KR20140021634A - Curable silicone resin composition and cured silicone resin - Google Patents

Abstract

(1): < EMI ID =
_{[CH 2 = CHSiO 3/2} ] n [R 1 SiO 3/2] m [R 2 SiO 3/2] j ... (One)
{In formula (1), R ₁ is the following general formula (2):
CH ₂ = CR ₃ -CO-OR _4- . (2)
A (meth) acryloyl group represented by [wherein 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.] Represents a group having R ² represents 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 formula (iv), h represents an integer selected from the group consisting of 8, 10, 12, and 14.] represents an integer that satisfies the condition, and when m and j are each 2 or more, R ₁ and R ₂ May be the same as or different from each other.} A curable silicone resin composition containing a cage silsesquioxane resin and a radical polymerization initiator, wherein the content of the resin is 10 to 80% by weight.

Description

Curable silicone resin composition and cured silicone resin {CURABLE SILICONE RESIN COMPOSITION AND CURED SILICONE RESIN}

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

In general, glass plates are widely used as transparent substrates such as substrates for liquid crystal displays, substrates for color filters, substrates for organic EL displays, substrates for electronic paper, substrates for TFTs, and substrates for solar cells. However, recently, the use of transparent plastic plates has been considered as a substitute for glass plates because they are fragile, do not bend and are not suitable for light weight due to their high specific gravity.

On the other hand, silsesquioxane having a basket structure has attracted attention in various fields because it is possible to express a specific function by using its characteristic structure. Since the hardened | cured material of cage silsesquioxane resin especially is excellent in heat resistance, weather resistance, optical characteristics, dimensional stability, etc., it is expected as a material of the transparent plastic plate replacing a glass plate.

As a hardened | cured material of such cage silsesquioxane resin, For example, Unexamined-Japanese-Patent No. 2009-79163 (patent document 1) WHEREIN: The compound which has cage silsesquioxane and SiH group which have a vinyl group as a curable functional group, Disclosed is a silsesquioxane cured product obtained by hydrosilylation a compound having a vinyl group. However, although the cured product described in the above literature has achieved a high level of heat resistance and transparency, when used as an alternative material for glass plates, the coefficient of linear expansion is large, and the platinum catalyst generally used in hydrosilylation reactions is expensive. It had a problem of economic disadvantage.

Also, [RSiO _3/2] is represented by n (meth) type basket having an acryloyl group as a functional group consisting of a silsesquioxane silicone resin with an unsaturated compound such as Japanese Unexamined Patent Application Publication No. 2006-89685 (Patent Document 2) The silicone resin copolymer obtained by radical copolymerizing a resin composition is described.

In addition, the [RSiO _3/2] it is represented by n (meth) acryloyl group, a cage-like silsesquioxane having any one of a glycidyl group and vinyl group, Japanese Unexamined Patent Application Publication No. 2004-143449 (Patent Document 3) Resin is disclosed. In addition, International Patent Publication No. 2008/099850 (Patent Document 4) discloses a basket cleavage type silsesquioxane resin having a vinyl group or the like.

Japanese Unexamined Patent Publication No. 2009-79163 Japanese Laid-Open Patent Publication No. 2006-89685 Japanese Patent Laid-Open No. 2004-143449 International Publication No. 2008/099850

Although the silicone resin copolymer described in the patent document 2 has high transparency and somewhat small coefficient of linear expansion, all silicon sources in the cage silsesquioxane skeleton like the silicone resin copolymer described in the document are The present inventors have found that the cured resin having a (meth) acryloyl group which is a hydrophilic group that is a hydrophilic phase has a problem of high water absorption and a large coefficient of linear expansion.

Moreover, hardened | cured material is manufactured using the resin which has only a vinyl group, for example among the cage silsesquioxane resin described in the said patent document 3, and the basket cleavage silsesquioxane resin described in the said patent document 4. Then, the inventors found that problems such as cracking or clouding of the resulting cured product occur.

This invention is made | formed in view of the subject which the said prior art has, The curable silicone resin composition which can obtain the silicone resin hardened | cured material which has outstanding transparency, moldability, and low water absorption, and whose linear expansion coefficient is sufficiently small, and the silicone resin diameter obtained by hardening this is It is aimed at providing cargo.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said objective, in the silicone resin composition, the curable silicone resin composition containing cage silsesquioxane resin of the specific structure which has a vinyl group and a (meth) acryloyl group is obtained. By hardening | curing, it discovered that the silicone resin hardened | cured material which has outstanding transparency, moldability, and low water absorption, and whose linear expansion coefficient is sufficiently low was obtained, and completed this invention.

That is, the curable silicone resin composition of the present invention,

(1): < EMI ID =

_{[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-OR ^4- (2)

[In Formula (2), R <^3> represents a hydrogen atom or a methyl group, and R <^4> represents any 1 type selected from the group which consists of an alkylene group, an alkylidene group, and a phenylene group.]

Represents a group having a (meth) acryloyl group represented by 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)-(iv):

n≥1 (i),

m≥1 (ii),

j≥0 (iii),

n + m + j = h (iv)

[Wherein h represents any integer selected from the group consisting of 8, 10, 12 and 14]

Represents an integer that satisfies the condition indicated by. When m and j are each 2 or more, R ¹ and R ² may be the same as or different from each other.

It contains cage silsesquioxane resin represented by the following, 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 and the number of (meth) acryloyl groups (the total number of vinyl groups: the total number of (meth) acryloyl groups) is preferably 1: 4 to 13 :: 1. Do. Moreover, as curable silicone resin composition of this invention, it is preferable to further contain the unsaturated compound which has a (meth) acryloyl group, and it is preferable that content of the said radical polymerization initiator is 0.01-10 mass%. Moreover, the silicone resin hardened | cured material of this invention is obtained by radically polymerizing the said curable silicone resin composition.

On the other hand, it is not clear why the above object is achieved due to the configuration of the present invention, but the present inventors speculate as follows. That is, in the curable silicone resin composition of the present invention, a vinyl group and a (meth) acryloyl group are contained in combination as a curable functional group, surprisingly, only excellent properties of both functional groups are exhibited without being lost, thereby exhibiting excellent transparency and formability. At the same time, the present inventors conjecture that a silicone resin cured product having low water absorption and low linear expansion coefficient can be obtained. In addition, in this invention, a (meth) acryloyl group means a methacryloyl group and acryloyl group.

