JP2000248067A - Organic resin modifier, silicone-modified organic resin and coating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic resin modifier comprising an organopolysiloxane having two hydroxyphenyl groups in a molecule, and to provide a silicone- modified organic resin and a coating agent obtained by copolymerization using the above modifier as a comonomer. SOLUTION: This organic resin modifier is a hydroxyphenyl group-containing silicone expressed by the formula [wherein, Rs are each a monovalent hydrocarbon group not containing an aliphatic unsaturated bond; A is (substituted) hydroxyphenyl; Q is a polydiorganosiloxane chain; (d) is an integer of 2-8]. This silicone-modified organic resin and coating agent are obtained by copolymerizing the above modifier with an organic resin monomer containing a functional group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an organic resin modifier, a silicone-modified organic resin, and a coating agent.
More specifically, the present invention relates to an organic resin modifier comprising an organopolysiloxane having two hydroxyphenyl groups in one molecule, a silicone-modified organic resin modified by the modifier, and a coating agent.

[0002]

2. Description of the Related Art Organopolysiloxanes having organic functional groups are used in a wide variety of fields as modifiers for organic resins, surfactants, fiber treatment agents and the like. In particular, when used as a modifier of an organic resin, when used as a raw material of a so-called copolymer in which organopolysiloxane is incorporated into an organic resin molecule, it can be copolymerized with the organic resin. It is necessary to select a suitable organic functional group. For example, when the organic resin is obtained mainly by a polycondensation reaction such as a polycarbonate resin, a linear organopolysiloxane containing a hydroxyphenyl group is generally used as a modifier thereof. (See JP-A-3-79626).

On the other hand, among organosiloxanes containing a hydroxyphenyl group, those having a p-hydroxyphenyl group are known to have excellent reactivity. Such p-hydroxyphenyl group-containing organosiloxane can be obtained, for example, by a method of hydrosilylating p-hydroxystyrene with a silicon-bonded hydrogen atom-containing organosiloxane (see Japanese Patent Application Laid-Open No. Hei 8-127559), A method of subjecting a hydrogen atom-containing organosiloxane to a hydrosilylation reaction of p-butoxyallylbenzene and then hydrolyzing a butoxy group bonded to a benzene ring to convert it to a hydroxy group (see JP-A-2-225524). Can be manufactured. However, in the former hydrosilylation reaction with p-hydroxystyrene, both α-adduct and β-adduct are formed, so that the reaction product contains isomers, and
When butoxyallylbenzene is used, there is a disadvantage that hydrolysis after the addition reaction is slow and it is difficult to be converted into a hydroxy group, and a highly pure p-hydroxyphenyl group-containing organosiloxane cannot be efficiently obtained.

[0004]

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 an organic resin modifier comprising an organopolysiloxane having two hydroxyphenyl groups in one molecule, a silicone-modified organic resin obtained by copolymerizing the modifier, and a coating agent. It is in.

[0005]

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, A is a substituted or unsubstituted hydroxyphenyl group, Q is a polydiorganosiloxane chain, and d is A hydroxyphenyl group-containing silicone represented by the general formula (2) to (8), and a silicone-modified organic compound obtained by copolymerizing the modifier with a functional group-containing organic resin monomer. It relates to a resin and a coating agent.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION First, the organic resin modifier of the present invention will be described in detail. The organic resin modifier of the present invention,
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, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl Groups, octyl groups, nonyl groups, decyl groups and other alkyl groups; phenyl groups, tolyl groups,
Aryl group such as xylyl group; aralkyl group such as benzyl group and phenethyl group; 3,3,3-trifluoropropyl group, 1H, 1H, 2H, 2H-perfluorohexyl group,
Halogen-substituted alkyl groups such as 1H, 1H, 2H, 2H-perfluorodecyl groups are exemplified. Among them, a methyl group or a phenyl group is preferable. The R may be the same or different. A is a substituted or unsubstituted hydroxyphenyl group, preferably having the formula:

Embedded image A p-hydroxyphenyl group represented by In the above formula,
R ¹ is an alkyl group having 1 to 4 carbon atoms, an alkoxy group or a halogen atom, and a is an integer of 0 to 4. As such a hydroxyphenyl group, specifically, 4-
Examples thereof include a hydroxyphenyl group, a 4-hydroxy-3-methylphenyl group, and a 4-hydroxy-2-methylphenyl group. Q is a polydiorganosiloxane chain, which is any polydiorganosiloxane chain having two silicon atoms as bonds. Preferably, the formula:

Embedded image Or a linear siloxane chain represented by the formula:

Embedded image Is a cyclic siloxane chain represented by In the above formula, R is the same as described above. m is an integer of 1 to 300,
It is preferably in the range of 200, more preferably in the range of 4 to 100. n is an integer of 1 to 13, and particularly preferably 2 or 3. In the above formula, (n + 2) is a number indicating the degree of polymerization of the cyclic siloxane chain. x is an integer of 0 or more and n or less, and these n and x may be the same or different. d is 2
It is an integer of 8, but is usually 2 or 3.

