JPWO2012133080A1 - Curable silicone resin composition and silicone resin cured product - Google Patents

Abstract

The following general formula (1): [CH2 = CHSiO3 / 2] n [R1SiO3 / 2] m [R2SiO3 / 2] j (1) {In formula (1), R1 represents the following general formula (2): CH2 = CR3-CO-O-R4- (2) [In the formula (2), R3 represents a hydrogen atom or a methyl group, and R4 is selected from the group consisting of an alkylene group, an alkylidene group, and a phenylene group. Any one kind to be shown. Wherein R2 represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, and an allyl group, and n, m and j are the following formulas (i) to (iv): n ≧ 1 (i), m ≧ 1 (ii), j ≧ 0 (iii), n + m + j = h. (Iv) [In the formula (iv), h represents an integer selected from the group consisting of 8, 10, 12, and 14. In the case where m and j are each 2 or more, R1 and R2 may be the same or different. } The curable silicone resin composition which contains the cage silsesquioxane resin represented by these, and radical polymerization initiator, and content of the said resin is 10-80 mass%.

Description

  The present invention relates to a curable silicone resin composition and a cured silicone resin. More specifically, the present invention relates to a curable silicone resin composition containing a cage silsesquioxane resin and a cured silicone resin obtained by curing the same.

  Generally, a glass plate is widely used as a transparent substrate such as a substrate for a liquid crystal display element, a substrate for a color filter, a substrate for an organic EL display element, a substrate for electronic paper, a substrate for TFT, or a substrate for solar cell. However, in recent years, the use of a transparent plastic plate as an alternative has been studied because glass plates are easily broken, cannot be bent, have a large specific gravity, and are not suitable for weight reduction.

  On the other hand, silsesquioxane having a cage structure has attracted attention in various fields because it can express a specific function by utilizing its characteristic structure. In particular, a cured product of a cage-type silsesquioxane resin is expected as a material for a transparent plastic plate that can be used as a substitute for a glass plate because it has excellent heat resistance, weather resistance, optical properties, dimensional stability, and the like.

  As a cured product of such a cage silsesquioxane resin, for example, in JP 2009-79163 A (Patent Document 1), a cage silsesquioxane having a vinyl group as a curable functional group and a SiH group. The silsesquioxane hardened | cured material obtained by hydrosilylating the compound which has this, and the compound which has a vinyl group is disclosed. However, in the cured product described in the same document, although high heat resistance and transparency are achieved to some extent, when used as an alternative material for a glass plate, the linear expansion coefficient is large, and further in the hydrosilylation reaction. Commonly used platinum catalysts have the problem of being expensive and economically disadvantageous.

In JP-A-2006-89685 (Patent Document 2), a cage silsesquioxane resin represented by [RSiO _3/2 ] n and having a (meth) acryloyl group as a functional group, an unsaturated compound, and the like A silicone resin copolymer obtained by radical copolymerization of a silicone resin composition comprising:

Furthermore, in JP 2004-143449 A (Patent Document 3), a cage type represented by [RSiO _3/2 ] n and having any one of a (meth) acryloyl group, a glycidyl group and a vinyl group. Silsesquioxane resins are disclosed. In addition, International Publication No. 2008/099850 (Patent Document 4) discloses a cage cleavage type silsesquioxane resin having a vinyl group or the like.

JP 2009-79163 A JP 2006-89685 A JP 2004-143449 A International Publication No. 2008/099850

  The silicone resin copolymer described in Patent Document 2 is highly transparent and has a linear expansion coefficient that is small to some extent. However, the silicone resin copolymer described in Patent Document 2 has a cage like the silicone resin copolymer described in the same document. The cured resin having a (meth) acryloyl group which is a hydrophilic group on all silicon atoms in the type silsesquioxane skeleton has a problem of high water absorption and a large linear expansion coefficient. The inventors have found.

  Further, among the cage silsesquioxane resin described in Patent Document 3 and the cage cleavage silsesquioxane resin described in Patent Document 4, for example, a resin having only a vinyl group is used. The present inventors have found that when a cured product is produced, the resulting cured product is cracked or the cured product becomes cloudy.

  This invention is made | formed in view of the subject which the said prior art has, and can obtain the silicone resin hardened | cured material which has the outstanding transparency, a moldability, and low water absorption, and has a sufficiently small linear expansion coefficient. An object is to provide a curable silicone resin composition and a cured silicone resin obtained by curing the composition.

  As a result of intensive studies to achieve the above object, the present inventors contain a cage silsesquioxane resin having a specific structure having a vinyl group and a (meth) acryloyl group in the silicone resin composition. It is found that by curing a curable silicone resin composition, a cured silicone resin having excellent transparency, moldability and low water absorption and a sufficiently small linear expansion coefficient can be obtained, and the present invention is completed. It came to.

That is, the curable silicone resin composition of the present invention is
The following general formula (1):
[CH ₂ = CHSiO _3/2 ] _n [R ¹ SiO _3/2 ] _m [R ² SiO _3/2 ] _j (1)
{In Formula (1), R ¹ is the following General Formula (2):
CH ₂ = CR ³ —CO—O—R ⁴ − (2)
[In Formula (2), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents any one selected from the group consisting of an alkylene group, an alkylidene group, and a phenylene group. ]
Wherein R ² represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, and an allyl group, and n, m and j are the following formulas (i) to (iv):
n ≧ 1 (i),
m ≧ 1 (ii),
j ≧ 0 (iii),
n + m + j = h (iv)
[In the formula (iv), h represents any integer selected from the group consisting of 8, 10, 12, and 14. ]
When m and j are each 2 or more, R ¹ and R ² may be the same or different. }
A cage-type silsesquioxane resin represented by: and a radical polymerization initiator,
Content of the said cage silsesquioxane resin is 10-80 mass%.

  In the cage silsesquioxane resin, the ratio of the number of vinyl groups to the number of (meth) acryloyl groups (total number of vinyl groups: total number of (meth) acryloyl groups) is preferably 1: 4 to 13: 1. . The curable silicone resin composition of the present invention preferably further contains an unsaturated compound having a (meth) acryloyl group, and the content of the radical polymerization initiator is 0.01 to 10% by mass. It is preferable. The cured silicone resin of the present invention is obtained by radical polymerization of the curable silicone resin composition.

  The reason why the object is achieved by the configuration of the present invention is not necessarily clear, but the present inventors infer as follows. That is, in the curable silicone resin composition of the present invention, the combination of a vinyl group and a (meth) acryloyl group as a curable functional group surprisingly has excellent characteristics of both functional groups. The present inventors speculate that it is possible to obtain a cured silicone resin having a low water absorption and a sufficiently low linear expansion coefficient, as well as being exhibited without loss, excellent transparency and moldability. . In the present invention, the (meth) acryloyl group means a methacryloyl group and an acryloyl group.

  Moreover, in the curable silicone resin composition of the present invention, since it contains two or more functional groups, it has excellent compatibility with other compounds, and even if other compounds are contained, it is a uniform resin. A composition can be obtained. Therefore, the present inventors speculate that the cured silicone resin obtained exhibits excellent transparency and moldability.