Moreover, since curable silicone resin composition of this invention contains 2 or more types of functional groups, it is excellent in compatibility with other compounds, and even if it contains another compound, a uniform resin composition can be obtained. Therefore, the present inventors conjecture that the outstanding transparency and moldability are exhibited in the obtained silicone resin hardened | cured material.

Moreover, when manufacturing hardened | cured material using resin which has only vinyl group among resins described in the said patent document 3 and the said patent document 4, you may further contain the unsaturated compound which has a (meth) acryloyl group, and hardened | cured material Even if it is going to manufacture, since the polymerization reactivity of a vinyl group and a (meth) acryloyl group differs, cage silsesquioxane resin is liberated and turbid, but in this invention, it contains 2 or more types of functional groups as mentioned above. Therefore, even after hardening, cage-shaped silsesquioxane resin is free, and the resin hardened | cured material excellent in transparency can be obtained.

ADVANTAGE OF THE INVENTION According to this invention, the curable silicone resin composition which can obtain the silicone resin hardened | cured material which has outstanding transparency, moldability, and low water absorption, and whose linear expansion coefficient is sufficiently small, and the silicone resin hardened | cured material obtained by hardening this can be provided.

1 is a chromatogram showing the results of GPC of the resin mixture I obtained in Synthesis Example 1. FIG.
2A is a graph showing the ¹ H-NMR spectrum of the resin mixture I obtained in Synthesis Example I. FIG.
FIG. 2B is an enlarged view of FIG. 2A.
3 is a graph showing the ESI-MS spectrum of the resin mixture I obtained in Synthesis Example I. FIG.
4 is a chromatogram showing the results of GPC of the resin mixture II obtained in Synthesis Example II.
5 is a chromatogram showing the results of GPC of the resin mixture III obtained in Synthesis Example III.
6 is a chromatogram showing the results of GPC of the resin mixture IV obtained in Synthesis Example IV.
7 is a chromatogram showing the result of GPC of the resin mixture V obtained in Synthesis Example V. FIG.
8 is a chromatogram showing the GPC results of the resin mixture VI obtained in Synthesis Example VI.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on the preferable embodiment.

First, the curable silicone resin composition of this invention is demonstrated. Curable silicone resin composition of this invention contains cage silsesquioxane resin and a radical polymerization initiator, and content of the cage silsesquioxane resin is 10-80 mass%.

Basket silsesquioxane resin according to 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-OR ^4- (2)

The group which has a (meth) acryloyl group represented by is shown. In said formula (2), R <^3> represents a hydrogen atom or a methyl group. As R <^3> , a methyl group is especially preferable from a viewpoint that water absorption can be further reduced by the repulsive effect of a three-dimensional structure. In 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, and the coefficient of linear expansion is small. Is preferably from 1 to 3 carbon atoms, and the alkylidene group may be linear or branched, for example, propane-2-ylidene and the like, and the phenylene group may be, for example, In addition to the unsubstituted phenylene group, the 1, 2- phenylene etc. which have a lower alkyl group are mentioned, Especially, an alkylene group of 1-3 carbon atoms is preferable from a viewpoint of a raw material availability. Among these, as R ⁴ , a propylene group is more preferable from the viewpoint of obtaining raw materials, not increasing the distance between crosslinks, and decreasing the coefficient of linear expansion.

In Formula (1), 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. If the carbon number of the alkyl group exceeds the upper limit, the coefficient of linear expansion increases because molecular mobility increases. Among these, as R ² , a hydrogen atom, a methyl group, an ethyl group, a phenyl group, or an allyl group is more preferable from the viewpoint of decreasing the coefficient of linear expansion sufficiently.

In addition, n, m, and j in said Formula (1) are following formula (i)-(iv):

n≥1 (i),

m≥1 (ii),

j≥0 (iii),

n + m + j = h (iv)

[Wherein h represents any integer selected from the group consisting of 8, 10, 12 and 14]

Lt; / RTI &gt; Since n is satisfying the condition represented by said formula (i), since the cage silsesquioxane resin which concerns on this invention has one or more vinyl groups, the distance between bridge | crosslinks by radical polymerization becomes short and a linear expansion coefficient is fully satisfied. A small cured product can be obtained. In addition, since the cage silsesquioxane resin according to the present invention has one or more (meth) acryloyl groups because m is satisfied with the condition represented by the formula (ii), a transparent cured product is formed by radical polymerization. It becomes possible to obtain, especially when copolymerizing with the unsaturated compound which has a (meth) acryloyl group, since compatibility is improved, a more transparent hardened | cured material can be obtained. In addition, because the n, m, and j satisfy the conditions represented by the formulas (i) to (iv), the cage silsesquioxane resin according to the present invention becomes an almost completely condensed cage structure, so excellent transparency It is possible to obtain a silicone resin cured product having moldability, low water absorption, and sufficiently low coefficient of linear expansion. On the other hand, when m and j are two or more, respectively, R <^1> and R <^2> may be same or different, respectively.

In addition, n, m and j, from the viewpoint of obtaining a silicone resin cured product having a sufficiently small coefficient of linear expansion, the following formula (v):

(n + m) / j≥1 (v)

It is more preferable to satisfy the condition indicated by.

Moreover, in the cage silsesquioxane resin which concerns on this invention, it is more preferable that ratio (n: m) of said n and said m is 1: 4-13: 1, It is especially preferable that it is 1: 3-13: 1. desirable. When the number of n is less than the lower limit, the crosslinking density of the resin tends to decrease, and the linear expansion coefficient of the cured silicone resin tends to be increased. On the other hand, when the number of n exceeds the upper limit, the content of the vinyl group having low radical polymerizability increases. In the cured resin, many unreacted vinyl groups tend to remain, and when the unsaturated compound having a (meth) acryloyl group is further contained, the compatibility with the above-mentioned unsaturated compound is lowered. The oxane resin tends to free and the silicone resin cured product becomes cloudy.

In the curable silicone resin composition of this invention, by using this cage silsesquioxane resin, the silicone resin hardened | cured material which has the outstanding transparency, moldability, and low water absorption, and whose coefficient of linear expansion is sufficiently small can be obtained.

Preferred cage silsesquioxane resin used in the present invention, n is 7 of, for example, the general formula (1), wherein m is 1, j is 0, R ⁴ is (CH ₂₎ a _k, Formula (3):

[Formula 1]

[K shows the integer of 1-3 in Formula (3).]

