JPH11130865A - Silphenylene compound containing hydroxyphenyl group, silphenylene-modified organic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydroxyphenyl group-containing silphenylene compound having hydroxyphenyl groups at both the molecular chain ends, and to provided a silphenyl-modified polycarbonate resin and a silphenylene-modified polyarylate resin. SOLUTION: This hydroxyphenyl group-containing silphenylene compound is expressed by the formula [R is a hydrocarbon group not containing an aliphatic unsaturated bond; R<1> is an alkylene group or an alkyleneoxyalkylene group; Ph is phenylene ring; A is hydroxyphenyl group; B is a >=2C alkylene group or an alkyleneoxyalkylene group; (x), (y), (z) are each 1-1,000, (y)+(z) is >=1; (a) is 0 or 1]. A silphenylene-modified organic resin is obtained by copolymerizing the sliphenylene compound with an organic resin monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel hydroxyphenyl group-containing silphenylene compound and a silphenylene-modified organic resin. More specifically, a novel hydroxyphenyl group-containing silphenylene compound having hydroxyphenyl groups at both molecular chain terminals and a silphenylene-modified organic resin modified with the silphenylene compound, particularly, a silphenylene modified with the silphenylene compound The present invention relates to a modified polycarbonate resin and a silphenylene-modified polyarylate resin.

[0002]

2. Description of the Related Art Silphenylene compounds having organic functional groups at both ends of a molecular chain include, for example, a compound represented by the formula:

Embedded image (See JP-A-5-320350 and JP-A-9-59387), a compound represented by the formula:

Embedded image (See JP-A-1-236249), a compound represented by the formula:

Embedded image (See Japanese Patent Application Laid-Open No. 4-222815) is known. However, a silphenylene compound having a hydroxyphenyl group at both terminals is not known. On the other hand, polycarbonate resins have excellent heat resistance and impact resistance, and are therefore widely used for applications requiring such properties. However, this type of polycarbonate resin has problems that its moldability is not sufficient, and that it has low releasability and water repellency after molding. For this reason, a method of improving the moldability by adding an additive such as a plasticizer or a release agent to the polycarbonate resin, or a method of copolymerizing a polycarbonate resin with a polyorganosiloxane having a hydroxyphenyl group is used. Proposed. As the latter method, for example, a polycarbonate resin having a siloxane unit incorporated in the main chain thereof (Japanese Patent Application Laid-Open No.
No. 9626) and a polycarbonate resin obtained by graft-bonding a siloxane chain in order to further increase the freedom of movement of the polyorganosiloxane chain (Japanese Unexamined Patent Publication No.
JP-A-155999 and JP-A-7-165897) are known. However, polycarbonate resin incorporating such polyorganosiloxane,
Since the polyorganosiloxane chain is a polymer having high flexibility, there are problems such as a decrease in hardness.

[0003]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, an object of the present invention is to provide a novel hydroxyphenyl group-containing silphenylene compound having hydroxyphenyl groups at both molecular chain terminals and useful as an organic resin modifier, and the silphenylene compound A silphenylene-modified organic resin modified by, in particular,
An object of the present invention is to provide a silphenylene-modified polycarbonate resin and a silphenylene-modified polyarylate resin modified with the silphenylene compound.

[0004]

According to the present invention, there is provided a compound represented by the general formula:

Embedded image (Wherein, R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, and R ¹ has 2 to 10 carbon atoms.
Wherein -Ph- represents a substituted or unsubstituted phenylene ring, A is a substituted or unsubstituted hydroxyphenyl group, and B is an alkylene group having 2 or more carbon atoms or alkylene. It is an oxyalkylene group. x is 1 to 1,00
0 is an integer, y is an integer from 0 to 1,000, z
Is an integer of 0 to 1,000, and y + z is an integer of 1 or more. a is 0 or 1; The present invention relates to a hydroxyphenyl group-containing silphenylene compound represented by the formula (1), and a silphenylene-modified organic resin obtained by copolymerizing the silphenylene compound with an organic resin monomer.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the hydroxyphenyl group-containing silphenylene compound of the present invention will be described. The hydroxyphenyl group-containing silphenylene compound of the present invention has the general formula:

Embedded image It is represented by In the above formula, R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, and specifically,
Examples include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; an aryl group such as a phenyl group, a tolyl group and a xylyl group; and an aralkyl group such as a benzyl group and a phenethyl group. R ¹ is an alkylene group or an alkyleneoxyalkylene group having 2 to 10 carbon atoms, wherein the alkylene group is ethylene, methylethylene, ethylethylene, propylethylene, butylethylene, propylene, butylene, 1
-Methylpropylene group, pentylene group, hexylene group,
Examples thereof include linear or branched alkylene groups such as a heptylene group, an octylene group, a nonylene group, and a decylene group. Among these, an ethylene group, a propylene group, a butylene group, and a hexylene group are preferred. Examples of the alkyleneoxyalkylene group include an ethyleneoxypropylene group and an ethyleneoxybutylene group. -Ph- represents a substituted or unsubstituted phenylene ring, and specifically,
formula:

Embedded image (Wherein, R ⁴ is an alkyl group or alkoxy group having 1 to ⁴ carbon atoms or a halogen atom, and d is an integer of 0 to 4).
Examples of such a phenylene group include a p-phenylene group,
m-phenylene group, o-phenylene group, 2-methyl-
Examples thereof include a 1,4-phenylene group and a 2-methoxy-1,4-phenylene group. Among these, a p-phenylene group is preferred. A is a substituted or unsubstituted hydroxyphenyl group, preferably having the formula:

