JPH08127657A - Production of cured diphenylsiloxane and cured product - Google Patents

Abstract

PURPOSE: To obtain a diphenylsiloxane cured product useful as a siloxane-based material having improved processability while keeping the thermal stability, rigidity, electrical characteristics, etc., of the base resin by curing a diphenylsiloxane oligomer having both terminals terminated with specific functional groups. CONSTITUTION: A diphenylsiloxane oligomer of the formula [at least one of R<1> to R<3> and at least one of R<6> to R<8> are each H or a 2-10C (un)saturated hydrocarbon group (excluding phenyl and alkyl-substituted phenyl) and the remaining R<1> to R<3> and R<6> to R<8> groups are each methyl, phenyl, etc.; R<4> , R<5> , R<9> and R<10> are each an organic group; R<4> and R<5> or R<9> and R<10> are not phenyl at the same time; (m) is 1-50; (k) and (n) are each 0-3] is cured in the presence of a catalyst for curing, in the presence of a polymerization initiator or a polymerization catalyst or in the absence of a curing catalyst and polymerization initiator under heating or irradiation with light. Concretely, a hexaphenyltrisiloxane having both terminals terminated with (4-vinylphenyl) dimethylsilyl groups is heated at 300 deg.C for 2min to effect the curing of the siloxane by polymerization reaction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cured product containing diphenylsiloxane as a main component and a method for producing the same. The curable synthetic resin composition of the present invention has high heat resistance, high transparency, and a critical value of a certain value or more when heated at a temperature between 50 ° C. and 500 ° C. or irradiated with ultraviolet rays at a temperature of 300 ° C. or lower. A cured product having surface tension can be formed.

[0002]

2. Description of the Related Art Polydiphenylsiloxane is a white crystalline polymer having excellent thermal stability and has a high flexural modulus of 4.4 GPa at room temperature. Diphenyl siloxane homopolymer is also a polymer having excellent electrical properties such as low hygroscopicity, high insulation and low dielectric constant.

However, when the degree of polymerization of diphenylsiloxane homopolymer exceeds about 50, the solubility thereof is extremely lowered, and only a small amount is dissolved in a solvent such as diphenyl ether, terphenyl or dichlorobenzene heated to a high temperature. Casting from solution is virtually impossible.

At temperatures below 260 ° C. this polymer is
Since it has high crystallinity and is brittle, it lacks moldability. At about 260 ° C, the crystalline phase transitions to the intermediate phase, but the intermediate phase also has poor fluidity and exhibits fluidity at a temperature above the melting point at about 500 ° C, but at the same time, thermal decomposition of the polymer also starts, There is no temperature range in which molding can be performed. As described above, the polydiphenylsiloxane homopolymer is a material having extremely poor workability in terms of processability.

Polydiphenylsiloxane homopolymer is a material having a high elastic modulus, but its strength is extremely low and it is unsuitable as a structural material. In addition, it is cloudy due to its high crystallinity, and has poor light transmittance. As described above, the diphenylsiloxane homopolymer has good processability, mechanical properties,
It is a material with poor practicability in any of its optical characteristics.

As a more general siloxane material,
There are polydimethylsiloxane, polymethylphenylsiloxane, dimethylsiloxane-diphenylsiloxane copolymer, dimethylsiloxane-methylphenylsiloxane copolymer, etc., but these polymers having an essentially low glass transition temperature are soft at room temperature or high temperature and have a rubber behavior. Present. Also, the methyl group bonded to silicon has lower thermal stability than the phenyl group bonded to the silicic group,
Therefore, there is a problem in use at high temperature. Another drawback of these siloxanes is the formation of volatile by-products, and cyclic oligomers such as trimers, tetramers, etc., which are produced during the production of raw materials or during the curing reaction, have volatility, resulting in insulation at contacts. In particular, there is a problem in electric material applications at high temperatures.

[0007]

Polydiphenylsiloxane is a polymer having excellent properties such as thermal stability and electrical properties. However, as described above, the homopolymer of this polydiphenylsiloxane has very poor processability represented by solubility and melting characteristics and flowability in the mesophase state, and also has brittleness and low light due to high crystallinity. There is a problem with transparency. Therefore, it is an object of the present invention to provide an industrially useful material by imparting processability while maintaining the advantages of the present polymer, that is, thermal stability, rigidity, electrical characteristics, and the like.

[0008]

The present inventors have conducted research on oligomers and homopolymers of polydiphenylsiloxane and found the following facts which are the basis of the present invention. That is, when the degree of polymerization n of the polymer is about 50 or less, the relationship between the degree of polymerization of the polymer and its melting point is shown in FIG.
Therefore, the melting point of the polymer can be selected from room temperature to 500 ° C. by appropriately selecting the degree of polymerization n. It has also been found that at temperatures above the melting point, these polymers exhibit good flowability when the degree of polymerization n is below about 50. As mentioned above, diphenylsiloxane has very high heat resistance,
Sufficiently withstands processing at temperatures near 0 ° C.

Further, the degree of polymerization n has a certain correlation with the solubility of the present polymer in an organic solvent, and although the influence of the terminal group cannot be ignored, a polymer having n of about 3 to 6 can be used in most organic solvents at room temperature. Soluble in n, from about 7 to 11
The oligomer at the position is soluble in a polar solvent such as tetrahydrofuran, chloroform, dimethylsulfoxide or the like at room temperature, and is also dissolved in an aromatic organic compound such as benzene or toluene by some heating. When the degree of polymerization is about 12 to 18, a solvent such as hot toluene, hot xylene or hot tetrahydrofuran, hot chloroform, hot N-methylpyrrolidone is required. The polymer having a degree of polymerization higher than this is almost insoluble in a general organic solvent, but up to a degree of polymerization of about 50, a polar high boiling point organic solvent such as phenyl ether, orthotorphenyl, N, N-.
It can be dissolved in dimethylformamide, etc. at a high temperature of 150 ° C or higher.

The present inventors have also proposed a synthetic technique in which a reactive functional group is introduced into both ends of a polydiphenylsiloxane having a degree of polymerization of about 50 or less (hereinafter, this type of polydiphenylsiloxane is referred to as a diphenylsiloxane oligomer). Developed (Japanese Patent Application No. 6-52009 and 6-52010), these diphenylsiloxane oligomers having reactive functional groups at both ends are basically similar in melting and dissolution behavior to the above diphenylsiloxane. Was confirmed.

The diphenylsiloxane oligomer having reactive functional groups at both ends can be produced as follows. That is, a cyclic trimer of diphenylsiloxane (hexaphenylcyclotrisiloxane) is converted into R ¹¹ R ¹² R ¹³ Si (O
_{^{R 14 R 15 Si) s O}} - Li + ( wherein ^{R 11, R 12, R 13} ,
At least one substituent of R ¹⁴ and R ¹⁵ is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 2 to 10 carbon atoms (excluding phenyl group and alkyl-substituted phenyl group having 7 to 10 carbon atoms). And the remainder is a methyl group, a phenyl group or an alkyl-substituted phenyl group having 7 to 10 carbon atoms, and two of R ¹¹ , R ¹² and R ¹³ jointly form a cyclic hydrocarbon. Also, 0 ≦ s ≦ 3)
Is polymerized by a ring-opening reaction using lithium silanolate as an initiator, and new lithium silanolate thus produced is converted into R ¹⁶ R ¹⁷ R ¹⁸ Si (OR ¹⁹ R ²⁰ Si) _t
X (wherein R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , and R ²⁰ are defined in the same manner as R ^{11 to} R ¹⁵ and 0 ≦ t ≦ 3, and X is a halogen selected from chlorine, bromine, and iodine. Group, or an acyloxy group represented by an acetoxy group and a propoxy group.

The present inventors have further extended the above-mentioned investigation of melting and dissolution behavior to polydiphenylsiloxane having more diverse functional groups partially having hetero atoms such as oxygen, nitrogen, and sulfur to obtain diphenyl By researching the excellent processability of the siloxane oligomer and the reactivity of the above functional groups, the invention relating to a composition which gives a cured product containing diphenylsiloxane as a main component was completed.

The diphenylsiloxane oligomer having a reactive functional group partially having a hetero atom such as oxygen, nitrogen and sulfur at both ends can be produced as follows. That is, the first method is to introduce a functional olefin or a functional acetylene into a diphenylsiloxane oligomer having a SiH group at a part of both ends by hydrosilylation reaction. As functional acetylene, allyl glycidyl ether, allyl methacrylate, allyl acrylate,
Examples include allylamine, N-methylallylamine, N-trimethylsilylallylamine, allyl chloride, isobutenyl chloride, propargyl methacrylate, propargyl acrylate and the like. SiH on a part of both ends
As the diphenylsiloxane oligomer having a group,
1,1,3,3,5,5-hexaphenyltrisiloxane, 1,1,3,3,5,5,7,7,9,9-decaphenylpentasiloxane, 1,3,3,5,5 5, 7,
Diphenylsiloxane oligomers consisting only of phenyl groups and Si-H groups, represented by 7,9-octaphenylpentasiloxane, 1,1,9,9-tetramethyl-3,3,5,5,7,7- Hexaphenylpentasiloxane, 1,1,13,13-tetramethyl-
3,3,5,5,7,7,9,9,11,11-decaphenylheptasiloxane, a diphenylsiloxane oligomer having a phenyl group as a substituent and a dimethylhydrogensiloxy group, 1,9- Diphenylsiloxane oligomers having functional groups other than SiH and phenyl groups such as diethyl-1,3,3,5,5,7,7,9-octaphenylpentasiloxane can be exemplified. In order to carry out the hydrosilylation reaction of the present method, a hydrosilylation reaction catalyst represented by a platinum compound, a rhodium compound, a nickel compound and the like can be added to the above raw materials and this can be carried out.