In the compound represented by the above Formula (1), n is 6, m is 2, j is 0, R ⁴ is (CH ₂ ) _k , and the following Formula (4):

(2)

[K shows the integer of 1-3 in Formula (4).]

In the compound represented by the above Formula (1), n is 4, m is 4, j is 0, R ⁴ is (CH ₂ ) _k , and the following Formula (5):

(3)

[K shows the integer of 1-3 in Formula (5).]

In the compound represented by the above Formula (1), n is 8, m is 2, j is 0, R ⁴ is (CH ₂ ) _k , and the following Formula (6):

[Chemical Formula 4]

[K shows the integer of 1-3 in Formula (6).]

In the compound represented by the formula (1), n is 6, m is 2, j is 2, R ⁴ is (CH ₂ ) _k , R ² is CH ₃ CH _2- , and the following formula ( 7):

[Chemical Formula 5]

[K shows the integer of 1-3 in Formula (7).]

In the compound represented by the formula (1), n is 7, m is 3, j is 0, R ⁴ is (CH ₂ ) _k , and the following Formula (8):

[Chemical Formula 6]

[K shows the integer of 1-3 in Formula (8).]

In the compound represented by the above Formula (1), n is 6, m is 4, j is 0, R ⁴ is (CH ₂ ) _k , and the following Formula (9):

[Formula 7]

[K shows the integer of 1-3 in Formula (9).]

In the compound represented by the above Formula (1), n is 11, m is 1, j is 0, R ₄ is (CH ₂ ) _k , and the following Formula (10):

[Formula 8]

[K shows the integer of 1-3 in Formula (10).]

In the compound represented by the above Formula (1), n is 10, m is 2, j is 0, R ⁴ is (CH ₂ ) _k , and the following Formula (11):

[Chemical Formula 9]

[K shows the integer of 1-3 in Formula (11).]

In the compound represented by the above Formula (1), n is 8, m is 4, j is 0, R ⁴ is (CH ₂ ) _k , and the following Formula (12):

[Formula 10]

[K shows the integer of 1-3 in Formula (12).]

In the compound represented by the formula (1), n is 10, m is 4, j is 0, R ⁴ is (CH ₂ ), and the following formula (13):

[Formula 11]

In compound (1), n is 6, m is 4, j is 4, R ⁴ is (CH ₂ ), R ² is CH ₃ CH _2- , and the following formula (14) The compound represented by) is mentioned.

[Chemical Formula 12]

In the curable silicone resin composition of this invention, as said cage silsesquioxane resin, you may use individually by 1 type, or may use in combination of 2 or more type. Content of the said cage silsesquioxane resin needs to be 10-80 mass% of total mass of the cage silsesquioxane resin with respect to curable silicone resin composition of this invention. When content of the said cage silsesquioxane resin is less than the said minimum, physical properties, such as transparency, low thermal expansion property, low water absorption, and compatibility, fall in hardened | cured silicone resin. On the other hand, when it exceeds the said upper limit, the viscosity of curable silicone resin composition will increase and manufacture of a molded object will become difficult. Moreover, it is especially preferable that content of the said cage silsesquioxane resin is 15-80 mass% from a viewpoint that transparency, low thermal expansion property, and low water absorption become more favorable.

Furthermore, in the curable silicone resin composition of this invention, in the whole said cage silsesquioxane resin, ratio of the number of vinyl groups and the total number of (meth) acryloyl groups (the total number of vinyl groups: the total number of (meth) acryloyl groups) ) Is preferably 1: 4 to 13 :: 1. When the content of the vinyl group is less than the lower limit, the crosslinking density of the resin tends to decrease, and the linear expansion coefficient of the cured silicone resin tends to increase, whereas when the content of the vinyl group exceeds the upper limit, the proportion of the vinyl group having low radical polymerizability increases. There exists a tendency for many unreacted vinyl groups to remain in the silicone resin hardened | cured material. Moreover, it is more preferable that the ratio (total vinyl group number: total (meth) acryloyl group number) is 1: 3 to 13 :: 1 from the viewpoint of low thermal expansion and low water absorption.

Meanwhile, in the present invention, the ratio of 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: heavy chloroform, It can obtain | require from the integral ratio of the peak of the vinyl group and (meth) acryloyl group measured using temperature: 23 degreeC, 400MHz).

As a manufacturing method of such cage silsesquioxane resin, for example, the following general formula (15):

CH ₂ = CHSiX ₃ (15)

[In Formula (15), X represents any 1 type of hydrolysable group chosen from the group which consists of an alkoxy group, an acetoxy group, a halogen atom, and a hydroxyl group.]

Silicon compound (A) represented by following formula and the following general formula (16):

R ¹ SiY ₃ (16)

[Equation (16) of R ¹ is the same meaning as R ¹ in the formula (1), Y represents a hydrolyzable group of any one selected from an alkoxy group, an acetoxy group, a halogen atom and a group consisting of hydroxy .]

Silicon compound (B) represented by following formula (17):

R ² SiZ ₃ (17)

[Equation (17) of R ² is the meaning of the same as R ² in the formula (1), Z is an alkoxy group, an acetoxy group, a halogen atom and a hydroxy group hydrolyzable groups of any one type of compound selected from the group consisting of Is displayed.]

The silicon compound (C) represented by is mixed and subjected to hydrolysis in a nonpolar solvent and / or a polar solvent in the presence of a basic catalyst and partially condensed, so that the obtained hydrolysis reaction product is also recycled in the presence of a nonpolar solvent and a basic catalyst. The method of condensation is mentioned.

Vinyl trimethoxysilane, vinyl triethoxysilane, vinyl trichlorosilane, etc. are mentioned as said silicon compound (A), These may be used independently, or may be used in combination of 2 or more type. Especially, it is preferable to use vinyl trimethoxysilane from a viewpoint of easy raw material acquisition.

As said silicon compound (B), methacryloxymethyl trimethoxysilane, methacryloxymethyl triethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryl An oxypropyl trimethoxysilane, 3-acryloxypropyl triethoxysilane, etc. are mentioned, These may be used independently or may be used in combination of 2 or more type. Especially, it is preferable to use 3-methacryloxypropyl trimethoxysilane from a viewpoint of easy raw material acquisition.