  Furthermore, for example, when producing a cured product using a resin having only a vinyl group among the resins described in Patent Document 3 and Patent Document 4, an unsaturated compound having a (meth) acryloyl group is further added. Even if it is intended to produce a cured product, the cage silsesquioxane resin is liberated and becomes cloudy due to the difference in polymerization reactivity between the vinyl group and the (meth) acryloyl group. Since it contains two or more types of functional groups as described above, a caged silsesquioxane resin is not liberated even after curing, and a cured resin product having excellent transparency can be obtained.

  According to the present invention, a curable silicone resin composition having excellent transparency, moldability and low water absorption, and capable of obtaining a cured silicone resin having a sufficiently small linear expansion coefficient, and obtained by curing the same. It is possible to provide a cured silicone resin.

2 is a chromatogram showing the results of GPC of the resin mixture I obtained in Synthesis Example 1. 2 is a graph showing a ¹ H-NMR spectrum of a resin mixture I obtained in Synthesis Example I. It is an enlarged view of FIG. 2A. 4 is a graph showing an ESI-MS spectrum of a resin mixture I obtained in Synthesis Example I. It is a chromatogram which shows the result of GPC of the resin mixture II obtained by the synthesis example II. It is a chromatogram which shows the result of GPC of the resin mixture III obtained by the synthesis example III. It is a chromatogram which shows the result of GPC of the resin mixture IV obtained by the synthesis example IV. 6 is a chromatogram showing a GPC result of a resin mixture V obtained in Synthesis Example V. It is a chromatogram which shows the result of GPC of the resin mixture VI obtained by the synthesis example VI.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

  First, the curable silicone resin composition of the present invention will be described. The curable silicone resin composition of the present invention contains a cage silsesquioxane resin and a radical polymerization initiator, and the content of the cage silsesquioxane resin is 10 to 80% by mass. .

The cage silsesquioxane resin according to the present invention has the following general formula (1):
[CH ₂ = CHSiO _3/2 ] _n [R ¹ SiO _3/2 ] _m [R ² SiO _3/2 ] _j (1)
It is represented by

In the formula (1), R ¹ represents the following general formula (2):
CH ₂ = CR ³ —CO—O—R ⁴ − (2)
The group which has (meth) acryloyl group represented by these is shown. In the formula (2), R ³ represents a hydrogen atom or a methyl group. R ³ is particularly preferably a methyl group from the viewpoint that water absorption can be further reduced due to the repulsive effect of the three-dimensional structure. In the formula (2), R ⁴ represents any one selected from the group consisting of an alkylene group, an alkylidene group, and a phenylene group, and the alkylene group may be linear or branched. From the viewpoint that the linear expansion coefficient is small, the number of carbon atoms is preferably 1 to 3, and the alkylidene group may be linear or branched, Examples thereof include propan-2-ylidene, and the phenylene group includes, for example, 1,2-phenylene having a lower alkyl group in addition to the unsubstituted phenylene group. From the viewpoint of being, an alkylene group having 1 to 3 carbon atoms is preferable. Among these, as R ⁴ , a propylene group is more preferable from the viewpoint that the raw materials are easily available, the distance between crosslinks is not increased, and the linear expansion coefficient is decreased.

Further, the formula (1), R ² is a hydrogen atom, a kind one selected from the group consisting of alkyl group, a phenyl group and an allyl group having 1 to 6 carbon atoms. When the number of carbon atoms in the alkyl group exceeds the upper limit, the molecular mobility increases and the linear expansion coefficient increases. Among these, R ² is more preferably a hydrogen atom, a methyl group, an ethyl group, a phenyl group, or an allyl group from the viewpoint that the linear expansion coefficient is sufficiently small.

Furthermore, in said Formula (1), n, m, and j are following formula (i)-(iv):
n ≧ 1 (i),
m ≧ 1 (ii),
j ≧ 0 (iii),
n + m + j = h (iv)
[In the formula (iv), h represents any integer selected from the group consisting of 8, 10, 12, and 14. ]
An integer satisfying the condition represented by When the n satisfies the condition represented by the above formula (i), the cage silsesquioxane resin according to the present invention has one or more vinyl groups. It becomes possible to obtain a cured product having a sufficiently small coefficient. Moreover, since the cage silsesquioxane resin according to the present invention has one or more (meth) acryloyl groups by satisfying the condition represented by the above formula (ii), the transparent curing by radical polymerization. In particular, when copolymerizing with an unsaturated compound having a (meth) acryloyl group, the compatibility is improved, so that a more transparent cured product can be obtained. Furthermore, since the n, m and j satisfy the conditions represented by the above formulas (i) to (iv), the cage silsesquioxane resin according to the present invention has a cage structure which is almost completely condensed. Thus, it is possible to obtain a cured silicone resin having excellent transparency, moldability and low water absorption, and having a sufficiently small linear expansion coefficient. When m and j are each 2 or more, R ¹ and R ² may be the same or different.

Moreover, as n, m, and j, from the viewpoint that a cured silicone resin having a sufficiently small linear expansion coefficient can be obtained, the following formula (v):
(N + m) / j ≧ 1 (v)
It is more preferable that the condition represented by

  Furthermore, in the cage silsesquioxane resin according to the present invention, the ratio of n to m (n: m) is more preferably 1: 4 to 13: 1, and 1: 3 to 13: 1 is particularly preferred. When the number of n is less than the lower limit, the crosslink density of the resin tends to decrease and the linear expansion coefficient of the cured silicone resin tends to increase. Since the content of the group increases, a large amount of unreacted vinyl groups tend to remain in the cured silicone resin, and when the unsaturated compound having a (meth) acryloyl group is further contained, Since the compatibility with the compound decreases, the cage silsesquioxane resin tends to be liberated and the cured silicone resin tends to become cloudy.

  In the curable silicone resin composition of the present invention, by using such a cage-type silsesquioxane resin, a silicone having excellent transparency, moldability and low water absorption, and having a sufficiently small linear expansion coefficient. A cured resin can be obtained.