As a second method, there can be mentioned a method in which a specific cyclic silicon compound is allowed to act on a silanol functional diphenylsiloxane oligomer having both terminals. In this case, the diphenylsiloxane oligomer is 1,1,1.
3,3,5,5-hexaphenyltrisiloxane-1,
5-diol, 1,1,3,3,5,5,7,7,9,
An oligomer such as 9-decaphenylpentasiloxane-1,9-diol can be exemplified, and the cyclic silicon compound is 1,2,2,4-tetramethyl-1-aza-2-silacyclopentane, 1-phenyl- Into 1-isopropenyl-2,2-dimethyl-1-aza-2-silacyclopentane, which can introduce an aminoalkyl group represented by 2,2,3-trimethyl-1-aza-2-silacyclobutane, Representative ones capable of introducing an amide-modified alkyl group, 2,2-dimethyl-1-oxa-2-silacyclopentane, 2,2-dimethyl-1-thia-2-silacyclopentane, 2,2,4 -Trimethyl-5-oxo-1-
Examples thereof include oxa-2-silacyclopentane and the like, into which a hydroxyalkyl group, a mercaptoalkyl group and a carboxyalkyl group can be introduced, respectively. In this method, a diphenylsiloxane oligomer having a reactive functional group can be produced by bringing the diphenylsiloxane oligomer into contact with the above cyclic silicon compound or in the presence of a small amount of an acid or base catalyst.

In the third method, a silane compound having a reactive functional group is allowed to act on a silanol functional diphenylsiloxane oligomer having terminals at both ends, as in the second method. Eg 3
In addition to functional alkyl groups such as aminopropyl group, 3- (methacryloxy) propyl group and 3- (glycidoxy) propyl group, it has reactive substituents such as chloro, acetoxy group and methoxy group. Specifically 3-
(Methacryloxy) propyldimethylchlorosilane, 3
Examples thereof include- (glycidoxy) propyldimethylmethoxysilane.

The fourth method is a method of producing an oligomer having a new reactive functional group by reacting an existing diphenylsiloxane oligomer having a reactive functional group, which comprises a diphenylsiloxane oligomer having a chloropropyl group and an alkylamine. Production of oligomer having 3- (N-alkylamino) propyl group by reaction, production of oligomer having amide group by reaction of diphenylsiloxane oligomer having aminopropyl group and acyl chloride, diphenyl having N-methylaminopropyl group A method for producing an oligomer having an ester group by a Michael addition reaction between a siloxane oligomer and an acrylate compound can be exemplified.

The present invention is a diphenylsiloxane which causes a curing reaction of a diphenylsiloxane oligomer represented by the following formula (1) by heating or light irradiation under conditions selected from the following (i), (ii) and (iii). It is a method for producing a cured product.

[0018]

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(In the formula, at least one substituent of R ¹ , R ² and R ³ and at least one substituent of R ⁶ , R ⁷ and R ⁸ is a hydrogen atom or a carbon atom of 2 to 2). 10 saturated or unsaturated hydrocarbon groups which may contain a hetero atom selected from nitrogen, oxygen, sulfur and silicon (excluding phenyl group and alkyl-substituted phenyl group), and R ¹ , R ² and R ³ may together form a cyclic hydrocarbon, and R ⁶ , R ⁷ and R ⁸ are the same as R ¹ , R ² and R ³ ,
The remaining groups of R ¹ , R ² , R ³ , R ⁶ , R ⁷ , and R ⁸ , if any, are methyl groups, phenyl groups, or alkyl-substituted phenyl groups having 7 to 10 carbon atoms; ⁴ and R ⁵
Is an organic group and does not become a phenyl group at the same time,
R ⁹ and R ¹⁰ are organic groups and cannot be phenyl groups at the same time; 1 ≦ m ≦ 50; k and n are independently 0 ≦
k ≦ 3, 0 ≦ n ≦ 3) (i) In the presence of a curing catalyst, (ii) In the presence of a polymerization initiator or a polymerization catalyst, (iii) In the absence of a curing catalyst and a polymerization initiator. under.

When the curing reaction in the production method of the present invention is a polymerization reaction, the diphenylsiloxane oligomer can be roughly divided into three types of curing depending on the type of the substituent. First, in the diphenylsiloxane oligomer represented by the formula (1), at least one of R ¹ , R ² , and R ³ is an organic group having a polymerization-reactive unsaturated group,
And at least one of R ⁶ , R ⁷ and R ⁸ may have a polymerizable reactive unsaturated group. In this case, R ¹
The remaining groups to R ³ and R ⁶ to R ^8, if any, methyl group, phenyl group or an alkyl-substituted phenyl group having 7 to 10 carbon atoms, for example tolyl group, xylyl group, can be a ethylphenyl .

Examples of the polymerization-reactive unsaturated group include:
Vinyl group, allyl group, propenyl group, isopropenyl group, crotyl group, hexenyl group, alkenyl group and other alkenyl groups having 2 or more carbon atoms, ethynyl group, propynyl group,
Propargyl group, butynyl group, alkynyl group represented by phenylethynyl group, 4-vinylphenyl group, 3-vinylphenyl group, 4-vinylbenzyl group, 3-vinylbenzyl group, β- (4-vinylphenyl) ethyl group Examples thereof include styrene-based substituents, acryloyl, methacryloyl, acrylamide, methacrylamide, diacrylamide, dimethacrylamide, and the like.

The compound (1) can be cured by the polymerization in air or in an inert atmosphere, and a method selected from the following three methods can be used. That is, the first method is to irradiate ultraviolet rays at a temperature of 300 ° C. or lower. The second method is to add a polymerization initiator and polymerize at a temperature of 20 ° C to 500 ° C. The third method is to heat at a temperature of 100 ° C to 500 ° C without adding a polymerization initiator. In the first method, it is desirable to add a photopolymerization initiator, and examples of the initiator include benzophenone-based compounds and benzoin-based compounds, and the addition amount is appropriately 0.1 to 10% by weight. . In the case of a thermal reaction, a temperature range of 150 ° C to 500 ° C is more suitable, and when a polymerization initiator or a polymerization catalyst is used, a temperature range of 50 to 500 ° C is optimum. Examples of the polymerization initiator include azo compounds represented by azobisisobutyronitrile, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and peroxides such as dicumyl peroxide. 0.1 to 5% by weight is suitable.

Secondly, in the diphenylsiloxane oligomer represented by the formula (1), at least two substituents of R ¹ , R ² and R ³ are connected to each other to form a trimethylene group or a substituted trimethylene group, and thus sila. It forms a cyclobutane structure, and R ⁶ , R ⁷ and R ⁸ may be the same as R ¹ , R ² and R ³ . In this case, the remaining groups of R ^{1 to} R ³ and R ^{6 to} R ⁸ are methyl group, phenyl group or alkyl-substituted phenyl group having 7 to 10 carbon atoms, if any, such as tolyl group, xylyl group, It can be an ethylphenyl group.

A catalyst selected from platinum compounds and rhodium compounds can be used in the crosslinking reaction or chain extension reaction of those having a functional group of silacyclobutane structure. The proper addition amount is 0.1 ppm to 100 ppm.
The optimum reaction temperature and reaction time are correlated, but in order to obtain a cured product in a short time, 1 at a temperature of 80 ° C or higher and 300 ° C or lower.
It is desirable to heat in the range from minutes to 2 hours.

Thirdly, in the diphenylsiloxane oligomer represented by the formula (1), at least one of R ¹ , R ² and R ³ is an epoxy group-containing alkyl group, alkenyl group or aryl group, and R ⁶ , At least one of R ⁷ and R ⁸ may be an alkyl group containing an epoxy group, an alkenyl group, or an aryl group. In this case, the remaining groups among R ^{1 to} R ³ and R ^{6 to} R ⁸ are methyl groups, if any,
It may be a phenyl group or an alkyl-substituted phenyl group having 7 to 10 carbon atoms, such as a tolyl group, a xylyl group, an ethylphenyl group.

For the polymerization of the epoxy group-containing oligomer, tertiary amines such as benzyldimethylamine, triethanolamine, triethylenediamine and diazacycloundecene, an amine complex of boron fluoride, or diphenyliodonium of HA _s F ₆ is used. Salts can be used as catalysts. Addition amount is 1 to 10% by weight, 50
It is desirable to heat and cure at a temperature between ˜200 ° C. for 0.1 to 10 hours.

The curing reaction in the production method of the present invention is an oxidation.
In the case of a reaction-based siloxane formation reaction, the formula (1)
In the diphenyl siloxane oligomer represented by
R¹, R², R³At least one of them is a hydrogen atom,
Chain or branched saturated hydrocarbon group, alkenyl group,
Alkyl group, aralkyl group and R¹, R², R³Of 2
Two substituents are bonded to each other to form a trimethylene group, tetramethyl group.
Silacyclo structure selected from len group and pentamethylene group
R is a kind selected from those that form a structure. ⁶,
R⁷, R⁸Also R¹~ R³Is defined in the same way as
sell. These groups may participate in the above oxidation reaction. This place
R¹~ R³, R⁶~ R⁸If the rest of the groups are
For example, a methyl group, a phenyl group or an alkyl group having 7 to 10 carbon atoms.
Alkyl substituted phenyl group such as tolyl group, xylyl group,
It can be an ethylphenyl group.

Examples of the functional group capable of participating in the siloxane-forming reaction based on the above-mentioned oxidation reaction include a hydrogen atom, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group,
Saturated n-alkyl group represented by n-hexyl group, n-heptyl group, n-octyl group; isopropyl group, se
c-butyl group, 2-methylpropyl group, t-butyl group,
A saturated branched alkyl group represented by isopentyl group, sec-hexyl group and 2-ethylhexyl group; vinyl group,
Allyl group, propenyl group, isopropenyl group, crotyl group, hexenyl group, alkenyl group such as octenyl group, or ethynyl group, propynyl group, propargyl group, butynyl group, alkynyl group represented by phenylethynyl group, or benzyl group, An aralkyl group such as a phenethyl group, and among R ¹ , R ² and R ³ , R ⁶ , R ⁷ and
Examples of R ⁸ include those in which two substituents are connected to each other to form a silacyclo structure, such as a trimethylene group, a tetramethylene group, and a pentamethylene group.

In the present invention, what is important in the selection of the functional group that forms a siloxane bond by the oxidation reaction (easily oxidizable functional group) and the crosslinking reaction condition (that is, the oxidation reaction condition) is that the easily oxidizable functional group is under the crosslinking reaction condition. In, it is easily oxidized as compared with a phenyl group bonded to silicon. As is generally well known, the order of oxidation resistance stability of a hydrocarbon group bonded to silicon by silicone is phenyl group >> methyl group> vinyl group> other alkyl group (p.530). , L. H. Brown, Trea
Tise on coatings, vol. 1, Pa
rt III "Film-Forming Compos
editions ", Ed.RR Myers and
J. S. Long, Published by Mar
cel Dekker, Inc. , New York,
1972) When the substituent is a functional group which is easily oxidized as described above, the polymer molecule is heated in air at a temperature of 250 ° C. or higher for 1 second to 5 hours so that the silicon-phenyl bond is not damaged. The functional group can be oxidized to cure the copolymer. The optimum reaction temperature and reaction time are correlated, but it is desirable to heat at a temperature of 300 ° C. or higher and 450 ° C. or lower for 1 minute to 2 hours in order to obtain a cured product in a short time.