Examples of the silicon compound (C) include phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane and n-propyltrimethoxysilane , n-propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, p-styryltri Methoxysilane, p-styryltriethoxysilane, etc. are mentioned, These may be used independently or may be used in combination of 2 or more type.

As a mixing ratio of the said silicon compound (A), the said silicon compound (B), and the said silicon compound (C), the molar ratio (mole number of A: mole number of B) of the said silicon compound (A) and the said silicon compound (B) is 1 : 4 to 13: 1, the molar ratio of the silicon compound (C) to the sum of the silicon compound (A) and the silicon compound (B) (mole number of A + B: mole of C) is 1: 0 to 5 It is preferable to mix so that it is: 2.

As a basic catalyst used for the said hydrolysis reaction, Alkali metal hydroxides, such as potassium hydroxide, sodium hydroxide, cesium hydroxide; Ammonium hydroxide salts, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyl trimethylammonium hydroxide, and benzyl triethylammonium hydroxide, are mentioned. Among these, it is preferable to use tetramethylammonium hydroxide from a viewpoint of high catalytic activity. It is preferable that the quantity of such a basic catalyst is 0.01-20 mass% with respect to the total mass of the said silicon compound (A)-(C). On the other hand, the basic catalyst is usually used as an aqueous solution.

The presence of water is essential for the hydrolysis reaction, which may be supplied from an aqueous solution of the basic catalyst or may be added separately from water. The amount of water may be any mass or more sufficient to hydrolyze the hydrolyzable group, but is preferably 1.0 to 1.5 times the theoretical amount (mass) of the hydrolyzable group calculated from the mass of the silicon compounds (A) to (C).

In addition, it is preferable to use a nonpolar solvent and / or a polar solvent in the said hydrolysis reaction. In the case of using only a non-polar solvent, the reaction system is not uniform and the hydrolysis reaction does not proceed sufficiently, so that both the non-polar solvent and the polar solvent are used, or only the polar solvent is used. It is preferable. As said polar solvent, alcohol, such as methanol, ethanol, 2-propanol, or another polar solvent can be used. Especially, it is preferable to use the C1-C6 lower alcohols which have solubility with water, and it is more preferable to use 2-propanol. It is preferable that the usage-amount of the said nonpolar solvent and / or the said polar solvent is a range in which the total molar concentration (mol / liter: M) of the said silicon compound (A)-(C) becomes 0.01-10 M.

As reaction conditions of the said hydrolysis, it is preferable that reaction temperature is 0-60 degreeC, and it is more preferable that it is 20-40 degreeC. When the reaction temperature is less than the lower limit, the reaction rate is slowed, so that the hydrolyzable groups remain in the unreacted state and the reaction time tends to be long. On the other hand, when the reaction temperature exceeds the upper limit, the reaction rate is too fast, so that a complicated condensation reaction proceeds, and as a result, the high molecular weight of the hydrolysis reaction product tends to be promoted. Moreover, as reaction conditions of the said hydrolysis, it is preferable that reaction time is 2 hours or more. If the reaction time is less than the lower limit, the hydrolysis reaction does not proceed sufficiently, and the hydrolyzable groups tend to remain in the unreacted state.

As a method of recovering a hydrolysis reaction product after completion of the hydrolysis reaction, a method of firstly making the reaction solution neutral or acidic using a weakly acidic solution, and then separating water or a water-containing reaction solvent. Examples of the weakly acidic solution include sulfuric acid dilute solution, hydrochloric acid dilute solution, citric acid solution, acetic acid, ammonia chloride solution, malic acid solution, phosphoric acid solution, and oxalic acid solution. As a method of separating the water or the water-containing reaction solvent, a means such as washing the reaction solution with saline or the like to sufficiently remove moisture or other impurities, and then drying it with a drying agent such as anhydrous magnesium sulfate may be employed.

In addition, when the polar solvent is used as the solvent, a method of recovering the hydrolysis reaction product is first removed by evaporation of the polar solvent, followed by addition of a nonpolar solvent to dissolve the hydrolysis reaction product. Similarly, the method of washing and drying can be employ | adopted. In addition, when a nonpolar solvent is used as the solvent, the non-polar solvent can be separated by means of evaporation to recover the hydrolysis reaction product. If the non-polar solvent can be used as a nonpolar solvent to be used in the next recondensation reaction, it can be separated. There is no need.

In the hydrolysis reaction, condensation reaction of the hydrolyzate with hydrolysis occurs, so that most, preferably almost all, of the hydrolyzable groups in the silicon compounds (A) to (C) are substituted with OH groups in the hydrolysis reaction. In addition, 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, and the polycondensate is a resin (or oligomer) mixture having a number average molecular weight of 500 to 10,000, depending on the reaction conditions, and a plurality of cage types. , Consisting of siloxanes having incomplete basket-like, ladder-like, and random-type structures.

In the manufacturing method of the cage silsesquioxane resin which concerns on this invention, the said hydrolysis reaction product is further heated in presence of a nonpolar solvent and a basic catalyst, and condensation (recondensation) of a siloxane bond is carried out (basket) It is preferable to selectively prepare a siloxane having a mold structure.

The nonpolar solvent may be any solvent having little or no solubility in water, and is preferably a hydrocarbon solvent. Examples of the hydrocarbon solvent include nonpolar solvents having a low boiling point such as toluene, benzene, and xylene, and among them, toluene is preferable. It is preferable that the usage-amount of a nonpolar solvent is sufficient quantity to dissolve the said hydrolysis reaction product, and it is preferable that it is 0.1-20 times mass with respect to the total mass of the said hydrolysis reaction product.

As the basic catalyst, a basic catalyst used in the hydrolysis reaction may be used, and alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide; Ammonium hydroxide salts, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyl trimethylammonium hydroxide, and benzyl triethylammonium hydroxide, are mentioned. Especially, the catalyst which is soluble in nonpolar solvents, such as tetraalkylammonium, is preferable. It is preferable that the quantity of such a basic catalyst is 0.01-20 mass% of the said hydrolysis reaction product.

As reaction conditions of the said recondensation reaction, it is preferable that reaction temperature is 90-200 degreeC, and it is more preferable that it is 100-140 degreeC. If the reaction temperature is less than the lower limit, there is a tendency that the driving force is not sufficiently obtained to cause the recondensation reaction and the reaction does not proceed. On the other hand, when the reaction temperature exceeds the upper limit, reactive organic functional groups such as vinyl groups and (meth) acryloyl groups may cause self-polymerization reactions. Therefore, it is necessary to suppress the reaction temperature or add a polymerization inhibitor or the like. There is a tendency. Moreover, as reaction conditions of the said recondensation reaction, it is preferable that reaction time is 2 to 12 hours.