As a preferable cage-type silsesquioxane resin used in the present invention, for example, in the above general formula (1), n is 7, m is 1, j is 0, and R ⁴ is (CH _{2 K} ) and the following formula (3):

[In Formula (3), k shows the integer of 1-3. ]
In the compound represented by the general formula (1), n is 6, m is 2, j is 0, R ⁴ is (CH ₂ ) _k , and the following formula (4):

[In Formula (4), k shows the integer of 1-3. ]
In the compound represented by general formula (1), n is 4, m is 4, j is 0, R ⁴ is (CH ₂ ) _k , and the following formula (5):

[In formula (5), k shows the integer of 1-3. ]
In the compound represented by general formula (1), n is 8, m is 2, j is 0, R ⁴ is (CH ₂ ) _k , and the following formula (6):

[In Formula (6), k shows the integer of 1-3. ]
In the compound represented by formula (1), n is 6, m is 2, j is 2, R ⁴ is (CH ₂ ) _k , and R ² is CH ₃ CH ₂ —. And the following formula (7):

[In formula (7), k shows the integer of 1-3. ]
In the compound represented by the general formula (1), n is 7, m is 3, j is 0, R ⁴ is (CH ₂ ) _k , and the following formula (8):

[In formula (8), k shows the integer of 1-3. ]
In the compound represented by general formula (1), n is 6, m is 4, j is 0, R ⁴ is (CH ₂ ) _k , and the following formula (9):

[In formula (9), k shows the integer of 1-3. ]
In the compound represented by the general formula (1), n is 11, m is 1, j is 0, R ⁴ is (CH ₂ ) _k , and the following formula (10):

[In formula (10), k shows the integer of 1-3. ]
In the compound represented by general formula (1), n is 10, m is 2, j is 0, R ⁴ is (CH ₂ ) _k , and the following formula (11):

[In formula (11), k shows the integer of 1-3. ]
In the compound represented by the general formula (1), n is 8, m is 4, j is 0, R ⁴ is (CH ₂ ) _k , and the following formula (12):

[In formula (12), k shows the integer of 1-3. ]
In the compound represented by formula (1), n is 10, m is 4, j is 0, R ⁴ is (CH ₂ ), and the following formula (13):

In the compound represented by formula (1), n is 6, m is 4, j is 4, R ⁴ is (CH ₂ ), and R ² is CH ₃ CH ₂ —. Yes, a compound represented by the following formula (14) may be mentioned.

In the curable silicone resin composition of the present invention, as the cage silsesquioxane resin, one kind may be used alone, or two or more kinds may be used in combination. As content of the said cage silsesquioxane resin, the total mass of the said cage silsesquioxane resin needs to be 10-80 mass% with respect to the curable silicone resin composition of this invention. is there. When the content of the cage silsesquioxane resin is less than the lower limit, in the cured silicone resin, physical properties such as transparency, low thermal expansion, low water absorption, and compatibility are deteriorated. On the other hand, when the above upper limit is exceeded, the viscosity of the curable silicone resin composition increases, making it difficult to produce a molded product. Moreover, from the viewpoint that transparency, low thermal expansion, and low water absorption are better, the content of the cage silsesquioxane resin is particularly preferably 15 to 80% by mass.

  In the curable silicone resin composition of the present invention, the ratio of the number of vinyl groups to the number of all (meth) acryloyl groups in the entire cage silsesquioxane resin (total number of vinyl groups: total number of (meth) acryloyl groups). ) Is preferably 1: 4 to 13: 1. When the vinyl group content is less than the lower limit, the crosslink density of the resin tends to decrease and the linear expansion coefficient of the cured silicone resin tends to increase. Since the ratio of low vinyl groups increases, many unreacted vinyl groups tend to remain in the cured silicone resin. Moreover, from the viewpoint that the low thermal expansion property and the low water absorption become better, the ratio (total number of vinyl groups: total number of (meth) acryloyl groups) is more preferably 1: 3 to 13: 1.

In the present invention, the ratio between the number of vinyl groups and the total number of (meth) acryloyl groups in the cage silsesquioxane resin is ¹ H-NMR (device name: JNM-ECA400, manufacturer name: JEOL, (Solvent: deuterated chloroform, temperature: 23 ° C., 400 MHz), which can be determined from the integration ratio of peaks of vinyl group and (meth) acryloyl group.

As a method for producing such a cage silsesquioxane resin, for example, the following general formula (15):
CH ₂ = CHSiX ₃ (15)
[In the formula (15), X represents any one hydrolyzable group selected from the group consisting of an alkoxy group, an acetoxy group, a halogen atom and a hydroxy group. ]
A silicon compound (A) represented by the following general formula (16):
R ¹ SiY ₃ (16)
[In Formula (16), R ¹ is synonymous with R ¹ in Formula (1), and Y is any one kind of water selected from the group consisting of an alkoxy group, an acetoxy group, a halogen atom and a hydroxy group. Decomposable group is shown. ]
A silicon compound (B) represented by the following general formula (17):
R ² SiZ ₃ (17)
[In formula (17), R ² has the same meaning as R ² in formula (1), and Z is any one selected from the group consisting of an alkoxy group, an acetoxy group, a halogen atom and a hydroxy group. A hydrolyzable group is shown. ]
In the presence of a basic catalyst, and in the presence of a basic catalyst, it is hydrolyzed in a nonpolar solvent and / or polar solvent and partially condensed, and the resulting hydrolysis reaction product is Furthermore, a method of recondensing in the presence of a nonpolar solvent and a basic catalyst can be mentioned.

  Examples of the silicon compound (A) include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltrichlorosilane. These may be used alone or in combination of two or more. Among these, vinyltrimethoxysilane is preferably used from the viewpoint of easy availability of raw materials.

  Examples of the silicon compound (B) include methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, Examples thereof include 3-acryloxypropyltriethoxysilane, and these may be used alone or in combination of two or more. Especially, it is preferable to use 3-methacryloxypropyl trimethoxysilane from a viewpoint that the acquisition of a raw material is easy.

  Examples of the silicon compound (C) include phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, and n-propyltriethoxy. Silane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, etc. These may be used alone or in combination of two or more.

  As a mixing ratio of the silicon compound (A), the silicon compound (B), and the silicon compound (C), a molar ratio of the silicon compound (A) and the silicon compound (B) (number of moles of A: B Mole number) is 1: 4 to 13: 1, and the mole ratio of the silicon compound (C) to the sum of the silicon compound (A) and the silicon compound (B) (number of moles of A + B: number of moles of C). Is preferably mixed so that the ratio is 1: 0 to 5: 2.

  The basic catalyst used in the hydrolysis reaction includes alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, cesium hydroxide; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyl Examples thereof include ammonium hydroxide salts such as trimethylammonium hydroxide and benzyltriethylammonium hydroxide. Among these, it is preferable to use tetramethylammonium hydroxide from the viewpoint of high catalytic activity. The amount of such a basic catalyst is preferably 0.01 to 20% by mass with respect to the total mass of the silicon compounds (A) to (C). The basic catalyst is usually used as an aqueous solution.

  In the hydrolysis reaction, the presence of water is essential, but this can be supplied from an aqueous solution of the basic catalyst or added separately as water. The amount of water should just be more than the mass sufficient to hydrolyze a hydrolyzable group, and is the theoretical amount (mass) of the hydrolyzable group calculated from the mass of the silicon compounds (A) to (C). The amount is preferably 1.0 to 1.5 times.

  In the hydrolysis reaction, it is preferable to use a nonpolar solvent and / or a polar solvent. As such a solvent, if only a nonpolar solvent is used, the reaction system will not be uniform, and the hydrolysis reaction will not proceed sufficiently, and unreacted hydrolyzable groups tend to remain. It is preferable to use both a polar solvent and a polar solvent, or use only a polar solvent. As the polar solvent, alcohols such as methanol, ethanol, 2-propanol, or other polar solvents can be used. Among these, it is preferable to use lower alcohols having 1 to 6 carbon atoms that are soluble in water, and it is more preferable to use 2-propanol. The amount of the nonpolar solvent and / or the polar solvent used is preferably in a range where the total molar concentration (mol / liter: M) of the silicon compounds (A) to (C) is 0.01 to 10M. .