The curing reaction in the production method of the present invention may be an addition reaction or a condensation reaction via a crosslinking agent or a chain extender.

When the curing reaction in the production method of the present invention is an addition reaction for forming crosslinks between the polymer molecules represented by the general formula (1), the curing can be roughly divided into three types according to the kind of the substituent. . First, at least one of R ¹ , R ² and R ³ and at least one of R ⁶ , R ⁷ and R ⁸ is an alkenyl or alkynyl unsaturated hydrocarbon group, and A compound (crosslinking agent or chain extender) having two or more hydrogen atoms (Si-H) directly bonded to silicon in one molecule and a catalyst for addition reaction can be added to the united molecule. The remaining groups of R ^{1 to} R ³ and R ^{6 to} R ⁸ are a methyl group, a phenyl group or a carbon number of 7 to 1
It can be 0 alkyl-substituted phenyl groups. General formula (1)
Examples of the polymer represented by the following are those in which at least one of R ¹ , R ² and R ³ and at least one of R ⁶ , R ⁷ and R ⁸ is an alkenyl group or an alkynyl group:
1,1,9,9-tetraallyl-1,9-dimethyl-
3,3,5,5,7,7-hexaphenylpentasiloxane, 1,9-divinyl-1,1,9,9-tetramethyl-3,3,5,5,7,7-hexaphenylpentasiloxane , 1,5-divinyl-1,1,3,3,5,5
-Hexaphenyltrisiloxane, 1,9-di (vinylphenyl) -1,1,9,9-tetramethyl-3,3,3
Examples include 5,5,7,7-hexaphenylpentasiloxane. As a cross-linking agent or chain extender, 1,
1,3,3-tetramethyldisiloxane, 1,3,5
In addition to methyl hydrogen siloxane compounds represented by 7-tetramethylcyclotetrasiloxane, diphenyl siloxane oligomers 1, 1, 3, 3, 5,
Examples thereof include 5-hexaphenyltrisiloxane and 1,9-dimethyl-3,3,5,5,7,7-hexaphenylpentasiloxane. Here, the chain extender may be the compound of the above formula (1).

The molar ratio of SiH groups to alkenyl and / or alkynyl unsaturated groups in the composition is 0.5.
Any value between and 2.0 can be used. The curing reaction atmosphere may be air or an inert atmosphere, and the reaction is carried out in the presence of a hydrosilylation reaction catalyst represented by platinum compounds and rhodium compounds. A suitable amount of catalyst is between 0.1 ppm and 100 ppm. A cured product is obtained by heating from 50 ° C. to 350 ° C. in the presence of this catalyst. The optimum reaction temperature and reaction time are correlated,
In order to obtain a cured product in a short time, it is desirable to heat at a temperature of 100 ° C. or higher and 300 ° C. or lower for 1 minute to 2 hours.

Secondly, the polymerization represented by the above general formula (1)
The reaction that forms cross-links between body molecules is an addition reaction,
R¹, R², R³At least one of the
R⁶, R⁷, R⁸At least one of is a hydrogen atom
In this case, at least 2 in each molecule of the polymer
Having an alkenyl and / or alkynyl unsaturated group of
Can be added as a crosslinker or chain extender.
it can. The R¹~ R³And R ⁶~ R⁸The rest of the groups are
Cyl group, phenyl group or alkyl having 7 to 10 carbon atoms
It can be a substituted phenyl group. Weight represented by general formula (1)
R of combined molecule¹R²R³As a silyl group represented by Si
Is dimethylsilyl group, methylsilyl group, trihydrogen
Phenylsilyl group, phenylsilyl group, methylethylsilyl
Group, diethylsilyl group, ethylsilyl group, propylsilyl group
And the like. With cross-linking agent or chain extender
1,5-pentadiene, 1,
Tiredness represented by 6-hexadiene and divinylbenzene
Japanese hydrocarbon compounds and 1,3-divinyl-1,1,
3,3-tetramethyldisiloxane, 1,3,5-tri
Vinyl-1,3,5-trimethylcyclotrisiloxane
In addition to vinyl group-substituted siloxane compounds represented by
In the polymer molecule represented by the general formula (1), R is¹, R², R³of
At least one of the⁶, R⁷, R⁸Within
At least one is alkenyl group or alkynyl group
Is, for example, 1,1,9,9-tetraallyl-
Include 1,9 dimethyl hexaphenyl pentasiloxane
Can be

The molar ratio of SiH groups to alkenyl and / or alkynyl unsaturated groups in this composition is 0.
Any value between 5 and 2.0 is acceptable. The curing reaction atmosphere may be air or an inert atmosphere, and the reaction is carried out by heating for 1 second to 5 hours in the presence of a hydrosilylation reaction catalyst represented by a platinum compound and a rhodium compound.
A suitable amount of catalyst is between 0.1 ppm and 100 ppm. A cured product is obtained by heating a mixture of polymer molecules, a cross-linking agent, and a catalyst at 50 ° C to 350 ° C. The optimum reaction temperature and reaction time are correlated, but it is desirable to heat at a temperature of 100 ° C. or higher and 300 ° C. or lower for 1 minute to 2 hours in order to obtain a cured product in a short time.

As the hydrosilylation catalyst used in the present invention, chloroplatinic acid, platinum (0) vinyl siloxane complex and platinum supported on activated carbon are used for platinum compounds, and tristriphenylphosphine rhodium (I) chloride is used for rhodium compounds.
Examples thereof include a dimer of (1,5-cyclooctadiene) rhodium (I) chloride, but generally any platinum or rhodium compound having catalytic activity in the hydrosilylation reaction may be used.

Thirdly, in the above formula (1), R ¹ ,
At least one of R ² and R ³ is an organic group having an epoxy group, an organic group having an amino group, an organic group having a substituted amino group, an organic group having a carboxyl group, an organic group having a hydroxyl group, and a mercapto group. Having an organic group, is a kind selected from an organic group having an isocyanate group and an organic group having a vinyl group, the crosslinking agent or chain extender is an epoxy group reactive with the group, an amino group, a substituted amino group, It may have at least two functional groups selected from a carboxyl group, a hydroxyl group, a mercapto group, an isocyanate group and a vinyl group in one molecule.

The diphenylsiloxane oligomer having an epoxy group at the terminal is mixed with a curing agent having at least two amino groups in one molecule, which is represented by ethylenediamine, diethylenetriamine and triethylenetetramine, and is mixed at a temperature of 100 to 250 ° C. It can be cured by heating for 10 minutes to 20 hours. The ratio of the diphenylsiloxane oligomer to the curing agent in this case is not particularly limited as long as a cured product is obtained, but it usually depends on the molar ratio of each functional group, although it depends on the number of functional groups contained in the crosslinking agent. 0.5: 1 to 1: 0.5, more preferably 0.8: 1 to 1: 0.8 is suitable as a standard.

When the terminal functional group of the diphenylsiloxane oligomer is an amino group such as aminopropyl or a substituted amino group represented by N-methylaminopropyl group, it has a plurality of epoxy groups such as polyglycidylamine type. A cross-linking agent or a cross-linking agent having a plurality of isocyanate groups such as hexamethylene diisocyanate and toluylene diisocyanate is heated at a temperature of 100 to 250 ° C. for 10 minutes to 20 hours to cause an addition reaction, thereby obtaining a cured product. You can The ratio of the diphenylsiloxane oligomer to the curing agent in this case is not particularly limited as long as a cured product is obtained, but it usually depends on the molar ratio of each functional group, although it depends on the number of functional groups contained in the crosslinking agent. 0.5: 1 to 1: 0.5 based on
More preferably, 0.8: 1 to 1: 0.8 is suitable.
Similarly, by using a diphenylsiloxane oligomer having an amino group as a terminal group, a cross-linking agent having a plurality of chlorocarbonyl groups such as phthalic acid chloride, or a cross-linker having a plurality of carboxylic acid anhydride functional groups represented by pyromellitic acid anhydride. A heating reaction with the agent at a temperature of 50 to 300 ° C. for 10 minutes to 20 hours causes a condensation reaction, whereby a cured product can be obtained. The amount ratio of the diphenylsiloxane oligomer to the curing agent in this case is not particularly limited as long as a cured product is obtained, but it usually depends on the number of functional groups in the crosslinking agent, but usually the molar ratio of each functional group is 0.5: 1 to 1: 0.5, and more preferably 0.8: 1 to 1: 0.8 is suitable.

The terminal functional group of the diphenylsiloxane oligomer is a carboxyl group (for example, --CH ₂ CH ₂ CH ₂
In the case of COOH), a cross-linking agent having at least two amino groups in one molecule, represented by ethylenediamine, diethylenetriamine and triethylenetetramine, or a plurality of hydroxy groups represented by ethylene glycol and pentaerythritol is used. A condensation reaction is caused by heating at a temperature of 100 to 300 ° C. for 10 minutes to 20 hours together with the cross-linking agent, and thereby a cured product can be obtained. The amount ratio of the diphenylsiloxane oligomer to the curing agent in this case is not particularly limited as long as a cured product is obtained, but it usually depends on the number of functional groups in the crosslinking agent, but usually the molar ratio of each functional group is Based on 0.5: 1 to 1: 0.5, more preferably 0.8: 1
Approximately 1: 0.8 is suitable.

When the terminal functional group of the diphenylsiloxane oligomer is a hydroxy group such as hydroxypropyl, it is mixed with a crosslinking agent having a plurality of isocyanate groups such as hexamethylene diisocyanate and toluylene diisocyanate at a temperature of 100 to 250 ° C. for 10 minutes. By heating for about 20 hours, an addition reaction occurs, whereby a cured product can be obtained. In this case, it is appropriate that the molar ratio of the diphenylsiloxane oligomer and the curing agent is such that the molar ratio of each functional group is about 1: 1. Similarly, using a diphenylsiloxane oligomer having a hydroxy group as an end group, it has a cross-linking agent having a plurality of chlorocarbonyl groups such as phthalic acid chloride, or a plurality of carboxyl groups represented by terephthalic acid, adipic acid, and pyromellitic acid. 10 minutes to 20 at a temperature of 50 to 250 ° C. with a crosslinking agent
A heating reaction causes a condensation reaction, whereby a cured product can be obtained. The amount ratio of the diphenylsiloxane oligomer to the curing agent in this case is not particularly limited as long as a cured product is obtained, but it usually depends on the number of functional groups in the crosslinking agent, but usually the molar ratio of each functional group is 0.5: 1 to 1: 0.5, and more preferably 0.8: 1 to 1: 0.8 is suitable.