In addition, the hydrolysis reaction product used for recondensation is preferably washed and dried and concentrated as described above, but may be used even if such treatments are not carried out. Moreover, although water may exist in the said recondensation reaction, it does not need to be added actively, It is preferable to only be about the moisture supplied from a basic catalyst solution. However, in the case where the hydrolysis is not sufficiently performed, it is preferable to add more water than necessary to hydrolyze the remaining hydrolyzable group.

In the manufacturing method of the cage silsesquioxane resin which concerns on this invention, after the said recondensation reaction, the kind of functional group is contained in the recondensation product obtained by wash | cleaning a reaction solution, removing a catalyst, and concentrating by a rotary evaporator etc. Although it depends on reaction conditions and the state of a hydrolysis reaction product, the mixture of the cage-type silsesquioxane resin which concerns on several types of this invention represented by said Formula (3)-(14) etc. is obtained. It is preferable that content of cage silsesquioxane resin which concerns on this invention is 40 mass% or more of the said whole recondensation product (resin mixture).

As a radical polymerization initiator which concerns on this invention, a thermal polymerization initiator and a photoinitiator are mentioned. In the curable silicone resin composition of this invention, radical polymerization of the said cage silsesquioxane resin is accelerated | stimulated with the said radical polymerization initiator, and the silicone resin hardened | cured material which has the outstanding strength and rigidity can be obtained.

The said thermal polymerization initiator is used when thermosetting the curable silicone resin composition of this invention. As such a thermal polymerization initiator, an organic peroxide is preferable, and as said organic peroxide, ketone peroxides, diacyl chel peroxides, hydroperoxides, dialkyl peroxides, peroxy ketals, alkyl per esters, per Carbonates; and the like. 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-t-butyl peroxide, t-hexyl peroxy isopropyl monocarbonate, t-butyl peroxy-2-ethylhexanoate, and the like. As said thermal polymerization initiator, you may use individually by 1 type and may use it in combination of 2 or more type.

The said photoinitiator is used when photocuring the curable silicone resin composition of this invention. As such a photoinitiator, it is preferable to use compounds, such as acetophenone, benzoin, benzophenone, thioxanthone, an acylphosphine oxide. Specifically, trichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methyl Thiophenyl) -2-morpholinopropane-1-one, benzoin methyl ether, benzyldimethyl ketal, benzophenone, thioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, Camphorquinone, benzyl, anthraquinone, Michler's ketone and the like. As said photoinitiator, these may be used individually by 1 type, and may be used in combination of 2 or more type.

As a radical polymerization initiator which concerns on this invention, the said thermal polymerization initiator or the said photoinitiator may be used independently, respectively, and may be used in combination of both. It is preferable that it is 0.01-10 mass% in the curable silicone resin composition of this invention, and, as for content of such a radical polymerization initiator, it is more preferable that it is 0.05-5 mass%. When content is less than the said lower limit, since hardening of a composition will become inadequate, the intensity | strength and rigidity of the molded object obtained tend to become low, and when it exceeds the said upper limit, there exists a tendency which becomes a problem that a molded object will be colored.

It is preferable that the curable silicone resin composition of the present invention further contains an unsaturated compound having a (meth) acryloyl group. By containing such an unsaturated compound, the hardened | cured material which has desired physical properties, such as a viscosity, resin rigidity, and strength of a silicone resin composition, can be obtained.

As said unsaturated compound, what is necessary is just to have the (meth) acryloyl group which can be radically copolymerized with the said cage silsesquioxane resin, and it is not specifically limited, From a viewpoint that manufacture of hardened | cured material becomes difficult when the viscosity of curable silicone resin composition becomes high. Reactive oligomers, low molecular weight and / or low viscosity reactive monomers which are polymers having a repeating number of the structural unit of about 2 to 20 are preferable.

The reactive oligomer may be epoxy acrylate, epoxidized acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl acrylate, polyene / thiol, silicone acrylate, polystyrylethyl methacryl. The rate etc. are mentioned. In addition, the reactive monomers include butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate, dicyclopentenyloxyethyl acrylate, phenoxy Monofunctional monomers such as ethyl acrylate and trifluoroethyl methacrylate; Dicyclopentanyl diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol acrylate, dimethylol tricyclodecane diacrylate, bisphenol A diglycidyl ether di Polyacrylates such as acrylate, tetraethylene glycol diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate A functional monomer can be mentioned. As said unsaturated compound, you may use individually by 1 type, or may use it in combination of 2 or more type.

When it contains such an unsaturated compound, it is preferable that content is the mass whose mass ratio (basket-type silsesquioxane resin: unsaturated compound) with respect to the said cage silsesquioxane resin becomes 10: 90-80: 20. When the content is less than the above lower limit, the viscosity of the silicone resin composition increases, which tends to make the molding difficult, while when the content exceeds the upper limit, transparency, low thermal expansion, low water absorption, compatibility, and the like in the cured silicone resin The physical properties tend to be lowered.

The curable silicone resin composition of this invention can further contain other resin in the range which does not impair the effect of this invention.

As said other resin, the ladder type | mold siloxane, random type | mold siloxane, etc. which were produced | generated as a side reaction in manufacture of the said cage silsesquioxane resin are mentioned, for example. When it contains such resin, the content is a sum of content (mass) of the cage silsesquioxane resin concerning the said invention, content (mass) of the said unsaturated compound b, said ladder type siloxane, and random type siloxane. When content (mass) of these is set to c, the following formula:

10/90? A / (b + c)? 80/20

It is preferable to satisfy the condition represented by, and the following formula:

20/80? A / (b + c)? 75/25

It is more preferable to satisfy the condition indicated by. When content of the said cage silsesquioxane resin is less than the said minimum, there exists a tendency for physical properties, such as transparency, low thermal expansion property, low water absorption, compatibility, and the like of cured silicone resin to fall. On the other hand, when it exceeds the said upper limit, there exists a tendency for the viscosity of a silicone resin composition to increase and manufacture of a molded object becomes difficult.