Embedded image (Wherein R ² is an alkyl or alkoxy group having 1 to 4 carbon atoms or a halogen atom, and b is an integer of 0 to 4). Specific examples of such a hydroxyphenyl group include a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group,
4-hydroxy-2-methoxyphenyl group, 3-hydroxy-4-methoxyphenyl group, 3-hydroxy-2-
Examples thereof include a methoxyphenyl group, a 2-hydroxy-4-methoxyphenyl group, and a 2-hydroxy-3-methoxyphenyl group. B is an alkylene group or an alkyleneoxyalkylene group having 2 or more carbon atoms, and specific examples of the alkylene group include an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. , An ethyleneoxypropylene group and an ethyleneoxybutylene group. x
Is an integer of 1 to 1,000, preferably an integer of 2 or more on average, and particularly preferably 2 to 800. y and z are integers from 0 to 1,000;
Preferably it is 500. y + z is an integer of 1 or more, and preferably 2 to 500. It is preferable that the ratio of x, y, and z is x / (x + y + z)> 0.1. This is because if the ratio is less than 0.1, the strength as a silphenylene compound is less likely to be exhibited when used as an organic resin modifier. a is 0 or 1; In the silphenylene compound of the present invention,
formula:

Embedded image The sequence of each repeating unit in the molecular chain represented by is arbitrary, and may be regular or random. Above all, at both ends,
formula:

Embedded image It is preferred to have a silphenylene unit represented by

[0006] As such a hydroxyphenyl group-containing silphenylene compound of the present invention, a compound represented by the following formula is exemplified. In the following formula, Me represents a methyl group.

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The hydroxyphenyl group-containing silphenylene compound of the present invention can be prepared by reacting a silylene compound having a general formula:

Embedded image (Wherein, R, R ¹ , Ph, x, y and z are the same as described above), and a silphenylene compound having a silicon-bonded hydrogen atom represented by the following formula: After an addition reaction with a hydrocarbon compound having an aliphatic unsaturated bond having a phenol group in which a hydroxyl group is protected by a triorganosilyl group or the like, a protecting group such as a triorganosilyl group is preferably acidified. It can be produced by adding methanol and the like in the presence of a catalyst, heating and desorbing. The silphenylene compound having a silicon-bonded hydrogen atom represented by the above general formula is, for example, a compound represented by the general formula:

Embedded image (Wherein R and Ph are the same as described above), or a condensation reaction of a commercially available dihydroxydisilylphenylene represented by the general formula:

Embedded image (Wherein, R and z are the same as described above, and Y is a hydrolyzable group such as a halogen atom or a hydroxyl group), and then subjected to a condensation reaction together with siloxane represented by the formula: By capping the terminal with tetramethyldisilazane represented by HMe ₂ Si) ₂ NH, a silphenylene compound in which y = 0 in the above general formula can be produced. In addition, a silphenylene compound having a silicon-bonded hydrogen atom represented by the above general formula is, for example, a general formula:

Embedded image (Wherein R and Ph are the same as described above), and a general formula having less than equimolar amounts of the disilylphenylene:

Embedded image (Wherein, R is the same as above, and R ⁵ has 2 to 2 carbon atoms)
10 alkenyl groups or alkenyloxyalkylene groups. ) Can also be produced by a method of hydrosilylation polymerization in the presence of a hydrosilylation reaction catalyst such as a platinum-based catalyst, a supported platinum-based catalyst, or a peroxide. After the polymerization, it is desirable to mix and adsorb the platinum-based catalyst with activated carbon, silica gel, silica gel treated with aminosilane, silica gel treated with mercaptosilane, and to remove by filtration. Examples of the alkenyl group for R ^{5 in} the above formula include a vinyl group, an allyl group, a butenyl group, a hexenyl group, and an octenyl group. Examples of the alkenyloxyalkylene group include a vinyloxyethylene group, a vinyloxypropylene group, and an allyloxy group. Examples include an ethylene group, an allyloxypropylene group, and an allyloxybutylene group. Also, the general formula:

Embedded image (Wherein R, Ph and R ⁵ are the same as described above), and a general formula having less than equimolar amount to the disilylphenylene:

Embedded image (In the formula, R is the same as described above.) By performing hydrosilylation polymerization in the same manner as described above using a disiloxane represented by the above formula, x, y, and z are all 1 in the above general formula.
The above-mentioned silphenylene compound can be produced.

Since the above-mentioned hydroxyphenyl group-containing silphenylene compound of the present invention has hydroxyphenyl groups at both molecular chain terminals, it can be used as a modifier for various organic resins, that is, a copolymerization reaction component of various organic resins. Used as For example, when the hydroxyphenyl group-containing silphenylene compound of the present invention is copolymerized with an organic resin monomer having a functional group such as a carboxyl group, an isocyanate group, or an epoxy group, the silphenylene-modified silphenylene unit is block-copolymerized. An organic resin is obtained. The copolymerization reaction ratio (mol%) between the silphenylene compound and the organic resin monomer is preferably in the range of 1:99 to 70:30, and more preferably 1:99.
~ 50: 50. Examples of the organic resin modified with the hydroxyphenyl group-containing silphenylene compound of the present invention include a polycarbonate resin, a polyarylate resin (aromatic polyester resin), a polysulfone resin, a phenol resin, and an epoxy resin. Among them, the hydroxyphenyl group-containing silphenylene compound of the present invention is suitably used as a copolymerization reaction component of a polycarbonate resin or a polyarylate resin.