When the terminal functional group of the diphenylsiloxane oligomer is a mercapto group such as mercaptopropyl, 1,6-hexadiene, divinylbenzene, 1,
Addition reaction is caused by ultraviolet irradiation in the presence of a crosslinking agent having a plurality of alkenyl groups, represented by 3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane. As a result, a cured product can be obtained. The amount ratio of the diphenylsiloxane oligomer to the curing agent in this case is not particularly limited as long as a cured product is obtained, but it usually depends on the number of functional groups in the crosslinking agent, but usually the molar ratio of each functional group is Based on 0.5: 1 to 1: 0.5, more preferably 0.8: 1 to
1: 0.8 is suitable.

When the terminal functional group of the diphenylsiloxane oligomer is an isocyanate group such as isocyanatopropyl, a temperature of 50 to 200 ° C. is used together with a crosslinking agent having a plurality of amino groups represented by ethylenediamine, diethylenetriamine and triethylenetetramine. Heating for 10 minutes to 20 hours causes an addition reaction, whereby a cured product can be obtained. The amount ratio of the diphenylsiloxane oligomer to the curing agent in this case is not particularly limited as long as a cured product is obtained, but it usually depends on the number of functional groups in the crosslinking agent, but usually the molar ratio of each functional group is 0.5: 1 to 1: 0.5 based on
More preferably, 0.8: 1 to 1: 0.8 is suitable.

When the terminal functional group of the diphenylsiloxane oligomer is an alkenyl group such as a vinyl group or an allyl group, a crosslink having a plurality of mercapto groups represented by trimethylolpropane tris- (β-thiopropionate). UV irradiation in the presence of an agent causes an addition reaction, whereby a cured product can be obtained. The amount ratio of the diphenylsiloxane oligomer to the curing agent in this case is not particularly limited as long as a cured product is obtained, but it usually depends on the number of functional groups in the crosslinking agent, but usually the molar ratio of each functional group is 0.5: 1 to 1: based on
0.5, more preferably 0.8: 1 to 1: 0.8 is suitable.

In the polymer molecule represented by the above general formula (1), R ⁴ and R ⁵ are organic groups and do not become phenyl groups at the same time. One or both of them are R ¹ , R ² and R ³ . An organic group similar to at least one of epoxy group, amino group, substituted amino group, carboxyl group, hydroxyl group,
It may contain either a mercapto group or an isocyanate group. R ⁹ and R ¹⁰ are organic groups and do not become phenyl groups at the same time, and one or both of them is R ⁶ , R
An organic group similar to at least one of ⁷ and R ⁸ and containing any of an epoxy group, an amino group, a substituted amino group, a carboxyl group, a hydroxyl group, a mercapto group and an isocyanate group may be used.

Generally, a resin containing dimethylsiloxane as a main component has a lower critical surface tension than that of a surface of a base material such as a general polymer or glass, compatibility with the polymer, a polymer product,
It has the drawback of poor paintability and adhesion to the surface of glass or the like. The critical surface tension of the cured product of the present invention can be calculated using the measured value of the contact angle of the organic liquid such as ethylene glycol, dimethyl sulfoxide, 2-ethoxyethanol, and dimethylformamide with the surface of the cured product. The main factor that determines the critical surface tension of the cured product of the present invention is the critical surface tension of a homopolymer of diphenylsiloxane (about 27 mN
/ M) and the contribution of the polymerization or condensate portion of the crosslinkable functional group, but when the latter is a non-polar component such as a silacyclobutane ring-opening polymer, it is slightly lower than diphenylsiloxane homopolymer, while acrylic or When it is composed of a polar component represented by a polymer of a methacrylic group or a condensate of an epoxy group and an amino group, it has a slightly higher critical surface tension than a diphenylsiloxane homopolymer. The cured product of the present invention preferably has a critical surface tension of 26 mN / m or more.

[0046]

EFFECTS OF THE INVENTION According to the present invention, a cured product containing diphenylsiloxane as a main component can be produced by a crosslinking reaction between diphenylsiloxane oligomers whose both ends are terminated with specific functional groups. Unlike the conventionally known diphenylsiloxane homopolymer, the diphenylsiloxane oligomer used in the present invention is soluble in a wide range of organic solvents,
In addition, since it exhibits meltability at a temperature of 500 ° C. or less, it becomes possible to perform molding by a method used for processing a polymer such as casting, a solution using a solution, injection, press working, etc. By the cross-linking reaction involving both terminal functional groups, it is possible to produce a cured product of diphenylsiloxane.

[0047]

The present invention is described in detail below with reference to examples and reference examples, but the present invention is not limited to these. 1H-NMR, 13C {1H} -NMR, 29 in the description of product characterization in the examples shown below.
Si {1H} -NMR represents a proton nuclear magnetic resonance spectrum, a carbon-13 nuclear magnetic resonance spectrum (proton decouple), and a silicon 29 nuclear magnetic resonance spectrum (proton decouple), respectively. CDCl ₃ represents deuterated chloroform, and s, d, t, m, d shown in () in the proton nuclear magnetic resonance spectrum data display.
d, tt, and br represent singlet, doublet, triplet, multiplet, doublet doublet, triplet triplet, and broad (wide width), and 1H, 2H, 3H, etc. are 1, 2, 3 and 3, respectively. It means the spectrum intensity corresponding to the individual pieces. J indicates a spin-spin coupling constant (unit: Hertz). All the chemical shifts in the 1H-NMR spectrum are values when the resonance position of residual CHCl ₃ in the CDCl ₃ solvent is 7.24 ppm. 13C-NMR
In the spectrum, the carbon chemical shift of CDCl ₃ is 7
It is a value when it is 7.0 ppm. The chemical shift of 29 Si-NMR spectrum is a value in which the chemical shift of silicon of tetramethylsilane (CDCl ₃ solution) as an external standard is 0 ppm. GLC is for gas chromatography, GC-MS is for gas chromatography-mass spectrometry,
PC stands for gel permeation chromatograph.

Reference Example 1 (Starting terminal lithium (n-
Synthesis of butyldimethylsilanolate) 20 parts of tetrahydrofuran in a reaction vessel purged with nitrogen,
15.8 parts of hexamethylcyclotrisiloxane were added, and then 44 parts of 1.72 mol / L hexane solution of n-butyllithium was added, and this was stirred for 5 minutes and lithium n-
Butyl dimethyl silanolate was prepared.

Reference Example 2 (Starting terminal lithium (n-
Synthesis of butylmethylvinylsilanolate)) A three-necked flask equipped with a dropping funnel and a water-cooled condenser was added with a magnetic stirrer, 20 parts of tetrahydrofuran, 18 parts of trimethyltrivinylcyclotrisiloxane, and then 47 parts of 1 A hexane solution of n-butyllithium (0.72 mol / L) was added and stirred for 30 minutes to prepare lithium (n-butylvinylmethylsilanolate).

Reference Example 3 (Initial terminal lithium (n-
Synthesis of butyldiethylsilanolate) A three-necked flask equipped with a dropping funnel and a water-cooled condenser was added with a magnetic stirrer, 20 parts of tetrahydrofuran, 22 parts of hexaethylcyclotrisiloxane, and then 45 parts of 1.72. A mol / L n-butyllithium hexane solution was added and stirred for 30 minutes to prepare lithium (n-butyldiethylsilanolate).

(Reference Example 4) (Synthesis of oligo (diphenylsiloxane) terminated with butyldimethylsilyl group at one end and dimethylsilyl group at the other end) 12 parts of hexaphenyltrisiloxane and 12 parts of diphenylether were heated to 160 ° C. under argon, and The lithium silanolate prepared in Reference Example 1 was added so that the ratio of silanolate to diphenylsiloxane group was 1:17, and the mixture was reacted for 40 minutes. To this, 3 equivalents of dimethylchlorosilane was added and heated for 10 minutes. After the reaction solution was cooled to room temperature, 200 parts of methanol was added and the resulting precipitate was added to 20
It was washed with 0 part of acetone and dried to obtain 8.9 parts of a butyldimethylsilyl group-dimethylsilyl group-terminated oligo (diphenylsiloxane) white solid. Analysis result: GPC analysis (polystyrene conversion) Number average molecular weight 3600, dispersity (weight average molecular weight / number average molecular weight) = 1.14, infrared absorption spectrum: Si-H212
7 cm ^-1 , 1H-NMR (ppm): -0.1 to +1.4,
4.9, 6.8-7.7.

(Reference Example 5) (Synthesis of oligo (diphenylsiloxane) terminated with butylvinylmethylsilyl group at one end and dimethylvinylsilyl group at the other end) 15 parts of hexaphenyltrisiloxane and 15 parts of diphenylether were heated to 160 ° C. under argon, The lithium silanolate prepared in Reference Example 2 was added thereto and the mixture was reacted for 35 minutes so that the ratio of silanolate to diphenylsiloxane group was 1:14. To this was added 3 equivalents of dimethylvinylchlorosilane and heated for 10 minutes. After cooling to room temperature, 200 parts of methanol was added to obtain a white precipitate, which was washed with 200 parts of acetone and dried to obtain 12 parts of butylvinylmethylsilyl group dimethylvinylsilyl group-stopped oligo (diphenylsiloxane). As a result, GPC analysis (polishing) was performed. Ren equivalent) number average molecular weight 3200. polydispersity (weight average molecular weight / number average molecular weight) = 1.26.1H-NMR (ppm): - 0.02~
+1.4, 5.5-6.0, 6.7-7.5.