In addition, the curable silicone resin composition of the present invention has a thermal polymerization accelerator, a photoinitiation aid for the purpose of improving the physical properties of the cured silicone resin and / or the purpose of promoting radical polymerization within a range that does not impair the effects of the present invention ( (Iii) and a preservative may be further contained. In addition, the curable silicone resin composition of the present invention is 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, an antistatic agent, a mold release agent, a foaming agent, a coloring agent, You may contain various additives, such as a crosslinking agent, a dispersion adjuvant, and a resin component.

Next, the silicone resin hardened | cured material of this invention is demonstrated. The silicone resin cured product of the present invention is obtained by radical polymerization of the curable silicone resin composition. As said radical polymerization method, the method of thermosetting by heating and the photocuring by light irradiation are mentioned. In the present invention, any one of the above-mentioned thermosetting and photocuring may be used alone, or both methods may be used in combination.

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

As said photocuring method, the method of irradiating the said curable silicone resin composition to the ultraviolet-ray of wavelength 10-400 nm and visible light of wavelength 400-700 nm for 1 to 1200 second, for example is mentioned. Although the said wavelength is not specifically limited, It is preferable that it is a near-ultraviolet ray of wavelength 200-400 nm. As a lamp used as a source of ultraviolet rays, for example, a low pressure mercury lamp (output: 0.4 to 4 W / cm), a high pressure mercury lamp (40 to 160 W / cm), an ultra high pressure mercury lamp (173 to 435 W / cm), metal halide Lamps 80-160 W / cm etc. can be mentioned, According to the kind of the said photoinitiator, the said photoinitiator, and the said preservative to be used, it can select suitably. In the present invention, for example, the curable silicone resin composition is injected into a mold made of a transparent material such as quartz glass, cured by radical polymerization, and then demolded from the mold to produce a molded article having a desired shape. The molded object of a desired shape can be obtained by the method of hardening on a steel belt, etc.

Example

Hereinafter, although this invention is demonstrated further more concretely based on an Example and a comparative example, this invention is not limited to a following example. In addition, the measurement and mass spectrometry of GPC and ¹ H-NMR were performed by the method shown below in each synthesis example, respectively.

(GPC (gel permeation chromatography))

Gel permeation chromatography (GPC) (device name: HLC-8320GPC (manufactured by Tosoh Corporation), solvent: THF, column: ultra-fast semi-micro SEC column SuperH series, temperature: 40 ° C, rate: 0.6 ml / min) . The number average molecular weight and molecular weight distribution (weight average molecular weight / number average molecular weight (Mw / Mn)) were calculated | required as conversion value by standard polystyrene (brand name: TSK-GEL, Tosoh Corporation make).

(Measurement of ¹ H-NMR)

^It measured using ¹ H-NMR measuring device (apparatus name: JNM-ECA400 (made by JEOL company), solvent: medium chloroform, temperature: 23 degreeC, 400 MHz). The integral value of the peak of each obtained structural unit was calculated | required, and the molar ratio of the number of vinyl groups and the number of (meth) acryloyl groups was determined from these ratios.

(Mass analysis)

Electrospray ionization mass spectrometry (ESI-MS) device (device name: LC device; Separation module 2690 (manufactured by Waters), MS device; ZMD4000 (manufactured by Micromass), measurement conditions: electrospray ionization method, capillary Li voltage: 3.5 kV, cone voltage: +30 V).

Synthesis Example I

First, 120 ml of 2-propanol (IPA), 150 ml of toluene, and 30.0 ml of 5% aqueous tetramethylammonium hydroxide solution (TMAH aqueous solution) as a basic catalyst were added to a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer. Next, 53.36 g (0.36 mol) of vinyltrimethoxysilane (KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-methacryloxypropyltrimethoxysilane (SZ-6300, Torre Dow Corning Silicone Co., Ltd.) Kaisha) 29.80 g (0.12 mol) was mixed and placed in a dropping funnel, and dropped into the reaction vessel over 30 minutes at room temperature (about 25 ° C) while stirring. It stirred for 2 hours, without heating after completion | finish of dripping. After the solution (reaction solution) in the reaction vessel after stirring was adjusted to neutral (pH 7) with an aqueous citric acid solution, pure water was added, the solution was separated into an organic phase and an aqueous phase, and 10 g of anhydrous magnesium sulfate was added to the organic phase. Dehydrated. 48.49 g of hydrolysis reaction products (silsesquioxane) were obtained by filtering-separating the said anhydrous magnesium sulfate and concentrating with a rotary evaporator. This hydrolysis reaction product was a colorless viscous liquid soluble in various organic solvents.

Subsequently, 45.0 g of the hydrolysis reaction product obtained above, 270 ml of toluene, and 6.5 ml of 10% aqueous TMAH solution were added to a reaction vessel equipped with a stirrer, Dean Stark, and a cooling tube, and the mixture was gradually heated to distill off water. Furthermore, it heated to 130 degreeC and performed the recondensation reaction at the reflux temperature of toluene. In addition, the temperature at this time was 106 degreeC. After toluene reflux, the mixture was stirred for 2 hours and then the reaction was terminated. The solution (reaction solution) in the reaction vessel after stirring was adjusted to neutral (pH 7) with an aqueous citric acid solution, pure water was added, the solution was separated into an organic phase and an aqueous phase, and 10 g of anhydrous magnesium sulfate was added to the organic phase and dewatered. The anhydrous magnesium sulfate was filtered off and concentrated with 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, the peak 1 (Mw = 4,959, Mw / Mn = 1.23) containing the cage silsesquioxane resin, ladder siloxane, and random siloxane in which (n + m) of General formula (1) is larger than 14, ) And peak 2 (Mw = 1,322, Mw / Mn = 1.11) containing a cage silsesquioxane resin having (n + m) of 14 or less are detected, and the resulting resin mixture I is represented by 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 was a resin mixture containing cage silsesquioxane resin represented by

Also shows a graph in Fig. 2a ~ Figure 2b represents the ¹ H-NMR spectrum of the obtained resin mixture I. From this result, the peak of a vinyl group is detected in 6.1-5.7 ppm, and the peak of a methacryloyl group is detected in 5.5 ppm, These peak integration ratios are vinyl group 2.96 with respect to methacryloyl group 1, and the cage shape obtained It was confirmed that the ratio of the number of vinyl groups and the number of methacryloyl groups in the silsesquioxane resin (the total number of vinyl groups: the total number of methacryloyl groups) was 2.96: 1. 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 the methacryloyl group at the time of preparation was obtained.