Next, the silphenylene-modified polycarbonate resin of the present invention will be described. The silphenylene-modified polycarbonate resin of the present invention is a compound comprising a structural unit represented by the following structural formula (A) and a structural unit represented by the structural formula (B). Structural formula (A):

Embedded image Structural formula (B):

Embedded image In the above formula, R, R ¹ , R ² , -Ph-, B, x, y, z, a
And b are the same as above. R ³ is a halogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and specific examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group. You. E is a divalent hydrocarbon group having 1 to 20 carbon atoms, -O-, -S-,-
It is a group selected from the group consisting of CO- and -SO2-. Examples of the divalent hydrocarbon group include an alkylidene group, an aryl-substituted alkylidene group, an alkylene group, and an arylene group. The structure of the alkylidene group is linear, branched,
Any of cyclic groups may be used, and specific examples thereof include groups represented by the following formula.

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Embedded image Examples of the aryl-substituted alkylidene group include groups represented by the following formula.

Embedded image Examples of the alkylene group include a methylene group, an ethylene group, and an isopropylene group, and examples of the arylene group include a phenylene group. c is an integer of 0-4. The copolymerization ratio between the structural unit represented by the structural formula (A) and the structural unit represented by the structural formula (B) is 0.1 to 100 mol%: 9
9.9 to 0 mol%, preferably 1 to 70 mol%:
99 to 30 mol%, more preferably 1 to 50 mol%: 99 to 50 mol%. The molecular weight of the silphenylene-modified polycarbonate resin of the present invention is not particularly limited, but the number average molecular weight is preferably in the range of 5,000 to 300,000.

The silphenylene-modified polycarbonate resin of the present invention comprises the above-mentioned structural unit. If necessary, an antioxidant, a light stabilizer, a photocatalyst such as titanium oxide, a coloring agent, an inorganic or Organic fillers, reinforcing agents such as carbon fibers and glass fibers, lubricants such as Teflon powder, and antistatic agents can be added and blended.

Such a silphenylene-modified polycarbonate resin of the present invention can be prepared, for example, by mixing a hydroxyphenyl group-containing silphenylene compound of the present invention with a general formula:

Embedded image (Wherein R ³ , E and c are the same as described above), and phosgene, a carbonic acid diester or a polycarbonate oligomer is reacted with the dihydric phenol compound represented by the formula (1). In this production method, generally, a general production method of an aromatic polycarbonate resin is used, and examples thereof include a transesterification method by reaction with a carbonic acid diester and a phosgene method by reaction with phosgene. Examples of the phosgene method include an interfacial polymerization method and a pyridine method.

The dihydric phenol compounds represented by the above general formula include bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) ether, bis (4-
Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane,
2,2-bis (4-hydroxyphenyl) propane, 2,
2-bis (4-hydroxyphenyl) butane, 1,1-
Bis (4-hydroxyphenyl) cyclohexane, 2,
2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-
Dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane,
Examples include 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, and bis (4-hydroxyphenyl) diphenylmethane. Among these, 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane are preferred.

When the silphenylene-modified polycarbonate resin of the present invention is produced by a transesterification method, for example, a method of melt-polycondensing the hydroxyphenyl group-containing silphenylene compound of the present invention, the above-mentioned dihydric phenol compound and diphenyl carbonate. Is mentioned.
At this time, since the transesterification method is an equilibrium reaction, it is necessary to raise the temperature to 150 to 300 ° C. under vacuum to remove phenol as a by-product outside the system. The catalyst used here includes hydrides, hydroxides, oxides, alcoholates, phenolates, alkali metal and alkaline earth metal hydrides.
Organic and inorganic weak acid salts are exemplified. In addition, those generally used as transesterification catalysts may be used. If necessary, a molecular weight regulator (terminal terminator) can be used. Examples of the molecular weight regulator include organic compounds having a monovalent phenolic hydroxyl group, and specific examples thereof include phenol, p-tert-butylphenol, tribromophenol, long-chain alkylphenol, aliphatic carboxylic acid chloride, and aliphatic. carboxylic acid,
Examples thereof include hydroxybenzoic acid alkyl esters, hydroxyphenylic acid alkyl esters, and alkyl ether phenols. You may use these compounds in mixture of 2 or more types. The addition amount of this molecular weight regulator is 10 in total of the above-mentioned silphenylene compound and dihydric phenol compound.
It is preferably in the range of 100 to 0.5 mol, more preferably in the range of 50 to 2 mol, per 0 mol. The timing of adding the molecular weight regulator is not particularly limited as long as it is between the start and the end of the polymerization reaction. Further, by adding and blending a branching agent, a branched silphenylene-modified polycarbonate resin can also be produced. Phloroglysin, 2,6-
Dimethyl-2,4,6-tri (4-hydroxyphenyl)
Heptene-3,4,6-dimethyl-2,4,6-tri (4
-Hydroxyphenyl) heptene-2,1,3,5-tri (2-hydroxyphenyl) benzol, 1,1,1-tri (4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5 -Methylbenzyl) -methylphenol, α, α ', α'-tri (4-hydroxyphenyl)
Polyhydroxy compounds such as -1,3,5-triisopropylbenzene; 3,3-bis (1-hydroxyaryl) oxindole (= isatin bisphenol);
5-chlorisatin, 5,7-dichlorisatin, 5-
Bromoisatin is exemplified. The amount of the branching agent to be added is 0.01 to 3.0 mol% with respect to the total amount of the silphenylene compound and the dihydric phenol compound, particularly 0.1 to 1.0 mol. % Is preferable. This reaction can be carried out in the presence of an organic solvent inert to the polymerization reaction. Examples of such organic solvents include chlorination of dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, 1,1,1-trichloroethane, carbon tetrachloride, monochlorobenzene, dichlorobenzene and the like. Hydrocarbons; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; and ether compounds such as diethyl ether. These organic solvents may be used as a mixture of two or more. Further, an organic solvent having an affinity for water, such as ethers, ketones, esters, and nitriles, other than the above, is added within a range in which the mixed solvent system after the addition thereof is not completely compatible with water. If you can use it.