Reference Example 6 (Synthesis of Oligo (diphenylsiloxane) Terminated with Butylvinylmethylsilyl Group at One End and Dimethylvinylsilyl Group at Other End) An oligomer having a smaller molecular weight than that of Reference Example 5 was prepared in the same manner as in Reference Example 5. Synthesized. That is, 12 parts of hexaphenyltrisiloxane and 12 parts of orthoxylene were heated to reflux under argon, and the lithium silanolate prepared in Reference Example 2 was added thereto so that the ratio of silanolate to diphenylsiloxane group was 1: 7. Reacted for 90 minutes. 2 to this
Part of dimethylvinylchlorosilane was added to complete the reaction. After cooling the reaction solution to room temperature, 200 parts of methanol was added to obtain a white precipitate. The precipitate was washed with 200 parts of acetone and dried to obtain 6.3 parts of a butylvinylmethylsilyl group-dimethylvinylsilyl group-terminated oligo (diphenylsiloxane) white solid. Analysis result: GPC analysis (polystyrene conversion) Number average molecular weight 1900. Dispersity (weight average molecular weight / number average molecular weight) = 1.14.

(Reference Example 7) (Synthesis of butylvinylmethylsilyl group at one end- (4-vinylphenyl) dimethylsilyl group at the other end) (Synthesis of oligo (diphenylsiloxane) terminated with 10 parts of hexaphenyltrisiloxane and 11 parts of orthoxylene) The mixture was heated under reflux under argon, and the lithium silanolate prepared in Reference Example 2 was added thereto so that the ratio of silanolate to diphenylsiloxane group was 1: 7, and the mixture was reacted for 90 minutes. After the reaction liquid was lowered to 60 degrees, 2.5 parts of 4-vinylphenyldimethylchlorosilane was added and heated for 60 minutes. After cooling the reaction solution to room temperature, 200 parts of methanol was added and the resulting precipitate was washed with 200 parts of acetone. This precipitate was dried to obtain 5 parts of a white solid of butylvinylmethylsilyl group (4-vinylphenyl) dimethylsilyl group-terminated oligo (diphenylsiloxane). Analysis result: GPC analysis (polystyrene conversion) Number average molecular weight 1700. Dispersion degree (weight average molecular weight / number average molecular weight) = 1.11. Infrared absorption due to silanol groups was not observed, indicating that the silylation was completed.

(Reference Example 8) (Synthesis of oligo (diphenylsiloxane) terminated with butyldiethylsilyl group at one end and triethylsilyl group at the other end) 15 parts of hexaphenyltrisiloxane and 19 parts of diphenylether were heated to 160 ° C. under argon, and The lithium silanolate prepared in Reference Example 3 was added so that the ratio of silanolate to diphenylsiloxane group was 1:14, and the reaction was carried out for 35 minutes. To this, 2 parts of triethylchlorosilane was added and heated for 10 minutes. After cooling the reaction solution to room temperature, 200 parts of methanol was added to obtain a white precipitate. This precipitate was washed with 200 parts of acetone and then dried 11.
A white solid of 7 parts of butyldiethylsilyl group-triethylsilyl group-terminated oligo (diphenylsiloxane) was obtained. Analysis result: GPC analysis (polystyrene conversion) Number average molecular weight 3000. Dispersion degree (weight average molecular weight / number average molecular weight) = 1.27. Infrared absorption due to silanol groups was not observed, indicating that the silylation was completed.

Reference Example 9 (Synthesis of oligo (diphenylsiloxane) terminated with butyldiethylsilyl group at one end and tripropylsilyl group at the other end) 15 parts of hexaphenyltrisiloxane and 19 parts of diphenylether were heated to 160 ° C. under argon, The lithium silanolate prepared in Reference Example 3 was added to this so that the ratio of silanolate to diphenylsiloxane group was 1:18, and the reaction was carried out for 35 minutes. To this, 2 parts of tripropylchlorosilane was added and heated for 10 minutes. After cooling the reaction solution to room temperature, 200 parts of methanol was added to obtain a white precipitate.
The precipitate was washed with 200 parts of acetone and then dried.
A white solid of 2.9 parts of butyldiethylsilyl group-tripropylsilyl group-terminated oligo (diphenylsiloxane) was obtained. Analysis result: GPC analysis (polystyrene conversion) Number average molecular weight 3000. Dispersion degree (weight average molecular weight / number average molecular weight) = 1.25. Infrared absorption due to silanol groups was not observed, indicating that the silylation was completed.

Reference Example 10 (Synthesis of oligo (diphenylsiloxane) terminated with vinyldimethylsilyl groups at both ends) Hexaphenyltrisiloxane-1,5-diol 20
10 parts of vinyldimethylchlorosilane and 10 parts of triethylamine were added to 100 parts of toluene, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was slowly added to 150 parts of stirred water to obtain a white precipitate. After adding 100 parts of water thereto, the organic layer was separated, washed with water several times, and then dehydrated with anhydrous sodium sulfate. After filtration, the organic solvent was distilled off to obtain 24.4 parts of a colorless oily substance. The oily product slowly crystallized. Analysis result: Infrared spectrum: 140 due to vinyl group
An 8 cm ^-1 peak was observed. 1H-NMR spectrum: 0 ppm (methyl group), 5.5
-5.6 ppm (vinyl group), 7.1-7.5 (phenyl group).

(Reference Example 11) (Synthesis of hexaphenyltrisiloxane terminated with (4-vinylphenyl) dimethylsilyl group at both ends) Hexaphenyltrisiloxane-1,5-diol 20
27 parts by dissolving in 45 parts of tetrahydrofuran
Part of n-butyllithium (1.9 mol / liter) in hexane was added to add hexaphenyltrisiloxane-1,
A dilithium salt of 5-diol was obtained. 4-Vinylphenyldimethylchlorosilane (15 parts) was added thereto at room temperature, and the mixture was heated under reflux at 65 ° C. for 1.5 hours. After this, trimethylchlorosilane and triethylamine (1 each
(Each part) was added to cap unreacted silanol groups. Pour the reaction mixture into 200 parts cold water and add 3 organics.
It was extracted with 00 parts of toluene. After the toluene extract was thoroughly washed with water, the solvent was removed to obtain 26 parts of oil-like hexaphenyltrisiloxane terminated with (4-vinylphenyl) dimethylsilyl group at both ends. Analysis result: Infrared spectrum: No residual silanol was observed. 1H-NMR spectrum: 0.1 ppm (methyl group),
5.2, 5.7, 6.7ppm (vinyl group), 7.1-
7.5 (phenyl group).

Reference Example 12 (Synthesis of hexaphenyltrisiloxane terminated with dimethylsilyl groups at both ends) Hexaphenyltrisiloxane-1,5-diol 5 parts by weight dissolved in 20 parts of toluene 1,1,3,3 3-
Tetramethyldisilazane (1.1 parts) and dimethylchlorosilane (0.8 parts) were added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was slowly added to 150 parts of water to obtain a white precipitate. After adding 100 parts of water thereto, the organic layer was separated, washed with water several times, and then dehydrated with anhydrous sodium sulfate. After filtration, the organic solvent was distilled off to obtain 6 parts of a colorless oily substance. Analysis result: Infrared spectrum: A peak attributable to the Si-H group was observed at 2131 cm ^-1 . 1H-NMR spectrum: 0 ppm (doublet, methyl group), 4.7 ppm (heptet, Si-H group), 7.1
-7.5 (phenyl group).

(Reference Example 13) (Synthesis of hexaphenyltrisiloxane terminated with diallylmethylsilyl groups at both ends) Hexaphenyltrisiloxane-1,5-diol 3 parts were dissolved in 9 parts of tetrahydrofuran to add 3 parts of 1 part.
A 5% n-butyllithium hexane solution was added to obtain a dilithium salt of hexaphenyltrisiloxane-1,5-diol. After 1.6 parts of diallylmethylchlorosilane was added thereto at room temperature, the mixture was heated and stirred at 65 ° C. for 2 hours. After cooling the reaction mixture to room temperature, the produced lithium salt was removed by filtration, 100 parts of ether was added to the filtrate, and the organic layer was washed with water three times. The ether layer was removed by a rotary evaporator to obtain 2.9 parts of oligo (diphenylsiloxane) terminated with diallylmethylsilyl groups at both ends. Analysis: NMR: 1H-NMR (CDCl 3): -
0.06 (s, 6H), 1.45 (m, 8H), 4.7
4 (m, 8H), 5.57 (m, 4H), 7.19-
7.55 (m, 30H). 29Si {1H} -NMR
_{(CDCl 3): 3.72, -46.44} , -46.7
6.

(Reference Example 14) (Synthesis of hexaphenyltrisiloxane terminated with methyl (cyclotrimethylene) silyl groups at both ends) Hexaphenyltrisiloxane-1,5-diol 8.
1 part by dissolving 5 parts in 30 parts tetrahydrofuran
Two parts of a 15% hexane solution of n-butyllithium was added to obtain a dilithium salt of hexaphenyltrisiloxane-1,5-diol. After adding 4.5 parts of 1-chloro-1-methylsilacyclobutane to this at room temperature, the mixture was heated with stirring at 65 ° C. for 2 hours. The reaction mixture was cooled to room temperature, the produced lithium salt was removed by filtration, the solvent was removed under reduced pressure, and the residue was extracted 3 times with 70 parts of hexane. Hexane was removed by a rotary evaporator to obtain 8.6 parts of hexaphenyltrisiloxane terminated with methyl (cyclotrimethylene) silyl groups at both ends. Analysis: NMR: 1H-NMR (CDCl 3): 0.
15 (s, 6H), 1.1 (m, 8H), 1.58
(M, 2H), 2.20 (m, 2H), 7.2-7.7
(M, 30H). 13C {1H} -NMR (CDC
l ₃ , ppm): 0.75, 13.5, 20.5, 12
7.9-135.5.29 Si {1H} -NMR (CD
_{Cl 3, ppm): - 46.2} , -46.0,7.3.

(Reference Example 15) (Synthesis of hexaphenyltrisiloxane-1,5-diol) 400 g of tetrahydrofuran and 55 g of hexaphenylcyclotrisiloxane were added to an Erlenmeyer flask and dissolved. This was charged with 3 g of hexylamine and 40 g of water, and this was stirred at room temperature for 30 minutes. After confirming the conversion to diol by thin layer chromatography, the reaction solution was poured into 500 g of water and neutralized with dilute hydrochloric acid. The organic matter was extracted with 600 g of toluene, washed with water several times, dried over anhydrous sodium sulfate, filtered, and the filtrate was removed by a rotary evaporator 15
After concentrating to 0 ml, hexane was added to give 9 crystals of hexaphenyltrisiloxane-1,5-diol.
Obtained in 3% yield. Analysis of hexaphenyltrisiloxane-1,5-diol: melting point 110-111C. Infrared absorption 3244 cm ^-1 .

