condensate according to any one of claims 9 to 12, wherein a polystyrene-reduced weight average molecular weight measured by gel permeation chromatography is in the range of 2,000 to 200,000.   A cured product obtained by curing the siloxane-based condensate according to claim 9.   A polysiloxane composition comprising the siloxane-based condensate according to any one of claims 9 to 13 and a filler. A polysiloxane composition comprising the siloxane-based condensate according to any one of claims 9 to 13 and a phosphor.