When the silphenylene-modified polycarbonate resin of the present invention is produced by an interfacial polymerization method,
For example, in the presence of an organic solvent and an aqueous alkali solution that are inert to the polymerization reaction, the hydroxyphenyl group-containing silphenylene compound of the present invention and the above-mentioned dihydric phenol compound, a molecular weight regulator (terminal terminator), After adding a branching agent and reacting these with phosgene, a method of performing interfacial polymerization using a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt may be mentioned. At this time, the mixing order of the silphenylene compound and the dihydric phenol compound is not particularly limited. For example, both can be reacted simultaneously, or a part of the silphenylene compound or dihydric phenol compound can be reacted with phosgene, and then reacted with the silphenylene compound or dihydric phenol compound. Examples of the polymerization catalyst include trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, tridecylamine, N, N-dimethylcyclohexylamine,
Tertiary amines such as pyridine, quinoline and dimethylaniline; trimethylbenzylammonium chloride;
And quaternary ammonium salts such as tetramethylammonium chloride and triethylbenzylammonium chloride. In addition, an antioxidant such as sodium sulfite or hydrosulfite may be appropriately added.

Next, the silphenylene-modified polycarbonate resin molded article of the present invention will be described. The molded article of the present invention is obtained by heating and melting the silphenylene-modified polycarbonate resin of the present invention, followed by molding and cooling and solidification, and a general molding method of an aromatic polycarbonate resin can be generally applied. Among these, the injection molding method is particularly preferably used. That is, after sufficiently drying the polycarbonate resin pellets, this is put into a hopper of an injection molding machine so as not to absorb moisture, and is then held.
It can be obtained by molding in a 320 ° C. cylinder.

A coating film can be obtained by dissolving the silphenylene-modified polycarbonate resin of the present invention as described above in an organic solvent such as methylene chloride and casting it on the surface of various substrates. Such a silphenylene-modified polycarbonate resin of the present invention has an advantage of excellent moldability. Further, the molded article of the silphenylene-modified polycarbonate resin has an advantage that the decrease in hardness is small and the mold releasability, water repellency, oil repellency, and mechanical properties are excellent.

Next, the silphenylene-modified polyarylate resin of the present invention will be described. The silphenylene-modified polyarylate resin of the present invention is a compound comprising a structural unit represented by the following structural formula (C) and a structural unit represented by the structural formula (D). Structural formula (C):

Embedded image Structural formula (D):

Embedded image In the above formula, R, R ¹ , R ² , R ³ , B, -Ph-, E, x,
y, z, a, b and c are the same as above. G is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, of which at least 50% is aromatic. Examples of the aromatic include an orthophenylene group, a metaphenylene group, a paraphenylene group, a naphthylene group, and a diphenylenealkane group. Examples of the divalent hydrocarbon group other than the aromatic group include an alkylene group, a cycloalkylene group, and a halogen substituent thereof. The copolymerization ratio of the structural unit represented by the structural formula (C) and the structural unit represented by the structural formula (D) is 0.1 to 100 mol%: 99.9.
０0 mol%, preferably 1-70 mol%: 99-
30 mol%, more preferably 1 to 50 mol%: 9
9 to 50 mol%. The molecular weight of the silphenylene-modified polyarylate resin of the present invention is not particularly limited,
Preferably, the weight average molecular weight is in the range of 5,000 to 300,000.

The silphenylene-modified polyarylate resin of the present invention comprises the above-mentioned constitutional unit. If necessary, the polyphenylene-modified polyarylate resin may be protected against oxidation of Teflon powder, other organic resins, sodium sulfite, hydrosulfite and the like. Agent,
Light stabilizers, photocatalysts such as titanium oxide, coloring agents, inorganic or organic fillers, reinforcing agents such as carbon fibers and glass fibers, lubricants, and antistatic agents can be added and blended.

Such a silphenylene-modified polyarylate resin of the present invention can be prepared, for example, by mixing a hydroxyphenyl group-containing silphenylene compound of the present invention with a general formula:

Embedded image (Wherein R ³ , E and c are the same as described above). The compound can be produced by subjecting a dihydric phenol compound represented by the following formula to a polycondensation reaction with an aromatic dicarboxylic acid. Examples of the reaction method include a usual melt polymerization method, an interfacial polymerization method, and a solution polymerization method.