  As reaction conditions for the hydrolysis, the reaction temperature is preferably 0 to 60 ° C, and more preferably 20 to 40 ° C. When the reaction temperature is less than the lower limit, the reaction rate becomes slow, so that the hydrolyzable group remains in an unreacted state, and the reaction time tends to be long. On the other hand, when the reaction temperature exceeds the above upper limit, the reaction rate is too high, so that a complex condensation reaction proceeds, and as a result, high molecular weight of the hydrolysis reaction product tends to be promoted. Moreover, as reaction conditions for the hydrolysis, the reaction time is preferably 2 hours or more. When the reaction time is less than the lower limit, the hydrolysis reaction does not proceed sufficiently and the hydrolyzable group tends to remain in an unreacted state.

  As a method for recovering the hydrolysis reaction product after completion of the hydrolysis reaction, first, the reaction solution is made neutral or acidic using a weakly acidic solution, and then water or a water-containing reaction solvent is separated. Can be mentioned. Examples of the weakly acidic solution include sulfuric acid diluted solution, hydrochloric acid diluted solution, citric acid solution, acetic acid, ammonium chloride aqueous solution, malic acid solution, phosphoric acid solution, oxalic acid solution and the like. In addition, as a method of separating the water or the water-containing reaction solvent, the reaction solution is washed with a saline solution or the like to sufficiently remove moisture and other impurities, and then dried with a drying agent such as anhydrous magnesium sulfate. Means can be employed.

  In addition, as a method for recovering the hydrolysis reaction product when a polar solvent is used as the solvent, first, the polar solvent is removed by evaporation under reduced pressure, and then a nonpolar solvent is added to the hydrolysis reaction product. A method of washing and drying in the same manner as described above can be employed after dissolving the above. In addition, when a nonpolar solvent is used as the solvent, the hydrolysis reaction product can be recovered by separating the nonpolar solvent by means such as evaporation. However, the nonpolar solvent is used in the next recondensation reaction. If it can be used as the nonpolar solvent to be used, it is not necessary to separate it.

  In the hydrolysis reaction, since a condensation reaction of the hydrolyzate occurs together with the hydrolysis, most of the hydrolyzable groups in the silicon compounds (A) to (C) in the hydrolysis reaction, preferably almost all, are OH. Further, most of the OH groups, preferably 80% or more, are condensed by the condensation reaction. Therefore, the hydrolysis reaction product contains a polycondensate produced by the condensation. Such a polycondensate varies depending on the reaction conditions, but has a number average molecular weight of 500 to 10,000 resin (or Oligomer) mixture, which is composed of siloxanes having a plurality of types of cage-type, incomplete cage-type, ladder-type, and random-type structures.

  In the method for producing a cage silsesquioxane resin according to the present invention, the hydrolysis reaction product is further heated in the presence of a nonpolar solvent and a basic catalyst to condense the siloxane bond (referred to as recondensation). Thus, it is preferable to selectively produce a recondensate (a siloxane having a cage structure).

  The nonpolar solvent may be any solvent that is not or hardly soluble in water, but is preferably a hydrocarbon solvent. Examples of the hydrocarbon solvent include nonpolar solvents having a low boiling point such as toluene, benzene, xylene, etc. Among them, it is preferable to use toluene. The amount of the nonpolar solvent used is preferably an amount sufficient to dissolve the hydrolysis reaction product, and is 0.1 to 20 times the mass of the total mass of the hydrolysis reaction product. preferable.

  As the basic catalyst, a basic catalyst used in the hydrolysis reaction can be used, and alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide; tetramerammonium hyhydroxide, tetraethylammonium Mention may be made of ammonium hydroxide salts such as hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide and benzyltriethylammonium hydroxide. Among these, a catalyst that is soluble in a nonpolar solvent such as tetraalkylammonium is preferable. The amount of such a basic catalyst is preferably 0.01 to 20% by mass of the hydrolysis reaction product.

  As reaction conditions for the recondensation reaction, the reaction temperature is preferably 90 to 200 ° C, more preferably 100 to 140 ° C. When the reaction temperature is lower than the lower limit, a sufficient driving force is not obtained to cause the recondensation reaction, and the reaction tends not to proceed. On the other hand, when the reaction temperature exceeds the above upper limit, a reactive organic functional group such as a vinyl group or a (meth) acryloyl group may cause a self-polymerization reaction. Etc. tend to arise. Moreover, as reaction conditions of the said recondensation reaction, it is preferable that reaction time is 2 to 12 hours.

  The hydrolysis reaction product used for recondensation is preferably washed and dried as described above, and further concentrated, but can be used even if these treatments are not performed. In the recondensation reaction, water may be present, but it is not necessary to add it positively, and it is preferable to keep the amount of water supplied from the basic catalyst solution. However, when the hydrolysis is not sufficiently performed, it is preferable to add more water than is necessary for hydrolyzing the remaining hydrolyzable groups.

  In the method for producing a cage silsesquioxane resin according to the present invention, after the recondensation reaction, the reaction solution is washed to remove the catalyst, and concentrated in a rotary evaporator or the like. Depending on the type of functional group, the reaction conditions, and the state of the hydrolysis reaction product, a mixture of a plurality of types of cage silsesquioxane resins according to the present invention represented by the above formulas (3) to (14), etc. can get. The content of the cage silsesquioxane resin according to the present invention is preferably 40% by mass or more of the entire recondensation product (resin mixture).

  Examples of the radical polymerization initiator according to the present invention include a thermal polymerization initiator and a photopolymerization initiator. In the curable silicone resin composition of the present invention, radical polymerization of the cage silsesquioxane resin is promoted by the radical polymerization initiator, and a cured silicone resin having excellent strength and rigidity can be obtained.

  The thermal polymerization initiator is used when the curable silicone resin composition of the present invention is thermally cured. Such a thermal polymerization initiator is preferably an organic peroxide, and examples of the organic peroxide include ketone peroxides, diacylalkyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, Examples thereof include alkyl peresters and percarbonates. Among these, dialkyl peroxide is preferable from the viewpoint of high catalytic activity. Specific examples of the dialkyl peroxide include cyclohexanone peroxide, 1,1-bis (t-hexaperoxy) cyclohexanone, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, diisopropyl peroxide, di- Examples thereof include t-butyl peroxide, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexanoate and the like. As the thermal polymerization initiator, one of these may be used alone, or two or more may be used in combination.

  The said photoinitiator is used when photocuring the curable silicone resin composition of this invention. As such a photopolymerization initiator, it is preferable to use compounds such as acetophenones, benzoins, benzophenones, thioxanthones, and acylphosphine oxides. Specifically, trichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2 -Morpholinopropan-1-one, benzoin methyl ether, benzyldimethyl ketal, benzophenone, thioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, camphorquinone, benzyl, anthraquinone, Michler's ketone, etc. It is done. As the photopolymerization initiator, one of these may be used alone, or two or more may be used in combination.