The hydroxyphenyl group-containing silicone used in the organic resin modifier of the present invention includes:
Examples include compounds represented by the following formula. In the following formula, Me represents a methyl group, and Ph represents a phenyl group.

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The organic resin modifier of the present invention can be prepared, for example, by reacting a compound represented by the formula: H
(R ₂ SiO) _m —SiR ₂ H (wherein R and m are the same as defined above), and a linear polydiorganosiloxane having silicon-bonded hydrogen atoms at both ends, or a compound represented by the formula :

Embedded image (Wherein R, n and x are the same as described above), and a cyclic diorganosiloxane having two silicon-bonded hydrogen atoms in one molecule represented by the formula (P):

Embedded image (Wherein R, R ¹ and a are the same as above, and R ³ is an alkenyl group having 2 to 8 carbon atoms) by an addition reaction with an alkenyl group-containing phenol silane compound represented by the formula: Can be manufactured. As the alkenyl group for R ^3, a vinyl group or an allyl group is preferable. Also,
As the alkenyl group-containing phenol silane compound, those in which the hydroxyl group in the phenol group is protected by a triorganosilyl group or the like are preferable. When such a phenol silane compound is used, after the addition reaction is completed, the protecting group may be removed by adding methanol or the like in the presence of an acid catalyst and heating. Examples of the catalyst for the hydrosilylation reaction include a platinum-based catalyst, a rhodium-based catalyst, a palladium-based catalyst, and an organic peroxide.
Of these, platinum-based catalysts are particularly preferable. Specifically, platinum black, platinum-supported silica fine powder, platinum-supported carbon powder, chloroplatinic acid, an alcohol solution of chloroplatinic acid,
A complex of platinum and vinyl siloxane and a complex of platinum and olefin are exemplified. This addition reaction can be performed under heating or in the presence of an organic solvent. Specific examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and nonane; cyclohexane, cycloheptane,
An alicyclic hydrocarbon solvent such as cyclooctane; and a fluorine-containing aromatic hydrocarbon solvent such as trifluoromethylbenzene and 1,3-bis (trifluoromethyl) benzene can be used.

The above-mentioned hydroxyphenyl group-containing silicone used in the organic resin modifier of the present invention has a structure in which a siloxane chain and a hydroxyphenyl group are bonded via a silalkylene group. This is synthesized by performing an addition reaction between a diorganosiloxane containing a silicon-bonded hydrogen atom and a phenolsilane containing an alkenyl group. According to this method, there is an advantage that the desired hydroxyphenyl group-containing silicone can be obtained with high purity. The hydroxyphenyl group-containing silicone is a viscous liquid at room temperature and has a surface tension between that of polydimethylsiloxane and an organic material (20 to 30 mN).
/ M). In addition, the molecular chain is not easily broken by an ionic substance such as an acid or an alkali, and the hydrolysis resistance is excellent. Therefore, the organic resin modifier of the present invention is useful as a general industrial material utilizing such characteristics.

Further, since the organic resin modifier of the present invention comprising a p-hydroxyphenyl group-containing silicone has good reactivity, it can be used, for example, in various organic compounds having a carboxyl group, isocyanate group, epoxy group or the like as a functional group. The copolymerization reaction with the resin monomer gives the formula:

Embedded image (Wherein, R, Q and d are the same as described above) to obtain a silicone-modified organic resin obtained by block copolymerization of a siloxane unit represented by the following formula: In the silicone-modified organic resin, the copolymerization reaction ratio between the organic resin modifier and the organic resin monomer is preferably in the range of 1:99 to 70:30, and more preferably 1:99 to 50: 5.
It is in the range of 0. Examples of the organic resin to be modified include a polycarbonate resin, a polyarylate resin, a polysulfone resin, a phenol resin, and an epoxy resin.
Among them, the organic resin modifier of the present invention is suitably used as a copolymerization reaction component of a polycarbonate resin or a polyarylate resin.

Next, the silicone-modified polycarbonate resin of the present invention will be described in detail. The silicone-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 In the above formula, R, R ¹ , Q, a and d are the same as described above. Structural formula (B):

Embedded image In the above formula, R ² is a halogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and specific examples of the monovalent hydrocarbon group include alkyl such as methyl, ethyl, propyl, and butyl. Groups: alkenyl groups such as vinyl group and allyl group. D is a divalent hydrocarbon group having 1 to 20 carbon atoms,-
O -, - S -, - CO -, - it is a group selected from the group consisting of - SO _2. Specifically as a divalent hydrocarbon group,
Examples include an alkylidene group, an aryl-substituted alkylidene group, an alkylene group, a cycloalkylene group, an arylene group, and a group obtained by bonding these groups. The structure of the alkylidene group may be linear, branched or cyclic, and specific examples include groups represented by the following formula.