(Reference Example 16) (Synthesis of hexaphenyltrisiloxane terminated with dimethylsilyl groups at both ends) Hexaphenyltrisiloxane obtained in Reference Example 15
1 part of 1,1,3,3-tetramethyldisilazane was prepared by dissolving 5 parts of 1,5-diol in 20 g of toluene.
1 g and 0.8 g of dimethylchlorosilane were added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was slowly added to 150 grams of water to give a white precipitate.
After adding 100 g of water thereto, the organic layer was separated, washed with water several times, and then dehydrated with anhydrous sodium sulfate. After filtration, the organic solvent was distilled off to obtain 6 g of a colorless oily substance. Analysis result: Infrared spectrum: A peak attributable to the Si-H group was observed at 2131 cm ^-1 . 1H-NMR spectrum: 0 ppm (doublet, methyl group), 4.7 ppm (heptet, Si-H group), 7.1
-7.5 (phenyl group).

(Reference Example 17) (Synthesis of oligo (diphenylsiloxane) terminated with N-methylaminoisobutyl groups at both ends) Hexaphenyltrisiloxane obtained in Reference Example 15
1,2,2,4-tetramethyl-1- was added to 6.1 grams of 1,5-diol dissolved in 30 grams of toluene.
4.3 g of aza-2-silacyclobutane was added, and the mixture was stirred at 40 ° C. for 0.5 hours. Volatiles were removed from the reaction mixture in vacuo and the residue was extracted with 50 grams of toluene. The toluene extract was separated, washed with water several times, and then dehydrated with anhydrous sodium sulfate. After filtration, the organic solvent was distilled off, and 6.7 g of colorless oily N-methylaminoisobutyl group-terminated oligo (diphenylsiloxane) was obtained as a colorless oil.
I got Analysis result: 1H-NMR spectrum: -0.07 (s,
12H), 0.2 (dd, 2H), 0.50 (dd, 2)
H), 0.70 (d, 6H), 0.8-1.1 (br,
2H), 1.6 (m, 2H), 2.0-2.2 (m, 4)
H), 2.2 (s, 6H), 7.1-7.6 (m, 30
H). 13C {1H} -NMR: 0.8, 1.0, 2
0.6, 23.9, 28.5, 36.2, 61.2, 1
27.2, 129.4, 129.6, 134.0, 13
4.3, 134.6, 135.2.29 Si {1H}-
NMR: -47.1, -46.7, 10.2.

(Reference Example 18) (Synthesis of 3- (methacryloyloxy) propyldimethylsilyl group-terminated hexaphenyltrisiloxane at both ends) Hexaphenyltrisiloxane obtained in Reference Example 15
After 8.8 grams of 3- (methacryloyloxy) propyldimethylchlorosilane was added at room temperature to a mixture of 12.2 grams of 1,5-diol and 4.4 grams of triethylamine in 45 milliliters of toluene at 40 ° C.
It was stirred for 18 hours. The reaction mixture was poured into 250 grams of water and the organics were extracted twice with 50 grams of toluene.
The toluene extract was first washed with dilute hydrochloric acid, then thoroughly washed with water, dehydrated with sodium sulfate, filtered, and then the solvent was removed to obtain 18.4 g of 3- (methacryloyloxy) propyldimethylsilyl group-terminated hexaphenyl. Trisiloxane was obtained. Analysis result: 1H-NMR spectrum: -0.08 (s,
12H), 0.35 (t, 4H), 1.3-1.5
(M, 4H), 1.9 (s, 6H), 3.9 (t, 4)
H), 5.5 (d, 2H), 6.0 (d, 2H), 7.
1-7.6 (m, 30H). 13C {1H} -NMR spectrum: -0.3, 13.7, 18.1, 22.1,
66.8, 124.9, 127.4, 129.6, 12
9.8, 134.1, 134.3, 134.6, 13
5.1, 136.3, 137.1.29Si {1H}-
NMR spectrum: -46.8, -46.4, 10.
3.

(Reference Example 19) (Synthesis of 3- (glycidoxy) propyldimethylsilyl group-terminated hexaphenyltrisiloxane at both ends) 1,1,9,9-tetramethyl-obtained in Reference Example 16
35 g of 3,0,3,5,5,7,7-hexaphenylpentasiloxane, 7.3 g, and a 0-valent platinum-vinylsiloxane complex containing 0.86% by weight of platinum were used.
It was dissolved in gram toluene, 2.8 g of allyl glycidyl ether was added thereto, and the mixture was stirred at 100 ° C. for 18 hours. 7. The solvent and volatile organic components were distilled off from the reaction mixture.
7 g of 3- (glycidoxy) propyldimethylsilyl group-terminated hexaphenyltrisiloxane at both ends was obtained. Analysis result: 1H-NMR spectrum: 0.08 (s, 1
2H), 0.43 (t, 4H), 1.4 (tt, 4
H), 2.6 (dd, 2H), 2.8 (dd, 2H),
3.1 (m, 2H), 3.2-3.35 (m, 6H),
3.6 (dd, 2H), 7.1-7.6 (m, 30
H). 13C {1H} -NMR spectrum: -0.4,
13.6, 22.8, 43.9, 50.4, 50.4,
70.9, 73.7, 127.2, 129.4, 12
9.6, 133.9, 134.2, 124.6, 13
5.1.

Reference Example 20 (Synthesis of 3-Aminopropyldimethylsilyl Group Terminated Hexaphenyltrisiloxane at Both Terminals) 1,1,9,9-tetramethyl-obtained in Reference Example 16
35 g of 3,0,3,5,5,7,7-hexaphenylpentasiloxane, 7.3 g, 4 liters of 0-valent platinum-vinylsiloxane complex containing 0.86% by weight of platinum.
Dissolve in milliliters of toluene, add 5.2 grams of N-trimethylsilylallylamine to this, and add 100 ° C.
It was stirred for 65 hours. After the reaction, 3.2 g of methanol was added and stirred, and then the solvent and volatile organic components were distilled off.
3 grams of hexaphenyltrisiloxane terminated with 3-aminopropyldimethylsilyl groups at both ends was obtained. Analysis result: 1H-NMR spectrum: -0.06 (s,
12H), 0.40 (t, 4H), 1.0 (br, 2
H), 1.15 (tt, 4H), 2.45 (t, 4)
H), 7.2-7.7 (m, 30H). 29Si {1
H} -NMR: 10.56, -46.6, -47.1.

Reference Example 21 0.45 g of oligo (diphenylsiloxane) terminated with N-methylaminoisobutyl groups at both ends obtained in Reference Example 17 was dissolved in 1 g of toluene, and pentaerythritol tetra (acrylate) 0 was added. 0.26 g was added to a solution dissolved in 0.5 g of toluene, and the mixture was allowed to stand overnight to prepare a Michael adduct of amino group to acryloyl group. According to GPC analysis, N-methylaminoisobutyl group-terminated oligo (diphenylsiloxane) at both ends (Mw = 454, Mn = 446: polystyrene conversion) was crosslinked by a Michael addition reaction, and M
A polymer having w = 1400 and Mn = 1010 was formed.

(Example 1) (One end butyldimethylsilyl group and other terminal dimethylsilyl group terminated oligo (cured product of diphenylsiloxane)) One terminal butyldimethylsilyl group and other terminal dimethylsilyl group terminated oligo obtained in Reference Example 4 ( 10 parts of diphenylsiloxane dissolved in 90 parts of hot toluene was cast on a slide glass and left in air for 30 minutes to evaporate the solvent.The slide glass was heated in an oven at 400 ° C for 45 minutes. Upon curing, it produced a transparent, brittle coating film.

(Example 2) (Cured product of oligo (diphenylsiloxane) terminated with butylvinylmethylsilyl group at one terminal and dimethylvinylsilyl group at the other terminal) Butylvinylmethylsilyl group at one terminal and dimethylvinyl terminal at the other terminal obtained in Reference Example 5 10 parts of silyl group-terminated oligo (diphenylsiloxane) dissolved in 90 parts of toluene was cast on a slide glass, which was left at room temperature to evaporate the solvent. This slide glass is 400 ℃
In an oven for 60 minutes. The evaluation of the transparent cured coating film after cooling showed a pencil hardness of 4H. Similarly, a coating film was prepared on a silicon wafer and an aluminum plate. The pencil hardness was also 4H.

(Example 3) (Cured product of oligo (diphenylsiloxane) terminated with butylvinylmethylsilyl group at one end and dimethylvinylsilyl group at the other end) Butylvinylmethylsilyl group at the other end and dimethylvinyl end at the other end obtained in Reference Example 6 Thirty parts of silyl group-terminated oligo (diphenylsiloxane) dissolved in 90 parts of toluene was cast on a slide glass, which was then placed in air for 30 minutes.
The solvent was evaporated by standing for a minute. This slide glass was heat-cured in an air oven at 400 ° C. for 1 hour. The pencil hardness of the transparent cured coating film after cooling was 4H.

(Example 4) (Butyl vinylmethylsilyl group at one end-cured product of oligo (diphenylsiloxane) terminated with (4-vinylphenyl) dimethylsilyl group at the other end) Butylvinylmethyl at one end obtained in Reference Example 7 Silyl group-other terminal (4-vinylphenyl) dimethylsilyl group-terminated oligo (diphenylsiloxane) 10 parts dissolved in 90 parts toluene was cast on a slide glass and left in the air for 30 minutes to prepare a solvent. Was evaporated. The slide glass was heat-cured in an oven at 350 ° C. for 10 minutes in the air. An evaluation of the transparent cured coating film after cooling showed a pencil hardness of 3H.

(Example 5) (Cured product of oligo (diphenylsiloxane) terminating with butyldiethylsilyl group at one end and triethylsilyl group at the other end) Oligo with terminating butyldiethylsilyl group at the other end and triethylsilyl group at the other end obtained in Reference Example 8 A solution prepared by dissolving 10 parts of (diphenylsiloxane) in 90 parts of toluene was cast on a slide glass and left in the air to evaporate the solvent. The slide glass was heated in an oven at 350 ° C. for 15 minutes and then heat-cured at 400 ° C. for 45 minutes. The pencil hardness of the transparent cured coating film after cooling is 3
It was H. Similarly, the coating film prepared on the silicon wafer also showed a pencil hardness of 3H.