  As the radical polymerization initiator according to the present invention, the thermal polymerization initiator or the photopolymerization initiator may be used alone, or both may be used in combination. The content of such radical polymerization initiator is preferably 0.01 to 10% by mass and more preferably 0.05 to 5% by mass in the curable silicone resin composition of the present invention. When the content is less than the lower limit, the composition is insufficiently cured, and thus the strength and rigidity of the obtained molded product tend to be low. On the other hand, when the content exceeds the upper limit, the molded product is colored. Tend to cause problems.

  The curable silicone resin composition of the present invention preferably further contains an unsaturated compound having a (meth) acryloyl group. By containing such an unsaturated compound, it becomes possible to obtain a cured product having desired physical properties such as viscosity, resin rigidity, and strength of the silicone resin composition.

  The unsaturated compound is not particularly limited as long as it has a (meth) acryloyl group capable of radical copolymerization with the cage silsesquioxane resin, and when the viscosity of the curable silicone resin composition is increased. From the viewpoint that it is difficult to produce a cured product, a reactive oligomer, a low molecular weight and / or low viscosity reactive monomer, etc., which is a polymer having a structural unit having about 2 to 20 repeating units, is preferred.

  Examples of the reactive oligomer include epoxy acrylate, epoxidized acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl acrylate, polyene / thiol, silicone acrylate, and polystyrylethyl methacrylate. Examples of the reactive monomer include butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate, dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methacrylate. Monofunctional monomers such as dicyclopentanyl diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol acrylate, dimethylol tricyclodecane diacrylate, bisphenol A diglycidyl ether di Acrylate, tetraethylene glycol diacrylate, hydroxypivalate neopentyl glycol diacrylate, trimethylo Le propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, include polyfunctional monomers such as dipentaerythritol hexaacrylate. As the unsaturated compound, one of these may be used alone, or two or more may be used in combination.

  When such an unsaturated compound is contained, the content thereof is 10:90 to 80:20 in which the mass ratio to the cage silsesquioxane resin (cage silsesquioxane resin: unsaturated compound) is 10:90 to 80:20. Is preferable. If the content is less than the lower limit, the viscosity of the silicone resin composition tends to increase, making it difficult to produce a molded product. On the other hand, if the content exceeds the upper limit, the cured silicone resin is transparent. Properties, low thermal expansion, low water absorption, compatibility and the like tend to be reduced.

  The curable silicone resin composition of the present invention can further contain other resins as long as the effects of the present invention are not impaired.

Examples of the other resins include ladder-type siloxanes and random-type siloxanes produced as by-products in the production of the cage silsesquioxane resin. When such a resin is contained, the content is a sum of the contents (mass) of the cage silsesquioxane resin according to the present invention, b is the content (mass) of the unsaturated compound, When the content (mass) of the ladder type siloxane and the random type siloxane is c, the following formula:
10/90 ≦ a / (b + c) ≦ 80/20
It is preferable to satisfy the condition represented by the following formula:
20/80 ≦ a / (b + c) ≦ 75/25
It is more preferable that the condition represented by When the content of the cage silsesquioxane resin is less than the lower limit, physical properties such as transparency, low thermal expansion, low water absorption, and compatibility of the cured silicone resin tend to be lowered. On the other hand, when the said upper limit is exceeded, it exists in the tendency for the viscosity of a silicone resin composition to increase, and manufacture of a molded article to become difficult.

  Further, as the curable silicone resin composition of the present invention, in order to further improve the physical properties of the cured silicone resin and / or to promote radical polymerization, as long as the effects of the present invention are not impaired, A thermal polymerization accelerator, a photoinitiator aid, a sharpener, and the like can be contained. Further, the curable silicone resin composition of the present invention includes an organic / inorganic filler, an inorganic filler, a plasticizer, a flame retardant, a heat stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a lubricant, and an antistatic agent. Further, various additives such as a mold release agent, a foaming agent, a colorant, a crosslinking agent, a dispersion aid, and a resin component may be contained.

  Next, the cured silicone resin of the present invention will be described. The cured silicone resin of the present invention is obtained by radical polymerization of the curable silicone resin composition. Examples of the radical polymerization method include a method of thermosetting by heating and a method of photocuring by light irradiation. In the present invention, any one of the thermosetting and photocuring methods may be used alone, or both methods may be used in combination.

  As the thermosetting conditions, by appropriately selecting the thermal polymerization initiator, thermal polymerization accelerator, etc., the reaction temperature is room temperature (about 25 ° C.) to about 200 ° C., and the reaction time is 0.5 to 10 hours. A wide range of degrees can be selected. Moreover, in this invention, it can be set as the molded object of a desired shape by carrying out the polymerization hardening of the said curable silicone resin composition in a metal mold | die or on a steel belt. As a method for obtaining such a molded body, all of general molding methods such as injection molding, extrusion molding, compression molding, transfer molding, calendar molding, and cast (casting) molding can be applied.

  Examples of the photocuring method include a method of irradiating the curable silicone resin composition with ultraviolet rays having a wavelength of 10 to 400 nm or visible rays having a wavelength of 400 to 700 nm for about 1 to 1200 seconds. The wavelength is not particularly limited, but is preferably near ultraviolet light having a wavelength of 200 to 400 nm. Examples of the lamp used as the ultraviolet ray generation source include a low pressure mercury lamp (output: 0.4 to 4 W / cm), a high pressure mercury lamp (40 to 160 W / cm), and an ultrahigh pressure mercury lamp (173 to 435 W / cm). ), Metal halide lamps (80 to 160 W / cm), and the like, and can be appropriately selected depending on the types of the photopolymerization initiator, the photoinitiator auxiliary, and the sharpening agent to be used. In the present invention, for example, the curable silicone resin composition is poured into a mold made of a transparent material such as quartz glass, cured by radical polymerization, and then removed from the mold to obtain a desired shape. A molded body having a desired shape can be obtained by a method of manufacturing a molded body, a method of curing on the steel belt, or the like.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In each synthesis example, GPC, ¹ H-NMR measurement, and mass spectrometry were performed by the following methods.

(GPC (gel permeation chromatography))
Gel permeation chromatography (GPC) (device name: HLC-8320GPC (manufactured by Tosoh Corporation), solvent: THF, column: ultra-high-speed semi-micro SEC column SuperH
Series, temperature: 40 ° C., speed: 0.6 ml / min). The number average molecular weight and molecular weight distribution (weight average molecular weight / number average molecular weight (Mw / Mn)) were determined as converted values using standard polystyrene (trade name: TSK-GEL, manufactured by Tosoh Corporation).