The dihydric phenol compound represented by the above general formula includes 2,2-bis (4-hydroxyphenyl)
Propane, 1,1-bis (4-hydroxyphenyl) 1
-Phenylethane, hydroquinone, resorcinol,
4,4'-dihydroxybiphenyl, 1,1-bis (4-
(Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ethane, bis (3,5- Dimethyl-4-hydroxyphenyl) methane, bis (3,5-diethyl-4-hydroxyphenyl) methane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1-bis (3 , 5-Diethyl-4-hydroxyphenyl) ethane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (3,5-diethyl-4
-Hydroxyphenyl) propane, 2,2-bis (3.5
-Diethyl-4-hydroxyphenyl) propane, 2,
2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-2-methylphenyl) propane, 2,2-bis (2-allyl-4-hydroxyphenyl) propane, 2 , 2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy) hexafluoropropane, 1,1-
Bis (3,5-dimethyl-4-hydroxyphenyl) butane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) butane, 1,1-bis (3,5-diethyl-4)
-Hydroxyphenyl) butane, 2,2-bis (3,5-
Diethyl-4-hydroxyphenyl) butane, 1,1-
Bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-diethyl-4-hydroxyphenyl) cyclohexane, bis (3,5-dimethyl-4-hydroxyphenyl) phenylmethane, Bis (3,5-diethyl-4-hydroxyphenyl) phenylmethane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3,5-diethyl) -4-hydroxyphenyl) -1-
Phenylethane, bis (3,5-dimethyl-4-hydroxyphenyl) diphenylmethane, bis (3,5-diethyl-4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) ether, bis (3.5
-Dimethyl-4-hydroxyphenyl) ether, bis (3,5-diethyl-4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3,5-diethyl-4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3,5-diethyl-4-)
Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (3,5-dimethyl-4-hydroxyphenyl) ketone, bis (3,5-diethyl-4)
-Hydroxyphenyl) ketone, 4,4'-dihydroxydiphenyl. Among these, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane is preferred. The dihydric phenol compound may be used alone or in combination of two or more.

Examples of the aromatic dicarboxylic acid include orthophthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4'-dicarboxydiphenyl, bis (p-
(Carboxyphenyl) alkane. Of these, orthophthalic acid, terephthalic acid and isophthalic acid are preferred. These orthophthalic acid, terephthalic acid,
Isophthalic acid may be used alone or may be used as a mixture, and the mixing ratio is not particularly limited. Further, in the silphenylene-modified polyarylate resin of the present invention, a part of the aromatic dicarboxylic acid may be replaced with another aromatic-free dicarboxylic acid as long as its properties are not practically impaired. . Such dicarboxylic acids include cyclohexanedicarboxylic acid,
Examples include alicyclic or aliphatic dicarboxylic acids such as adipic acid, sebacic acid, and glutaric acid, and halides thereof. Such a dicarboxylic acid accounts for not more than 50 mol% of all dicarboxylic acids,
The following is preferred.

When the silphenylene-modified polyarylate resin of the present invention is produced by a melt polymerization method, for example, an acetylated dihydric phenol compound, an aromatic dicarboxylic acid, and a hydroxyphenyl group-containing silphenylene compound of the present invention are used. May be polymerized at a high temperature under reduced pressure using a catalyst such as a Lewis acid, if necessary. When the silphenylene-modified polyarylate resin of the present invention is produced by an interfacial polymerization method, a solution obtained by dissolving terephthalic acid or isophthalic acid as an acid halide in an organic solvent incompatible with water is used. A solution in which a dihydric phenol compound is dissolved in an aqueous alkaline solution and a solution in which the hydroxyphenyl group-containing silphenylene compound of the present invention is suspended in an aqueous alkaline solution may be mixed and stirred.

Next, the coating agent of the present invention will be described. The coating agent of the present invention contains the silphenylene-modified polyarylate resin of the present invention as a main component, and is usually used in a form in which the polyarylate resin is dissolved in an organic solvent. As the organic solvent, a hydrocarbon solvent which is liquid at room temperature is used, and specifically, an aromatic hydrocarbon solvent such as toluene and xylene; an aliphatic hydrocarbon solvent such as hexane, heptane, octane and nonane; cyclohexane Alicyclic hydrocarbon solvents such as cyclohexane, cycloheptane and cyclooctane;
Fluorine-containing aromatic hydrocarbon solvents such as trifluoromethylbenzene, 1,3-bis (trifluoromethyl) benzene and methylpentafluorobenzene; methylene chloride, dichloromethane, 1,2-dichloroethane, 1,1,
2,2-tetrachloroethane, chloroform, 1,1,1
-Chlorinated hydrocarbon solvents such as trichloroethane, carbon tetrachloride, monochlorobenzene, dichlorobenzene and the like. The compounding amount is 20 to 10 parts per 100 parts by weight of the silphenylene-modified polyarylate resin.
000 is preferred. Further, the coating agent of the present invention may contain various conventionally known additives as long as the object of the present invention is not impaired. Examples of such various additives include polydiorganosiloxane-based friction modifiers such as polydimethylsiloxane and polymethylphenylsiloxane; aminoalkyl trialkoxy silanes, epoxy-functional alkoxy silanes, methacryloxy propyl trialkoxy silanes, vinyl tri Silane coupling agent-based adhesion improver such as alkoxysilane; silica gel, colloidal silica, titanium oxide,
Inorganic fillers such as alumina; and fluorine resins insoluble in organic solvents such as Teflon. By casting such a coating agent of the present invention on the surface of various substrates and removing the solvent, a high-hardness coating thin film having excellent water repellency can be obtained.