Example 6 (Butyldiethylsilyl group at one terminal-tripropylsilyl group at the other terminal cured product of oligo (diphenylsiloxane) terminated) The butyldiethylsilyl group at one terminal-tripropyl at the other terminal obtained in Reference Example 9 10 parts of silyl group-stopped oligo (diphenylsiloxane) dissolved in 90 parts of hot toluene was cast on a slide glass, and this was left in the air to evaporate the solvent. This slide glass in the air 4
It was heat-cured in an oven at 00 ° C. for 1 hour. The pencil hardness of the transparent cured coating film after cooling was 3H.

Example 7 (Cured product of oligo (diphenylsiloxane) terminated with vinyldimethylsilyl groups at both ends) 10 parts of oligo (diphenylsiloxane) terminated with vinyldimethylsilyl groups at both ends obtained in Reference Example 10 What was dissolved in toluene was cast on a slide glass, which was left in the air for 30 minutes to evaporate the solvent. This slide glass was heated and cured in an oven at 400 ° C. for 45 minutes in the air. The pencil hardness of the transparent cured coating film after cooling was 8H.

Example 8 (Cured product of hexaphenyltrisiloxane terminated with (4-vinylphenyl) dimethylsilyl group at both ends) Hexaphenyl terminated with (4-vinylphenyl) dimethylsilyl group obtained in Reference Example 11 Trisiloxane 10
Parts dissolved in 90 parts of toluene were cast on a slide glass and left in the air for 30 minutes to evaporate the solvent. The slide glass was cured by heating in an oven in air. A coating having a pencil hardness of 3H was formed in 2 minutes at 300 ° C. Similarly, a coating with a pencil hardness of 3H at 260 ° C in 3 minutes and 2H at 220 ° C in 35 minutes was produced.

Example 9 (Cured product of hexaphenyltrisiloxane terminated with (4-vinylphenyl) dimethylsilyl group at both ends) Hexaphenyl terminated with (4-vinylphenyl) dimethylsilyl group obtained in Reference Example 11 Trisiloxane was placed in a test tube and heat-cured at 300 ° C. for 10 minutes in a nitrogen atmosphere. The transparent cured product after cooling showed a pencil hardness of 3H and a Shore D hardness of 80.

Example 10 (Cured product of hexaphenyltrisiloxane terminated with (4-vinylphenyl) dimethylsilyl groups at both ends) Hexaphenyl terminated with (4-vinylphenyl) dimethylsilyl groups obtained in Reference Example 11 Trisiloxane 10
Parts dissolved in 90 parts of toluene were cast on a slide glass and left in the air for 30 minutes to evaporate the solvent. This slide glass in a nitrogen stream at 300 ℃
It was heat-cured for 10 minutes. An evaluation of the transparent cured coating film after cooling showed a pencil hardness of 3H. Similar results were obtained on a silicon wafer.

Example 11 (Cured product of hexaphenyltrisiloxane terminated with (4-vinylphenyl) dimethylsilyl group at both ends) Hexaphenyl terminated with (4-vinylphenyl) dimethylsilyl group obtained in Reference Example 11 Trisiloxane 10
To 90 parts of toluene was added 0.85% by weight of benzoyl peroxide based on hexaphenyltrisiloxane terminated with (4-vinylphenyl) dimethylsilyl group at both ends. This solution was cast on a slide glass and left in the air for 30 minutes to evaporate the solvent. The slide glass was heat-cured for 6 minutes in an oven at 110 ° C. under nitrogen. Evaluation of the transparent cured coating film after cooling gave a pencil hardness of 3H. 2,4-dichlorobenzoyl peroxide, dicumyl peroxide, or 1,1-bis (t-butylperoxy) -3,3 instead of benzoyl peroxide
The same coating was obtained by heating with 5-trimethylcyclohexane for 5 minutes at 150 ° C.

(Example 12) (Cured product of hexaphenyltrisiloxane terminated with (4-vinylphenyl) dimethylsilyl groups at both ends) Hexaphenyl terminated with (4-vinylphenyl) dimethylsilyl groups at both ends obtained in Reference Example 11 Trisiloxane 10
To 90 parts of toluene was added 0.35% by weight of benzoyl peroxide to hexaphenyltrisiloxane terminated with (4-vinylphenyl) dimethylsilyl groups at both ends, and this solution was cast on a slide glass. It was then left in the air for 30 minutes to evaporate the solvent.
The slide glass was heat-cured for 6 minutes in an oven at 130 ° C. under a nitrogen atmosphere. An evaluation of the transparent cured coating film after cooling showed a pencil hardness of 3H.

(Example 13) (Cured product of hexaphenyltrisiloxane terminated with dimethylsilyl groups at both ends) 7.2 parts of hexaphenyltrisiloxane terminated with dimethylsilyl groups at both ends obtained in Reference Example 12 and obtained in Reference Example 13 A mixture of 4.4 parts of hexaphenyltrisiloxane terminated with diallylmethylsilyl groups at both ends and 8 parts of toluene was added to a vinylsiloxane complex of 0-valent platinum with respect to siloxane (10 ppm as platinum) and CH ₃ Si (OC). (CH
₃ ) 2C≡CH) ₃ (100 ppm) was added. This solution was cast on a slide glass and left in the air for 1 hour to evaporate the solvent. This slide glass 1
It was heat-cured in an oven at 50 ° C. for 20 minutes. The pencil hardness of the transparent cured coating film after cooling was 2H.

Example 14 (Cured product of hexaphenyltrisiloxane terminated with diallylmethylsilyl groups at both ends) 6 parts of hexaphenyltrisiloxane terminated with diallylmethylsilyl groups at both ends obtained in Reference Example 13 and PhSi (OM)
3 parts of e ₂ SiH) ₃ dissolved in 10 parts of toluene, and a vinylsiloxane complex of 0-valent platinum with siloxane (10 ppm as platinum) and CH ₃ Si (OC (CH ₃ ).
₂ C≡CH) ₃ (100 ppm) was added. This solution was cast on a slide glass and left in the air for 1 hour to evaporate the solvent. 150 this slide glass
It was heat-cured in an oven at 0 ° C. for 20 minutes. The pencil hardness was F according to the evaluation of the transparent cured coating film after cooling.

Example 15 (Cured product of hexaphenyltrisiloxane terminated with diallylmethylsilyl groups at both ends) 10 parts of hexaphenyltrisiloxane terminated with diallylmethylsilyl groups at both ends obtained in Reference Example 13 was added to 90 parts of hexane. The melted product was cast on a slide glass and left in the air for 30 minutes to evaporate the solvent. The slide glass was heat-cured in air at 250 ° C. for 5 minutes. An evaluation of the transparent cured coating film after cooling revealed a pencil hardness of 2H. Similarly, the pencil hardness of what was cured by heating for 10 minutes was 3H.

(Example 16) (Cured product of hexaphenyltrisiloxane terminated with methyl (cyclotrimethylene) silyl groups at both terminals) Hexaphenyltrisiloxane terminated with methyl (cyclotrimethylene) silyl groups at both terminals obtained in Reference Example 14 A solution prepared by dissolving 10 parts of toluene in 90 parts of toluene was cast on a slide glass and left standing in the air for 30 minutes to evaporate the solvent. This slide glass was heated and cured at 150 ° C. for 1 hour in a nitrogen stream. The pencil hardness was H according to the evaluation of the transparent cured coating film after cooling. Similarly, a coating of pencil hardness H was obtained by heating in air at 240 ° C. for 60 minutes, at 260 ° C. for 30 minutes, and at 300 ° C. for 15 minutes.

(Example 17) (Cured product of hexaphenyltrisiloxane terminated with methyl (cyclotrimethylene) silyl groups at both terminals) Hexaphenyltrisiloxane terminated with methyl (cyclotrimethylene) silyl groups at both terminals obtained in Reference Example 14 A vinylsiloxane complex of 0-valent platinum was added to 10 parts of toluene dissolved in 90 parts of toluene so that the content of siloxane was 10 ppm. This solution was cast on a slide glass and left in the air for 30 minutes to evaporate the solvent.
The slide glass was heat-cured in air at 150 ° C. for 1 minute. The pencil hardness was H according to the evaluation of the transparent cured coating film after cooling. Similarly, heating at 110 ° C. for 70 minutes produced a coating having a pencil hardness of 1H.

(Example 18) (Cured product of oligo (diphenylsiloxane) terminated with vinyldimethylsilyl groups at both ends) 3.8 parts of oligo (diphenylsiloxane) terminated with vinyldimethylsilyl groups at both ends obtained in Reference Example 10 and PhSi
(OMe ₂ SiH) ₃ 2.8 parts dissolved in 3.7 parts toluene, 6.3 parts of the above both-terminal vinyldimethylsilyl group-terminated oligo (diphenylsiloxane) and this both-terminal vinyldimethylsilyl group-terminated oligo 20ppm of platinum (vinyl siloxane complex of 0-valent platinum) and a small amount (200ppm) of CH _{3 with} respect to (diphenylsiloxane)
Si (OC (CH ₃ ) ₂ C≡CH) ₃ dissolved in 3.6 parts of toluene was mixed at a ratio of 1: 1 and cast on a slide glass and left in the air for 1 hour. The solvent was evaporated. This slide glass in air at 150 ℃
When heat-cured for 10 minutes in the oven, a transparent cured coating film (pencil hardness H) was obtained.

(Example 19) (Curing of 3- (methacryloyloxy) propyldimethylsilyl group-terminated hexaphenyltrisiloxane at both ends) 3- (methacryloyloxy) propyldimethylsilyl group at both ends obtained in Reference Example 18 To a solution of stopped hexaphenyltrisiloxane in toluene (50%) was added 1% by weight of Darocurure 1173, based on the siloxane, which was spin coated onto a glass plate. This glass plate was irradiated with a high pressure mercury lamp for 10 minutes in a nitrogen atmosphere to obtain a cured film.
The cured film has a pencil hardness of 2H and a critical surface tension of 30 mN.
Was / m.