(Measurement of ¹ H-NMR)
^The measurement was performed using a ¹ H-NMR measuring instrument (device name: JNM-ECA400 (manufactured by JEOL), solvent: deuterated chloroform, temperature: 23 ° C., 400 MHz). The integrated value of the peak of each structural unit obtained was determined, and the molar ratio between the number of vinyl groups and the number of (meth) acryloyl groups was determined from these ratios.

(Mass spectrometry)
Electrospray ionization mass spectrometry (ESI-MS) apparatus (device name: LC apparatus; Separation module 2690 (manufactured by Waters), MS apparatus; ZMD4000 (manufactured by Micromass), measurement conditions: electrospray ionization method, capillary voltage: 3. 5 kV, cone voltage: +30 V).

(Synthesis Example I)
First, in a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 120 ml of 2-propanol (IPA) as a solvent, 150 ml of toluene, and 30.0 ml of a 5% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) as a basic catalyst. I put it in. Next, 53.36 g (0.36 mol) of vinyltrimethoxysilane (KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-methacryloxypropyltrimethoxysilane (SZ-6300, manufactured by Toray Dow Corning Silicone Co., Ltd.) 29.80 g (0.12 mol) was mixed, put into a dropping funnel, and dropped into the reaction vessel over 30 minutes at room temperature (about 25 ° C.) with stirring. After completion of dropping, the mixture was stirred for 2 hours without heating. The solution (reaction solution) in the reaction vessel after stirring is adjusted to neutral (pH 7) with a citric acid aqueous solution, and then pure water is added to separate the organic phase and the aqueous phase, and anhydrous magnesium sulfate is added to the organic phase. 10 g was added and dehydrated. The anhydrous magnesium sulfate was filtered off and concentrated by a rotary evaporator to obtain 48.49 g of a hydrolysis reaction product (silsesquioxane). This hydrolysis reaction product was a colorless viscous liquid soluble in various organic solvents.

  Next, 45.0 g of the hydrolysis reaction product obtained above, 270 ml of toluene, and 6.5 ml of 10% TMAH aqueous solution were placed in a reaction vessel equipped with a stirrer, Dean Stark, and a cooling tube. Water was distilled off. Further, the mixture was heated to 130 ° C. to carry out a recondensation reaction at the reflux temperature of toluene. The temperature at this time was 106 ° C. After refluxing toluene, the reaction was terminated after stirring for 2 hours. The solution (reaction solution) in the reaction vessel after stirring is adjusted to neutral (pH 7) with a citric acid aqueous solution, and then pure water is added to separate the organic phase and the aqueous phase, and anhydrous magnesium sulfate is added to the organic phase. 10 g was added and dehydrated. The anhydrous magnesium sulfate was filtered off and concentrated by a rotary evaporator to obtain 39.15 g of a resin mixture I. The obtained resin mixture I was a colorless viscous liquid soluble in various organic solvents.

The chromatogram which shows the result of GPC of the obtained resin mixture I is shown in FIG. From this result, peak 1 (Mw = 4,959, Mw / Mn = 1.M) including a cage-type silsesquioxane resin, ladder-type siloxane, and random-type siloxane in which (n + m) in general formula (1) is greater than 14. 23) and peak 2 (Mw = 1,322, Mw / Mn = 1.11) containing a cage-type silsesquioxane resin in which (n + m) is 14 or less, and the resulting resin mixture I Is the following formula (I):
[CH ₂ = CHSiO _3/2 ] _n [CH ₂ = C (CH ₃ ) COOC ₃ H ₆ SiO _3/2 ] _m (I)
It was confirmed that it is a resin mixture containing a cage silsesquioxane resin represented by

Further, FIG. 2A~ Figure 2B a graph showing the ¹ H-NMR spectrum of the resulting resin mixture I. From this result, a peak of vinyl group was detected at 6.1 to 5.7 ppm, and a peak of methacryloyl group was detected at 5.5 ppm, and the peak integration ratio of vinyl group 2 with respect to methacryloyl group 1 was 2. It was confirmed that the ratio of the number of vinyl groups to the number of methacryloyl groups in the resulting cage-type silsesquioxane resin (total number of vinyl groups: total number of methacryloyl groups) was 2.96: 1. It was done. In addition, this ratio shows that the condensate which has a functional group of the same ratio as the molar ratio of the vinyl group and methacryloyl group at the time of preparation is obtained.

  Furthermore, the graph which shows the ESI-MS spectrum of the obtained resin mixture I is shown in FIG. Table 1 shows the detected main peaks (m / z) and the corresponding numerical values of n and m in the above formula (I). The detected peak (m / z) is the above formula (I) (where n is 1-12, m is 6-14, and the sum of n and m is 8-14). ) Is a value obtained by adding ammonium ions to the molecular weight of the cage silsesquioxane resin. From this mass spectrometry result, it was confirmed that a cage-type silsesquioxane resin having a vinyl group and a methacryloyl group was obtained.

(Synthesis Example II)
Except for 110 ml of 2-propanol (IPA) and 230 ml of toluene, 70.76 g (0.48 mol) of vinyltrimethoxysilane, and 16.94 g (0.07 mol) of 3-methacryloxypropyltrimethoxysilane. In the same manner as in Synthesis Example I, 47.60 g of a hydrolysis reaction product (silsesquioxane) was obtained. This hydrolysis reaction product was a colorless viscous liquid soluble in various organic solvents.

  Next, 36.55 g of a resin mixture II was obtained in the same manner as in Synthesis Example I except that 43.0 g of the hydrolysis reaction product obtained above was used and toluene was changed to 260 ml. The obtained resin mixture II was a colorless viscous liquid soluble in various organic solvents.

A chromatogram showing the results of GPC of the obtained resin mixture II is shown in FIG. From this result, peak 1 (Mw = 5,581, Mw / Mn = 1.M) including a cage-type silsesquioxane resin, ladder-type siloxane, and random-type siloxane in which (n + m) in general formula (1) is greater than 14. 39) and peak 2 (Mw = 1,171, Mw / Mn = 1.11) containing a cage-type silsesquioxane resin in which (n + m) is 14 or less, and the obtained resin mixture II Was confirmed to be a resin mixture containing a cage silsesquioxane resin represented by the above formula (I). Moreover, the total number of vinyl groups: total number of methacryloyl groups in the cage silsesquioxane resin determined from the ¹ H-NMR spectrum of the obtained resin mixture II was 6.89: 1.

(Synthesis Example III)
Except for 80 ml of 2-propanol (IPA) and 160 ml of toluene, 28.68 g (0.19 mol) of vinyltrimethoxysilane and 48.06 g (0.19 mol) of 3-methacryloxypropyltrimethoxysilane. In the same manner as in Synthesis Example I, 48.68 g of a hydrolysis reaction product (silsesquioxane) was obtained. This hydrolysis reaction product was a colorless viscous liquid soluble in various organic solvents. Next, 38.33 g of a resin mixture III was obtained in the same manner as in Synthesis Example I except that 45.0 g of the hydrolysis reaction product obtained above was used. The obtained resin mixture III was a colorless viscous liquid soluble in various organic solvents.