The silphenylene-modified polyarylate resin of the present invention as described above has good solubility in a solvent. For example, when this is used in a form dissolved in a solvent, the solvent is volatilized after coating. By itself, there is an advantage that a high-hardness film having low surface tension and excellent in transparency, water repellency, heat resistance, weather resistance, mold release properties and the like can be formed without using a curing catalyst or the like. Therefore, the silphenylene-modified polyarylate resin of the present invention is suitably used as a coating agent or a paint. Furthermore, the silphenylene-modified polyarylate resin of the present invention has excellent moldability, and the resulting molded article has a small decrease in hardness, and has a releasability, water repellency,
It has the advantage of excellent oil repellency and mechanical properties.
The molded product is obtained by heating and melting the silphenylene-modified polyarylate resin of the present invention, followed by molding and solidification by cooling. Generally, a general molding method for polyarylate resin can be applied. Among these, the injection molding method is particularly preferably used. That is, after sufficiently drying the silphenylene-modified polyarylate resin pellets, throwing them into a hopper of an injection molding machine so as not to absorb moisture, holding them, and then molding them in a cylinder at a temperature of 250 to 320 ° C. Can be.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. In the examples, Me means a methyl group, and the viscosity and the refractive index are measured values at 25 ° C.

[0026]

Embodiment 1 Formula:

Embedded image 59 g of 1,4-bis (chlorodimethylsilyl) phenylene represented by the following formula is dissolved in 60 g of toluene, and
The solution was added dropwise to 3 g with stirring. After the addition was completed, the reaction mixture was mixed for 1 hour. Next, the toluene layer was separated and washed until neutral. Further azeotropic dehydration,
13 g of tetramethyldisilazane represented by the formula: (HMe ₂ Si) ₂ NH was added, the mixture was heated under reflux for 2 hours, and volatile components were removed under reduced pressure to obtain 46 g of a reaction product. When the reaction product was analyzed by infrared spectroscopy (hereinafter, IR), Si-H bonds were observed. Further, when analyzed by ¹³ C-nuclear magnetic resonance analysis (hereinafter, ¹³ C-NMR) and ²⁹ Si-nuclear magnetic resonance analysis (hereinafter, ²⁹ Si-NMR), this reaction product was represented by the following average structural formula. It was found to be a silphenylene compound having silicon-bonded hydrogen atoms at both ends. Hereinafter, this compound is referred to as “compound P1”.

Embedded image 24.2 g (SiH: 50 mmol) of this "Compound P1", and 15.1 g of trimethylsilyl-o-allylphenol.
5 g (75 mmol) and a complex of platinum and tetramethyldivinyldisiloxane were added in such an amount that the amount of platinum metal was 10 ppm based on the total amount of the two compounds.
The reaction mixture obtained by heating these at 100 ° C. for 2 hours was analyzed by IR, and it was found that the characteristic absorption of the Si—H group had disappeared. Subsequently, low-boiling substances were distilled off from the reaction mixture by heating under reduced pressure to obtain 31 g of a reaction product. The reaction product was analyzed by ¹³ C-NMR, ²⁹ Si-
Analysis by NMR and IR revealed that the reaction product was a silphenylene compound represented by the following structural formula.

Embedded image After 30 g of the silphenylene compound and 8 g of methanol were mixed and stirred at 50 ° C. for 3 hours, low-boiling substances were distilled off by heating under reduced pressure to obtain 25.5 g of a reaction product. The reaction product was analyzed by ¹³ C-NMR, ²⁹ Si-NMR and IR.
As a result, the reaction product was found to be a hydroxyphenyl group-containing silphenylene compound represented by the following structural formula.

Embedded image

[0027]

Embodiment 2 Formula:

Embedded image 78 g (0.4 mol) of 1,4-bis (dimethylsilyl) phenylene and 37 g (0.2 mol) of 1,3-
Divinyltetramethyldisiloxane, 179 g of toluene, and a complex of platinum and tetramethyldivinylsiloxane were blended in an amount such that the amount of platinum metal was 15 ppm based on the total amount of the two compounds, and was mixed at a reflux temperature of about Stir for 4 hours. After cooling this once, 64g
(0.48 mol) of o-allylphenol,
The mixture was again stirred and heated. Subsequently, aging was continued for 4 hours, and then toluene and volatile components were stripped under a condition of 2-3 mmHg / 150 ° C./1 hour to obtain 138 g of a liquid reaction product (yield: 85%). The refractive index of this reaction product was 1.54. This is also called IR, ¹³
Upon analysis by C-NMR and ²⁹ Si-NMR, the reaction product was of the formula:

Embedded image Was found to be a hydroxyphenyl group-containing silphenylene compound represented by the following formula:

[0028]