Moreover, the graph which shows ESI-MS spectrum of obtained resin mixture I is shown in FIG. Table 1 also shows the detected main peak (m / z) and the numerical values of n and m in the formula (I) corresponding thereto. On the other hand, the detected peak (m / z) is cage-shaped represented by the formula (I) (wherein n is 1 to 12, m is 6 to 14, and the sum of n and m is 8 to 14). It is the value which ammonium ion added to the molecular weight of silsesquioxane resin. It was confirmed also from this mass spectrometry that cage silsesquioxane resin which has a vinyl group and a methacryloyl group was obtained.

Synthesis Example II

Synthesis except 110 ml of 2-propanol (IPA), 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 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.

Subsequently, 36.55 g of resin mixture II was obtained similarly to the synthesis example I except using 43.0 g of hydrolysis reaction products obtained above and making 260 ml of toluene. Obtained resin mixture II was a colorless viscous liquid soluble in various organic solvents.

The chromatogram which shows the result of GPC of obtained resin mixture II is shown in FIG. From this result, the peak 1 containing cage silsesquioxane resin, ladder siloxane, and random siloxane in which (n + m) in General formula (1) is larger than 14 (Mw = 5,581, Mw / Mn = 1.39) and the peak 2 (Mw = 1,171, Mw / Mn = 1.11) containing cage silsesquioxane resin whose said (n + m) is 14 or less are detected, and the obtained resin mixture II is represented by said Formula (I) It was confirmed that it was a resin mixture containing cage silsesquioxane resin represented by Moreover, the number of total vinyl groups: total number of methacryloyl groups in the cage silsesquioxane resin calculated | required from the ¹ H-NMR spectrum of obtained resin mixture II was 6.89: 1.

Synthesis Example III

Synthesis except 80 ml of 2-propanol (IPA), 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 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. Subsequently, 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 obtained hydrolysis reaction product was used. Obtained resin mixture III was a colorless viscous liquid soluble in various organic solvents.

The chromatogram which shows the result of GPC of obtained resin mixture III is shown in FIG. From this result, the peak 1 containing cage silsesquioxane resin, ladder siloxane, and random siloxane in which (n + m) in General formula (1) is larger than 14 (Mw = 6,047, Mw / Mn = 1.05) and the peak 2 (Mw = 1,891, Mw / Mn = 1.41) containing cage silsesquioxane resin whose said (n + m) is 14 or less are obtained, and obtained resin mixture III is the said Formula (I) It was confirmed that it was a resin mixture containing cage silsesquioxane resin represented by Moreover, the number of total vinyl groups: total number of methacryloyl groups in the cage silsesquioxane resin calculated | required from the ¹ H-NMR spectrum of obtained resin mixture III was 0.98: 1.

Synthesis Example IV

100 ml of 2-propanol (IPA), 200 ml of toluene, 44.36 g (0.30 mol) of vinyltrimethoxysilane, 29.73 g (0.12 mol) of 3-methacryloxypropyltrimethoxysilane, and ethyl Hydrolysis reaction product (silsesquioxane) in the same manner as in Synthesis Example I, except that 8.99 g (0.06 mol) of trimethoxysilane (LS-890, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed and placed in a dropping funnel. Obtained 47.09 g. This hydrolysis reaction product was a colorless viscous liquid soluble in various organic solvents.

Subsequently, 45.0 g of the hydrolysis reaction product obtained above was used, and 38.20 g of resin mixtures IV were obtained like Example Synthesis I except that the reflux temperature of toluene was 105 degreeC. The obtained resin mixture IV was a colorless viscous liquid soluble in various organic solvents.

The chromatogram which shows the result of GPC of obtained resin mixture IV is shown in FIG. From this result, the peak 1 (Mw = 5,593, Mw /) containing the cage silsesquioxane resin, ladder siloxane, and random siloxane in which (n + m + j) in General formula (1) is larger than 14 Mn = 1.28) and peak 2 (Mw = 1,344, Mw / Mn = 1.11) containing a cage silsesquioxane resin having (n + m + j) equal to or less than 14 were detected, and the resulting resin mixture IV was Food (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 was a resin mixture containing cage silsesquioxane resin represented by In addition, 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 no synthesis of vinyltrimethoxysilane were used. In the same manner, 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.

Next, 45.0 g of the obtained hydrolysis reaction product was used, and 41.4 g of resin mixture V was obtained like Example Synthesis I except having made 260 ml of toluene. The obtained resin mixture V was a colorless viscous liquid soluble in various organic solvents.

The chromatogram which shows the result of GPC with respect to the obtained resin mixture V is shown in FIG. From this result, the peak 1 (Mw = 1,769, Mw / Mn = 1.08) containing all methacryloxypropyl cage silsesquioxane resin was detected, and the obtained resin mixture V is represented by following formula (V):

[CH ₂ = C (CH ₃ ) COOC ₃ H ₆ SiO _3/2 ] _m (V)

It was confirmed that it was a resin mixture containing cage silsesquioxane resin represented by

Synthesis Example VI

130 ml of 2-propanol (IPA), 260 ml of toluene, 93.65 g (0.632 mol) of vinyltrimethoxysilane, and no 3-methacryloxypropyltrimethoxysilane were used. In the same manner, 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, 42.0 g of the hydrolysis reaction product obtained above was used, and 38.24 g of resin mixture VI was obtained like Example 1 except having made 260 ml of toluene. Obtained resin mixture VI was a colorless viscous liquid soluble in various organic solvents.

The chromatogram which shows the result of GPC with respect to the obtained resin mixture V is shown in FIG. From this result, the peak 1 (Mw = 3,229, Mw / Mn = 1.40) containing the total vinyl cage silsesquioxane resin, ladder siloxane, and random siloxane in which j in General formula (1) is larger than 14 And peak 2 (Mw = 797, Mw / Mn = 1.41) containing a total vinyl cage silsesquioxane resin having j of 14 or less was detected, and the resulting resin mixture VI was represented by the following formula (VI):

_{[CH 2 = CHSiO 3/2} ] n (VI)

It was confirmed that it was a resin mixture containing cage silsesquioxane resin represented by

(Example 1)

First, a polymerization initiator with respect to 100 mass parts of resin mixture I (basket-type silsesquioxane resin content: 45 mass%) containing the cage silsesquioxane resin which has the vinyl group and methacryloyl group obtained by the synthesis example I. Curable silicone resin by mixing 1.0 parts by mass of 1-hydroxycyclohexylphenyl ketone (Irg184, manufactured by Chiba Japan) and 1.0 parts by mass of dicumylperoxide (PERCUMYL D, manufactured by Nihon Yushi Co., Ltd.) A composition was obtained.