(Example 20) (Curing of 3- (methacryloyloxy) propyldimethylsilyl group-terminated hexaphenyltrisiloxane at both ends) 3- (methacryloyloxy) propyldimethylsilyl group at both ends obtained in Reference Example 18 To a solution of 1 gram of stopped hexaphenyltrisiloxane in 2 grams of toluene was added 1% by weight of benzoyl peroxide based on the siloxane and the solution was cast onto a glass plate. After leaving it in the air at room temperature for 30 minutes to evaporate toluene, it was heated at 150 ° C. for 10 minutes in a nitrogen atmosphere to cure the siloxane. The pencil hardness of the film was 2H and the critical surface tension was 30 mN / m.

(Example 21) (Curing of hexaphenyltrisiloxane terminated with 3- (glycidoxy) propyldimethylsilyl group at both ends) Hexaphenyltri terminated with 3- (glycidoxy) propyldimethylsilyl group at both ends obtained in Reference Example 19 6.3 g of siloxane and 0.33 g of triethylene tetraamine were mixed and placed in a Teflon container, which was heated at 150 ° C. for 18 hours to obtain a cured product. The Shore A hardness of the cured product was 66. Critical surface tension is 31mN / m
Met.

(Example 22) (Curing of hexaphenyltrisiloxane terminated with 3-aminopropyldimethylsilyl groups at both ends) 0.5-hexaphenyltrisiloxane terminated with 3-aminopropyldimethylsilyl groups at both ends obtained in Reference Example 20 Gram and 1.3-gram of hexaphenyltrisiloxane terminated with 3- (glycidoxy) propyldimethylsilyl groups at both ends obtained in Reference Example 5 were dissolved in 1.7 gram of toluene and cast on a glass plate. It was left at room temperature for 30 minutes to evaporate toluene, and then heat-cured at 150 ° C. for 3 hours. The cured film had a pencil hardness of F and a critical surface tension of 31 mN / m.

(Example 23) (Curing of N-methylaminoisobutyl group-terminated oligo (diphenylsiloxane) at both ends) N-methylaminoisobutyl group-terminated oligo (diphenylsiloxane) at both ends obtained in Reference Example 21 and tetrakis ( To a toluene solution of an adduct of acryloyloxy) pentaerythritol, 1% by weight of an ultraviolet curing initiator Darocur 1173 with respect to a solute was added, and this was added in air 30
Toluene was removed by standing for a minute. This was exposed to a high pressure mercury lamp for 10 minutes in a nitrogen atmosphere and cured. The hardness of the film is 3
H and the critical surface tension was 32 mN / m.

(Example 24) (Curing of N-methylaminoisobutyl group-terminated oligo (diphenylsiloxane) at both terminals) N-methylaminoisobutyl group-terminated oligo (diphenylsiloxane) at both terminals obtained in Reference Example 21 and tetrakis ( To a toluene solution of an adduct of acryloyloxy) pentaerythritol, 1% by weight of benzoyl peroxide with respect to the solute was added, and this was left in the air for 30 minutes to remove toluene. This was heat-cured at 120 ° C. for 10 minutes in a nitrogen atmosphere. The hardness of the film is 3H and the critical surface tension is 3
It was 2 mN / m.

[Brief description of drawings]

FIG. 1 is a graph showing the molecular weight dependence of the phase change temperature of a diphenylsiloxane oligomer.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mamoru Tachikawa 2-20 Higashiootake 11 Isehara City Kanagawa Prefecture 11

Claims (10)

[Claims] 1. A diphenylsiloxane oligomer represented by the following formula (1) is converted into the following (i), (ii) and (iii)
A method for producing a cured product of diphenylsiloxane, which comprises causing a curing reaction by heating or light irradiation under a condition selected from the following. Embedded image (In the formula, at least one substituent of R ¹ , R ² , and R ³ and at least one substituent of R ⁶ , R ⁷ , and R ⁸ is a hydrogen atom or a saturated group having 2 to 10 carbon atoms. Alternatively, it may be an unsaturated hydrocarbon group containing a hetero atom selected from nitrogen, oxygen, sulfur and silicon (provided that
(Excluding a phenyl group and an alkyl-substituted phenyl group), and ^{two of} R ¹ , R ² and R ³ may jointly form a cyclic hydrocarbon, and R ⁶ , R ⁷ and R ⁸ R ¹ , R ² , and R ³ are the same as R ¹ , R ² ,
The remaining groups of R ³ , R ⁶ , R ⁷ and R ⁸ are methyl group, phenyl group or alkyl-substituted phenyl group having 7 to 10 carbon atoms, if any; R ⁴ and R ⁵ are organic. R ⁹ and R ¹⁰ are organic groups and cannot be phenyl groups at the same time; 1
≦ m ≦ 50; k and n are independently 0 ≦ k ≦ 3, 0 ≦
n ≦ 3) (i) in the presence of a curing catalyst, (ii) in the presence of a polymerization initiator or a polymerization catalyst, and (iii) in the absence of a curing catalyst and a polymerization initiator. 2. The curing reaction is a polymerization reaction, and in the diphenylsiloxane oligomer represented by the formula (1), at least one of R ¹ , R ² and R ³ has a polymerization-reactive unsaturated group. Yes and R ⁶ , R ⁷ , R
^At least one of ⁸ has a polymerizable reactive unsaturated group, and the remaining groups among R ¹ , R ² , R ³ , R ⁶ , R ⁷ and R ⁸ are methyl groups, if any. A phenyl group or an alkyl-substituted phenyl group having 7 to 10 carbon atoms, and the method for producing a diphenylsiloxane cured product according to claim 1, wherein one method selected from the following a, b, and c is adopted. a: UV irradiation at a temperature of 300 ° C or lower b: Heating at a temperature of 100 ° C to 500 ° C in the absence of a polymerization initiator c: Heating at a temperature of 50 ° C to 500 ° C in the presence of a polymerization initiator 3. The curing reaction is a polymerization reaction, and in the diphenylsiloxane oligomer represented by the formula (1), at least two substituents of R ¹ , R ² and R ³ are connected to each other to form a trimethylene group or a substituted trimethylene group. To form a silacyclobutane structure, and R ⁶ , R ⁷ and R ⁸ are also R ¹ ,
Similar to R ² and R ³ , R ¹ , R ² , R ³ , R ⁶ and R
The remaining group of ⁷ , R ⁸ is a methyl group, a phenyl group, or an alkyl-substituted phenyl group having 7 to 10 carbon atoms, if any, which is selected from platinum compounds, metallic platinum or rhodium compounds. The method for producing a diphenylsiloxane cured product according to claim 1, wherein the ring-opening polymerization is performed by heating at 100 ° C. or higher in the presence of a catalyst for use. 4. The diphenylsiloxane oligomer represented by the formula (1), wherein the curing reaction is a polymerization reaction, wherein at least one of R ¹ , R ² and R ³ contains an epoxy group such as an alkyl group, an alkenyl group or an aryl group. At least one of R ⁶ , R ⁷ and R ⁸ is an epoxy group-containing alkyl group, alkenyl group or aryl group, and R ¹ , R ² , R ³ , R ⁶ , R ⁷ and R ⁸ The remaining groups in the group are those which, if any, are a methyl group, a phenyl group, or an alkyl-substituted phenyl group having 7 to 10 carbon atoms, which is polymerized and cured in the presence of a polymerization catalyst. A method for producing a cured product of diphenylsiloxane. 5. Shiroki where the curing reaction is based on an oxidation reaction
It is a sun bond formation reaction and is represented by the formula (1).
R in siloxane oligomer¹, R², R³Horse
At least one of which is a hydrogen atom or a linear saturated hydrocarbon
Group, branched saturated hydrocarbon group, alkenyl group, alkynyl group
Group, aralkyl group and R¹, R², R³Two out of
The substituents bond to each other to form a trimethylene group, tetramethylene group.
Group, a silacyclo structure selected from pentamethylene group
R is one kind selected from those formed.⁶, R⁷, R
⁸Is the same as in¹, R², R³, R⁶, R
⁷, R⁸The remaining groups in are the methyl group,
Phenyl group or alkyl-substituted phenyl having 7 to 10 carbon atoms
That is a ruthelic group in an oxygen-containing gas at a temperature of 250 ° C or higher
The diphenyl sirox according to claim 1, which is heated at
Manufacturing method of sun cured product. 6. The method for producing a diphenylsiloxane cured product according to claim 1, wherein the curing reaction is an addition reaction or a condensation reaction via a crosslinking agent or a chain extender. 7. In the formula (1), R¹, R², R³of
At least one of them is alkenyl having 2 to 10 carbon atoms.
1 selected from a group, an alkynyl group and a styrenic substituent
The remaining groups are methyl groups, phenyl groups, if any.
Group or an alkyl-substituted phenyl group having 7 to 10 carbon atoms
And R⁶, R⁷, R⁸Also R¹~ R ³Defined as
The cross-linking agent or chain extender is contained in one molecule.
Hydrosilyl group having two or more ≡SiH groups
Curing by hydrosilylation reaction in the presence of
A method for producing a cured product of diphenylsiloxane according to claim 6.
Law. 8. In the formula (1), at least one of R ¹ , R ² and R ³ is a hydrogen atom, and the remaining group, if any, is a methyl group, a phenyl group or a carbon number of 2 to 2. 1
An alkyl-substituted phenyl group of 0, R ⁶ , R ⁷ , and R ⁸
Is also defined as R ^{1 to} R ³ , and the cross-linking agent or chain extender has one functional group selected from an alkenyl group, an alkynyl group and a styrene-based substituent in 2 molecules in one molecule.
The method for producing a cured product of diphenylsiloxane according to claim 6, wherein the cured product has one or more and is cured by a hydrosilylation reaction in the presence of a hydrosilylation catalyst. 9. In the formula (1), at least one of R ¹ , R ² and R ³ has an organic group having an epoxy group, an organic group having an amino group, an organic group having a substituted amino group, and a carboxyl group. It is one kind selected from an organic group, an organic group having a hydroxyl group, an organic group having a mercapto group, an organic group having an isocyanate group and an organic group having a vinyl group, and R ⁶ , R ⁷ and R ⁸ are also R ¹ to It is defined in the same manner as R ^3, and the epoxy group, the amino group, the substituted amino group, the carboxyl group, the hydroxyl group, the mercapto group, in which the crosslinking agent or the chain extender has reactivity with the above group,
1 functional group selected from isocyanate group and vinyl group
The method for producing a cured product of diphenylsiloxane according to claim 6, which has at least two in the molecule. 10. A cured product of diphenylsiloxane produced by the method according to claim 1 and having a critical surface tension of 26 mN / m or more.