A chromatogram showing the results of GPC of the obtained resin mixture III is shown in FIG. From this result, the peak 1 (Mw = 6,047, Mw / Mn = 1...) Including a cage-type silsesquioxane resin, ladder-type siloxane, and random-type siloxane with (n + m) greater than 14 in the general formula (1). 05) and peak 2 (Mw = 1,891, Mw / Mn = 1.41) containing a cage silsesquioxane resin in which (n + m) is 14 or less are obtained, and the obtained resin mixture III is the above It was confirmed that this was a resin mixture containing a cage silsesquioxane resin represented by the formula (I). Further, the total number of vinyl groups: the total number of methacryloyl groups in the cage silsesquioxane resin determined from the ¹ H-NMR spectrum of the obtained resin mixture III was 0.98: 1.

(Synthesis Example IV)
100 ml of 2-propanol (IPA) and 200 ml of toluene, 44.36 g (0.30 mol) of vinyltrimethoxysilane, 29.73 g (0.12 mol) of 3-methacryloxypropyltrimethoxysilane, Hydrolysis reaction product (Silsesukioki) in the same manner as in Synthesis Example I except that 8.99 g (0.06 mol) of methoxysilane (LS-890, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed and placed in the dropping funnel. Sun) was obtained. This hydrolysis reaction product was a colorless viscous liquid soluble in various organic solvents.

  Then, 45.0 g of the hydrolysis reaction product obtained above was used, and 38.20 g of a resin mixture IV was obtained in the same manner as in Synthesis Example I except that the reflux temperature of toluene was 105 ° C. The obtained resin mixture IV was a colorless viscous liquid soluble in various organic solvents.

A chromatogram showing the results of GPC of the obtained resin mixture IV is shown in FIG. From this result, peak 1 (Mw = 5,593, Mw / Mn = 1...) Including cage-type silsesquioxane resin, ladder-type siloxane, and random-type siloxane in which (n + m + j) in general formula (1) is greater than 14. 28) and peak 2 (Mw = 1,344, Mw / Mn = 1.11) containing a cage-type silsesquioxane resin in which (n + m + j) is 14 or less, and the obtained resin mixture IV Is the following formula (IV):
[CH ₂ = CHSiO _3/2 ] _n [CH ₂ = C (CH ₃ ) COOC ₃ H ₆ SiO _3/2 ] _m [CH ₃ CH ₂ SiO _3/2 ] _j (IV)
It was confirmed that it is a resin mixture containing a cage silsesquioxane resin represented by Further, the total number of vinyl groups: the total number of methacryloyl groups in the cage silsesquioxane resin determined from the ¹ H-NMR spectrum of the obtained resin mixture IV was 4.96: 2.

(Synthesis Example V)
60 ml of 2-propanol (IPA), 120 ml of toluene, 69.27 g (0.28 mol) of 3-methacryloxypropyltrimethoxysilane, and the same as in Synthesis Example I except that vinyltrimethoxysilane was not used. As a result, 48.36 g of a hydrolysis reaction product (silsesquioxane) was obtained. This hydrolysis reaction product was a colorless viscous liquid soluble in various organic solvents.

  Subsequently, 41.4 g of the resin mixture V was obtained in the same manner as in Synthesis Example I except that 45.0 g of the hydrolysis reaction product obtained above was used and 260 ml of toluene was used. The obtained resin mixture V was a colorless viscous liquid soluble in various organic solvents.

For the obtained resin mixture V, a chromatogram showing the results of GPC is shown in FIG. From this result, peak 1 (Mw = 1,769, Mw / Mn = 1.08) including all methacryloxypropyl cage silsesquioxane resins was detected, and the resulting resin mixture V was represented by the following formula (V) :
[CH ₂ = C (CH ₃ ) COOC ₃ H ₆ SiO _3/2 ] _m (V)
It was confirmed that it is a resin mixture containing a cage silsesquioxane resin represented by

(Synthesis Example VI)
The procedure was the same as in Synthesis Example I except that 130 ml of 2-propanol (IPA), 260 ml of toluene, 93.65 g (0.632 mol) of vinyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane were not used. As a result, 44.03 g of a hydrolysis reaction product (silsesquioxane) was obtained. This hydrolysis reaction product was a colorless viscous liquid soluble in various organic solvents.

  Next, 38.24 g of a resin mixture VI was obtained in the same manner as in Synthesis Example I except that 42.0 g of the hydrolysis reaction product obtained above was used and toluene was changed to 260 ml. The obtained resin mixture VI was a colorless viscous liquid soluble in various organic solvents.

For the obtained resin mixture V, a chromatogram showing the results of GPC is shown in FIG. From this result, peak 1 (Mw = 3,229, Mw / Mn = 1.M) including all vinyl cage silsesquioxane resins in which general formula (1) is greater than 14, ladder type siloxane, and random type siloxane. 40) and peak 2 (Mw = 797, Mw / Mn = 1.41) containing an all-vinyl cage silsesquioxane resin having j of 14 or less, and the resulting resin mixture VI is Formula (VI):
[CH ₂ = CHSiO _3/2 ] _n (VI)
It was confirmed that it is a resin mixture containing a cage silsesquioxane resin represented by

Example 1
First, with respect to 100 parts by mass of resin mixture I (cage-type silsesquioxane resin content: 45% by mass) containing a cage-type silsesquioxane resin having a vinyl group and a methacryloyl group obtained in Synthesis Example I , 1.0 part by mass of 1-hydroxycyclohexyl phenyl ketone (Irg184, manufactured by Ciba Japan Co., Ltd.) and 1.0 part by mass of dicumyl peroxide (Park Mill D, manufactured by Nippon Oil & Fats Co., Ltd.) as a polymerization initiator are mixed. A curable silicone resin composition was obtained.

Next, 2 g of the obtained curable silicone resin composition was applied on a glass plate, a metal spacer having a height of 0.2 mm was disposed, and the glass plate was further covered from above, and the resin composition was applied by its own weight. After casting to a thickness of 0.2 mm, a 30 W / cm high-pressure mercury lamp was used and cured with an integrated exposure amount of 2000 mJ / cm ² . Furthermore, it heated at 200 degreeC under nitrogen atmosphere for 1 hour, peeled from the glass plate, and obtained the film-form silicone resin hardened | cured material of about 100 mm x 100 mm x thickness 0.2mm.

(Example 2)
70 parts by mass of a resin mixture I containing a cage silsesquioxane resin having a vinyl group and a methacryloyl group obtained in Synthesis Example I, and dicyclopentanyl diacrylate (DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.) As a polymerization initiator, 1.0 part by mass of 1-hydroxycyclohexyl phenyl ketone (Irg184, manufactured by Ciba Japan Co., Ltd.) and dicumyl peroxide (Park Mill D, Japan) are mixed with 100 parts by mass of 30 parts by mass. 1.0 parts by mass of Ogyu Co., Ltd.) was mixed to obtain a curable silicone resin composition. Further, a cured silicone resin was obtained in the same manner as in Example 1 using the obtained curable silicone resin composition.