Example 3 In a reaction vessel, 114 g of 2,2-bis (4-hydroxyphenyl) propane, 29.2 g of the hydroxyphenyl group-containing silphenylene compound obtained in Example 2,
126 g of diphenyl carbonate, 100 g of toluene and 0.02 g of lithium hydrogen were added, and these were heated and stirred under a nitrogen atmosphere, and the solvent was refluxed for 30 minutes. Then, the pressure is gradually reduced to a gentle vacuum (100 to 50).
mmHg), and when the temperature was gradually increased, 160
Distillation of phenol was observed under the condition of ~ 180 ° C.
The temperature was raised more slowly to 250 ° C. and maintained at this temperature until the distillation of phenol was almost complete. Thereafter, the degree of vacuum was gradually increased to 1 mmHg or less, the temperature was set to 290 ° C., and the reaction was performed for 2 hours. After cooling,
The reaction polymer was reprecipitated using methylene chloride-isopropanol. The precipitate was filtered and dried to obtain a white powdery resin. The obtained resin was subjected to ¹³ C-NMR and
Analysis by ²⁹ Si-NMR revealed that this resin was a silphenylene-modified polycarbonate resin comprising structural units represented by the following structural formulas (A-1) and (B-1). The copolymerization ratio of these constituent units (A
-1): (B-1) was 7:93 (mol%).
The weight average molecular weight of the obtained resin was measured using gel permeation chromatography (GPC) and found to be 23,000. Structural formula (A-1):

Embedded image Structural formula (B-1):

Embedded image The silphenylene-modified polycarbonate resin thus obtained was dissolved in methylene chloride to prepare a 10% concentration solution. This is coated on an aluminum plate and the temperature is 120
It dried under the conditions of ° C and formed a transparent coat. The contact angle of the obtained coating film with water was measured with a contact angle meter. The pencil hardness was measured according to the method specified in JIS K5400. Table 1 shows the results of these measurements. Further, in the above, a coating film was formed by using a Teflon sheet instead of the aluminum plate, and then the Teflon sheet was peeled off, whereby a transparent thin plate was obtained.

[0029]

Comparative Example 1 In Example 3, a hydroxyphenyl group-containing silphenylene compound was used without using a compound represented by the formula:

Embedded image A white resin was obtained in the same manner as in Example 3, except that 47 g of a linear hydroxyphenyl group-containing dimethylpolysiloxane represented by the following formula was used and the amount of diphenyl carbonate (126 g) was changed to 123.7 g. . When the obtained resin was analyzed by ¹³ C-NMR and ²⁹ Si-NMR, the resin was found to have the following structural formula (A-2) and structural formula (B-
It was found that the resin was a silicone-modified polycarbonate resin comprising the structural unit represented by 2). Its weight average molecular weight was 19,000. Structural formula (A-2):

Embedded image Structural formula (B-2):

Embedded image A coating film was formed in the same manner as in Example 3 using the thus obtained silicone-modified polycarbonate resin. The contact angle with water and the pencil hardness of the obtained coating film were measured in the same manner as in Example 3. Table 1 shows the results of these measurements.

[0030]

[Table 1]

[0031]

EXAMPLE 4 4.57 g of 2,2-bis (4-hydroxyphenyl) propane was placed in a reaction vessel, and the hydroxyphenyl group-containing silphenylene compound 4.22 obtained in Example 2 was obtained.
g, sodium hydroxide 2.0 g, and water 150 g, and stirred at room temperature. Next, 2.54 g of terephthaloyl dichloride and 2.54 g of isophthaloyl dichloride were added thereto.
A solution dissolved in 00 g of dichloromethane was added. After stirring for 3 hours at room temperature to carry out emulsion polymerization, a large amount of acetone was added and the polymer was separated by filtration. Then, washing was repeatedly performed with water and acetone. Next, the polymer was dried to obtain a white powdery resin. When the obtained resin was analyzed by NMR, it was found that this resin was a silphenylene-modified polyarylate resin comprising structural units represented by the following structural formulas (C-1) and (D-1). . Copolymerization ratio of these constituent units (C-1):
(D-1) was approximately 20:80 in mol%. The weight average molecular weight of the obtained resin was measured by GPC and found to be 25,000.

Embedded image The silphenylene-modified polyarylate resin thus obtained was dissolved in methylene chloride to prepare a solution having a concentration of 10% by weight. After coating this on an aluminum plate, temperature 12
Drying was performed under the condition of 0 ° C. to form a transparent coating film. The contact angle of the obtained coating film with water was measured with a contact angle meter.
The pencil hardness was measured according to the method specified in JIS K5400. Table 2 shows the results.
Further, in the above, a coating film was formed by using a Teflon sheet instead of the aluminum plate, and then the Teflon sheet was peeled off. As a result, a transparent thin plate was obtained.

[0032]

Comparative Example 2 In Example 4, the compound represented by the following formula was used without using the hydroxyphenyl group-containing silphenylene compound.

Embedded image A white resin was obtained in the same manner as in Example 4 except that 8.4 g of a linear hydroxyphenyl group-containing dimethylpolysiloxane represented by the following formula was used. NMR analysis of the obtained resin revealed that it was a silicone-modified polyarylate resin comprising structural units represented by the following structural formulas (C-2) and (D-2). Its weight average molecular weight was 19,000.

Embedded image A coating film was formed in the same manner as in Example 4 using the obtained silicone-modified polyarylate resin. The contact angle with water and the pencil hardness of the obtained coating film were measured in the same manner as in Example 4. Table 2 shows the results.