Subsequently, 2 g of the obtained curable silicone resin composition was applied onto a glass plate, a metal spacer having a height of 0.2 mm was placed thereon, and then the glass plate was covered from above, and the resin composition was cast by the weight of the glass plate to give a thickness. After making it into 0.2 mm, it hardened | cured by the integrated exposure amount of 2000mJ / cm <2> using the high pressure mercury lamp of 30W / cm. Furthermore, it heated at 200 degreeC in 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 0.2 mm.

(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.) ) 1.0 part by mass of 1-hydroxycyclohexylphenyl ketone (Irg184, manufactured by Chiba Japan Co., Ltd.) and dicumyl peroxide (Percumyl D, Nihon Yushi Co., Ltd.) as a polymerization initiator with respect to a mixture of 100 parts by mass in total. 1.0 mass part) was obtained, and curable silicone resin composition was obtained. Moreover, using the obtained curable silicone resin composition, it carried out similarly to Example 1, and obtained the silicone resin hardened | cured material.

(Example 3)

A curable silicone resin composition and a cured silicone resin composition were obtained in the same manner as in Example 1 except that the resin mixture II (basket-type silsesquioxane resin content: 50 mass%) obtained in Synthesis Example II was used instead of the resin mixture I.

(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 instead of the resin mixture I.

(Example 5)

A curable silicone resin composition and a cured silicone resin composition were obtained in the same manner as in Example 1 except that the resin mixture III (basket-type silsesquioxane resin content: 75% by mass) obtained in Synthesis Example III was used instead of the resin mixture I.

(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 instead of the resin mixture I.

(Example 7)

A curable silicone resin composition and a cured silicone resin composition were obtained in the same manner as in Example 1 except that the resin mixture IV (basket-type silsesquioxane resin content: 45 mass%) obtained in Synthesis Example IV was used instead of the resin mixture I.

(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 instead 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 instead 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 instead 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 instead 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 instead 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 formability, measurement of water absorption, measurement of linear expansion coefficient, and measurement of total light transmittance were performed with the following method.

(Evaluation of Film Formability)

The following standards by visually cracking of the silicone resin cured product:

Evaluation A: No cracks or breaks observed on the film

Evaluation B: Reticulated cracks or fractures were observed in the film

It evaluated according to. The obtained results are shown in Table 2.

(Measurement of Absorption Rate)

First, the obtained silicone resin hardened | cured material was hold | maintained at 50 degreeC for 24 hours, and predrying was performed. Then, the water absorption was measured based on the plastic-absorption method (JISK7209). The obtained results are shown in Table 2.

(Measurement of linear expansion coefficient)

About the obtained silicone resin hardened | cured material (5 mm x 5 mm x thickness 1 mm (five pieces of 0.2 mm thickness test pieces were piled), it measured on the basis of a thermomechanical analysis method using the instrument name: TMA4000SA (product made from BRUKER) (heating rate: 5 ° C / min, compressive load: 0.1N, temperature range: 50-150 ° C).

The coefficient of linear expansion is

Linear expansion coefficient (ppm / K) = displacement amount / temperature displacement amount per 1m of test piece

Lt; / RTI &gt; 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 light was measured using NDH2000 (made by Nippon Denshoku Corporation).

Transmittance is the following formula:

Total light transmittance (%) = transmitted light intensity / incident light intensity

Lt; / RTI &gt; The obtained results are shown in Table 2.

As is apparent from the results shown in Table 2, it was confirmed that all of the cured silicone resins obtained in Examples 1 to 8 had excellent transparency, moldability and low water absorption, and had a sufficiently small coefficient of linear expansion. On the other hand, it was confirmed that the silicone resin cured material obtained in Comparative Examples 1 and 2 had a high water absorption and a high linear expansion coefficient, and the silicone resin cured product obtained in Comparative Examples 3 and 4 was inferior in film formability.

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

As described above, the present invention can provide a curable silicone resin composition capable of obtaining a silicone resin cured product having excellent transparency, moldability and low water absorption, and having a sufficiently low coefficient of linear expansion, and a silicone resin cured product obtained by curing the same. Will be.

Such cured silicone resin is a transparent substrate such as a substrate for liquid crystal display device, a substrate for color filter, a substrate for organic EL display device, a substrate for electronic paper, a substrate for TFT, a solar cell substrate, a touch panel, a film with a transparent electrode, a light guide plate , Optical film applications such as protective films, polarizing films, retardation films, lens sheets, glass substitute materials for various transportation machines, housing window materials and the like, and their use ranges are extensive, and their industrial utility value is very high.

Claims (5)

(1): &lt; EMI ID =
_{[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-OR ^4- (2)
[In Formula (2), R <^3> represents a hydrogen atom or a methyl group, and R <^4> represents any 1 type selected from the group which consists of an alkylene group, an alkylidene group, and a phenylene group.]
Represents a group having a (meth) acryloyl group represented by 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)-(iv):
n≥1 (i),
m≥1 (ii),
j≥0 (iii),
n + m + j = h (iv)
[Wherein h represents any integer selected from the group consisting of 8, 10, 12 and 14]
Represents an integer that satisfies the condition indicated by, and when m and j are each 2 or more, R ¹ and R ² may be the same as or different from each other.
It contains cage silsesquioxane resin represented by the following, and a radical polymerization initiator,
Curable silicone resin composition whose content of the said cage silsesquioxane resin is 10-80 mass%. The method of claim 1,
Curable silicone in the said cage silsesquioxane resin WHEREIN: The ratio of the number of vinyl groups and the number of (meth) acryloyl groups (the total number of vinyl groups: the number of all (meth) acryloyl groups) is 1: 4-13: 1. Resin composition. 3. The method according to claim 1 or 2,
Curable silicone resin composition containing the unsaturated compound which has a (meth) acryloyl group further. 4. The method according to any one of claims 1 to 3,
Curable silicone resin composition whose content of the said radical polymerization initiator is 0.01-10 mass%. The silicone resin hardened | cured material obtained by radically polymerizing the curable silicone resin composition of any one of Claims 1-4.

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