(Example 3)
A curable silicone resin composition as in Example 1 except that the resin mixture II obtained in Synthesis Example II (cage-type silsesquioxane resin content: 50% by mass) was used instead of the resin mixture I. And the cured silicone resin was obtained.

(Example 4)
A curable silicone resin composition and a cured silicone resin were obtained in the same manner as in Example 2 except that the resin mixture II obtained in Synthesis Example II was used in place of the resin mixture I.

(Example 5)
A curable silicone resin composition as in Example 1 except that the resin mixture III obtained in Synthesis Example III (cage-type silsesquioxane resin content: 75% by mass) was used instead of the resin mixture I. And the cured silicone resin was obtained.

(Example 6)
A curable silicone resin composition and a cured silicone resin were obtained in the same manner as in Example 2 except that the resin mixture III obtained in Synthesis Example III was used in place of the resin mixture I.

(Example 7)
A curable silicone resin composition as in Example 1 except that the resin mixture IV (cage-type silsesquioxane resin content: 45% by mass) obtained in Synthesis Example IV was used in place of the resin mixture I. And the cured silicone resin was obtained.

(Example 8)
A curable silicone resin composition and a cured silicone resin were obtained in the same manner as in Example 2 except that the resin mixture IV obtained in Synthesis Example IV was used in place of the resin mixture I.

(Comparative Example 1)
A curable silicone resin composition and a cured silicone resin were obtained in the same manner as in Example 1 except that the resin mixture V obtained in Synthesis Example V was used in place of the resin mixture I.

(Comparative Example 2)
A curable silicone resin composition and a cured silicone resin were obtained in the same manner as in Example 2 except that the resin mixture V obtained in Synthesis Example V was used in place of the resin mixture I.

(Comparative Example 3)
A curable silicone resin composition and a cured silicone resin were obtained in the same manner as in Example 1 except that the resin mixture VI obtained in Synthesis Example VI was used in place of the resin mixture I.

(Comparative Example 4)
A curable silicone resin composition and a cured silicone resin were obtained in the same manner as in Example 2 except that the resin mixture VI obtained in Synthesis Example VI was used in place of the resin mixture I.

  About the silicone resin hardened | cured material obtained in Examples 1-8 and Comparative Examples 1-4, evaluation of film moldability, the measurement of a water absorption, the measurement of a linear expansion coefficient, and the measurement of a total light transmittance were performed with the following method. It was.

(Evaluation of film formability)
Visually check for cracks in the cured silicone resin:
Evaluation A: No cracks or breaks are observed in the film. Evaluation B: Evaluation is made as a mesh-like crack or break is observed in the film. The obtained results are shown in Table 2.

(Measurement of water absorption)
First, the obtained cured silicone resin was kept at 50 ° C. for 24 hours and preliminarily dried. Next, the water absorption rate was measured based on the plastic-water absorption rate calculation method (JISK7209). The obtained results are shown in Table 2.

(Measurement of linear expansion coefficient)
About the obtained cured silicone resin (5 mm × 5 mm × thickness 1 mm (5 test pieces having a thickness of 0.2 mm)), a thermomechanical analysis method was performed using a device name: TMA4000SA (manufactured by BRUKER). Measurement was performed based on the temperature rise rate (temperature rising rate: 5 ° C./min, compression load: 0.1 N, temperature range: 50 to 150 ° C.).
The coefficient of linear expansion is:
The coefficient of linear expansion (ppm / K) was calculated from the displacement per 1 m of the test piece / temperature displacement. The obtained results are shown in Table 2.

(Measurement of total light transmittance)
About the obtained silicone resin hardened | cured material (thickness 0.2mm), the transmittance | permeability of all the light was measured using NDH2000 (made by Nippon Denshoku).
The transmittance is the following formula:
The total light transmittance (%) was calculated from transmitted light intensity / incident light intensity. The obtained results are shown in Table 2.

  As is clear from the results shown in Table 2, the cured silicone resins obtained in Examples 1 to 8 all have excellent transparency, moldability and low water absorption, and have a sufficient linear expansion coefficient. It was confirmed to be small. On the other hand, the cured silicone resin obtained in Comparative Examples 1 and 2 was confirmed to have a high water absorption rate and a high linear expansion coefficient, and the cured silicone resin obtained in Comparative Examples 3 to 4 was film moldability. It was confirmed to be inferior.

  Moreover, also in Examples 2, 4, 6, and 8 in which dicyclopentanyl diacrylate which is an unsaturated compound was further contained, it was confirmed that a cured silicone resin excellent in transparency was obtained. On the other hand, in Comparative Example 4, a white turbid silicone resin cured product was obtained. This is presumably because the cage silsesquioxane resin was liberated and phase-separated (white turbidity) due to the difference in polymerization reactivity between the vinyl group and the methacryloyl group.

  As described above, according to the present invention, a curable silicone resin composition capable of obtaining a cured silicone resin having excellent transparency, moldability and low water absorption, and having a sufficiently small linear expansion coefficient, and It becomes possible to provide a cured silicone resin obtained by curing this.

  Such silicone resin cured products include liquid crystal display element substrates, color filter substrates, organic EL display element substrates, electronic paper substrates, TFT substrates, solar cell substrates, and other transparent substrates, touch panels, and transparent electrodes. As an optical film application for films, light guide plates, protective films, polarizing films, retardation films, lens sheets, etc., as a glass substitute material for various transport machinery, housing window materials, etc., its range of use has become wide and its industrial utility value Is extremely high.

Claims (5)

The following general formula (1):
[CH ₂ = CHSiO _3/2 ] _n [R ¹ SiO _3/2 ] _m [R ² SiO _3/2 ] _j (1)
{In Formula (1), R ¹ is the following General Formula (2):
CH ₂ = CR ³ —CO—O—R ⁴ − (2)
[In Formula (2), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents any one selected from the group consisting of an alkylene group, an alkylidene group, and a phenylene group. ]
Wherein R ² represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, and an allyl group, and n, m and j are the following formulas (i) to (iv):
n ≧ 1 (i),
m ≧ 1 (ii),
j ≧ 0 (iii),
n + m + j = h (iv)
[In the formula (iv), h represents any integer selected from the group consisting of 8, 10, 12, and 14. ]
In the case where m and j are each 2 or more, R ¹ and R ² may be the same or different. }
A cage-type silsesquioxane resin represented by: and a radical polymerization initiator,
Curable silicone resin composition whose content of the said cage silsesquioxane resin is 10-80 mass%.   The ratio of the number of vinyl groups to the number of (meth) acryloyl groups (total number of vinyl groups: total number of (meth) acryloyl groups) in the cage silsesquioxane resin is 1: 4 to 13: 1. The curable silicone resin composition described in 1.   The curable silicone resin composition according to claim 1 or 2, further comprising an unsaturated compound having a (meth) acryloyl group.   Content of the said radical polymerization initiator is 0.01-10 mass%, The curable silicone resin composition as described in any one of Claims 1-3.   A cured silicone resin obtained by radical polymerization of the curable silicone resin composition according to any one of claims 1 to 4.