[0033]

[Table 2]

[0034]

The hydroxyphenyl group-containing silphenylene compound of the present invention is a novel compound having a hydroxyphenyl group at both ends of the molecular chain and is used as an organic resin modifier, particularly a polycarbonate resin modifier or a polyarylate resin modifier. It has the feature of being useful. Further, the silphenylene-modified polycarbonate resin of the present invention obtained by copolymerizing the silphenylene compound has excellent moldability, and the resulting molded article has excellent releasability and water repellency. The silphenylene-modified polyarylate resin of the present invention has a feature that it forms a high hardness film having excellent water repellency and is useful as a coating agent.

[Brief description of the drawings]

FIG. 1 is an IR spectrum chart of a hydroxyphenyl group-containing silphenylene compound produced in Example 2.

FIG. 2 is a ¹³ C-NMR spectrum chart of a hydroxyphenyl group-containing silphenylene compound produced in Example 2.

FIG. 3 is a ²⁹ Si-NMR spectrum chart of a hydroxyphenyl group-containing silphenylene compound produced in Example 2.

FIG. 4 is an IR spectrum chart of a silphenylene-modified polyarylate resin produced in Example 4.

FIG. 5 shows the silphenylene modified product prepared in Example 4.
Polyarylate resin ¹³C-NMR spectrum char
It is.

FIG. 6 is a graph showing the change in silphenylene produced in Example 4.
Polyarylate resin ²⁹Si-NMR spectrum
It is.

──────────────────────────────────────────────────の Continuing on the front page (51) Int.Cl. ⁶ Identification code FI C08G77 / 448 C08G77 / 448 (72) Inventor Tohru Masatomi 2-2 Chikusa-kaigan, Ichihara-shi, Chiba Dow Corning Toray Toray Co., Ltd. R & D headquarters

Claims (8)

[Claims] 1. A compound of the general formula: (Wherein, R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, and R ¹ has 2 to 10 carbon atoms.
Wherein -Ph- represents a substituted or unsubstituted phenylene ring, A is a substituted or unsubstituted hydroxyphenyl group, and B is an alkylene group having 2 or more carbon atoms or alkylene. It is an oxyalkylene group. x is 1 to 1,00
0 is an integer, y is an integer from 0 to 1,000, z
Is an integer of 0 to 1,000, and y + z is an integer of 1 or more. a is 0 or 1; ) A hydroxyphenyl group-containing silphenylene compound represented by the formula: 2. The hydroxyphenyl group of A is of the formula: (Wherein R ² is an alkyl group or alkoxy group having 1 to 4 carbon atoms or a halogen atom, and b is an integer of 0 to 4). A phenyl group-containing silphenylene compound. 3. The hydroxyphenyl group-containing silphenylene compound according to claim 1, which is an organic resin modifier. 4. A silphenylene-modified organic resin obtained by subjecting the organic resin modifier according to claim 3 to a copolymerization reaction with an organic resin monomer. 5. A structural unit represented by the following structural formula (A):
0.1 to 100 mol% of the structural unit represented by the structural formula (B)
The sill according to claim 4, comprising: 99.9 to 0 mol%.
Phenylene-modified polycarbonate resin. Structural formula (A):(Wherein R is the same or different and does not contain an aliphatic unsaturated bond)
Species of monovalent hydrocarbon radicals, R¹Is 2 to 10 carbon atoms
An alkylene group or an alkyleneoxyalkylene group
Yes, R^TwoIs an alkyl group having 1 to 4 carbon atoms or
A alkoxy group or a halogen atom, and -Ph-
Or B represents an unsubstituted phenylene ring, wherein B is the number of carbon atoms
Two or more alkylene groups or alkyleneoxyalkylene
Group. x is an integer from 1 to 1,000, and y is 0
Is an integer of ~ 1,000, and z is an integer of 0 ~ 1,000
However, y + z is an integer of 1 or more. a is 0 or 1
And b is an integer of 0 to 4. ) Structural formula (B):(Where R^ThreeIs a halogen atom or a group having 1 to 4 carbon atoms.
E is a monovalent hydrocarbon group, and E is a divalent having 1 to 20 carbon atoms.
Hydrocarbon group, -O-, -S-, -CO-, -SO _Two-Or
A group selected from the group consisting of: c is an integer of 0 to 4
is there. ) 6. A molded article of a silphenylene-modified polycarbonate resin obtained by molding the silphenylene-modified polycarbonate resin according to claim 5. 7. A structural unit represented by the following structural formula (C):
The silphenylene-modified polyarylate resin according to claim 4, comprising 0.1 to 100 mol% and a structural unit represented by the structural formula (D): 99.9 to 0 mol%. Structural formula (C): [Wherein, R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, and R ¹ has 2 to 10 carbon atoms.
R ² is an alkyl or alkoxy group having 1 to 4 carbon atoms or a halogen atom, -Ph- represents a substituted or unsubstituted phenylene ring, and B is a carbon atom G is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms (provided that at least 50% of G is aromatic) is there.). x is 1 to 1,000
Y is an integer of 0 to 1,000, z is an integer of 0 to 1,000, and y + z is an integer of 1 or more. a is 0 or 1, and b is an integer of 0-4. Structural formula (D): Wherein R ³ is a halogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, E is a divalent hydrocarbon group having 1 to 20 carbon atoms, —O—, —S—, —CO —, —SO ₂ —, a group selected from the group consisting of
0 is a substituted or unsubstituted divalent hydrocarbon group (provided that at least 50% of G is aromatic), and c is an integer of 0 to 4. ] 8. A coating agent comprising the silphenylene-modified polyarylate resin according to claim 7 as a main component.