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. Other than these, a group represented by the following formula is exemplified.

Embedded image b is an integer of 0-4.

In the silicone-modified polycarbonate resin of the present invention, the copolymerization ratio of the structural unit represented by the structural formula (A) to the structural unit represented by the structural formula (B) is 0.1 to 10;
0 mol%: 99.9 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 is not particularly limited, but the weight average molecular weight is 5,000.
It is preferably in the range of 0 to 300,000.

The silicone-modified polycarbonate resin of the present invention comprises the above-mentioned constitutional unit. Depending on the intended use, an antioxidant such as polytetrafluoroethylene powder or other organic resin, sodium sulfite or hydrosulfite is used. , A light stabilizer, a photocatalyst such as titanium oxide, a coloring agent, an inorganic or organic filler, a reinforcing agent such as carbon fiber and glass fiber, a lubricant, and an antistatic agent.

[0014] Such a silicone-modified polycarbonate resin of the present invention may be, for example, an organic resin modifier of the present invention and a compound represented by the following general formula:

Embedded image (Wherein R ² , D and b 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 (I). Usually, a general method for producing an aromatic polycarbonate resin is used, for example,
Examples 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.

As the dihydric phenol compound represented by the above general formula, 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 (2-allyl-4-hydroxyphenyl) propane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 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, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-
Bis (4-hydroxyphenyl) -1-phenylethane and bis (4-hydroxyphenyl) diphenylmethane are exemplified. Among these, 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane are preferred.

When the silicone-modified polycarbonate resin of the present invention is produced by a transesterification method, for example, a method of melt polycondensation of the organic resin modifier of the present invention, the above-mentioned dihydric phenol compound and diphenyl carbonate is mentioned. Can be At this time, since the transesterification method is an equilibrium reaction, the temperature is set to 150 to 300 ° C. under vacuum.
It is necessary to remove phenol by-product out of the system. The catalysts used here include alkali metals,
Examples include alkaline earth metal hydrides, hydroxides, oxides, alcoholates, phenolates, and organic and inorganic weak acid salts. In addition, those generally used as transesterification catalysts may be used. Also, if necessary,
Molecular weight regulators (terminal terminators) 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, hydroxybenzoic acid alkyl ester, hydroxyphenyl acid alkyl ester,
Examples are alkyl ether phenols. You may use these compounds in mixture of 2 or more types. The amount of the molecular weight modifier to be added is preferably in the range of 100 to 0.5 mol, more preferably in the range of 50 to 1 mol, per 100 mol of the total of the organic resin modifier and the dihydric phenol compound. More preferred. 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. By adding and blending a branching agent,
A branched silicone-modified polycarbonate resin can also be produced. Examples of the branching agent include 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 polyhydroxy compounds such as, α ', α'-tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene; 3,3-bis (1-
(Hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin, 5,7-dichlorisatin, 5-bromoisatin are exemplified. The amount of the branching agent to be added is from 0.01 to 3.0 mol%, especially from 0.1 to 1.0 mol%, based on the total amount of the organic resin modifier and the dihydric phenol compound. It is preferable that the amount is as follows. This reaction can be carried out in the presence of an organic solvent inert to the polymerization reaction. Such organic solvents include dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, 1,1,1-trichloroethane, carbon tetrachloride,
Chlorinated hydrocarbons such as monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; and ether compounds such as diethyl ether are exemplified. 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 silicone-modified polycarbonate resin of the present invention is produced by an interfacial polymerization method, for example, the organic resin-modified polycarbonate resin of the present invention is prepared in the presence of an organic solvent inert to the polymerization reaction and an aqueous alkali solution. After adding an agent and the above-mentioned dihydric phenol compound, molecular weight regulator (terminal terminator) and branching agent to react them with phosgene, a polymerization catalyst such as tertiary amine or quaternary ammonium salt To perform interfacial polymerization. At this time, the mixing order of the organic resin modifier and the dihydric phenol compound is not particularly limited. For example, both can be reacted simultaneously, or a part of the organic resin modifier or the dihydric phenol compound can be reacted with phosgene, and then reacted with the remaining organic resin modifier or the 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.

The silicone-modified polycarbonate resin of the present invention as described above is dissolved in an organic solvent such as methylene chloride, and then cast on the surface of various substrates to obtain a releasability, water repellency and oil repellency. An excellent high hardness coating film can be obtained. Therefore, it is suitably used as a coating agent. The molded article of the silicone-modified polycarbonate resin of the present invention has a releasability, water repellency, oil repellency,
Excellent mechanical properties. This molded article is obtained by heating and melting the polycarbonate resin, followed by molding and solidification by cooling. As a molding method, a method usually applied to a method for molding an aromatic polycarbonate resin can be used, and an injection molding method is particularly preferably used. That is, after sufficiently drying the silicone-modified polycarbonate resin pellet, it is put into a hopper of an injection molding machine so as not to absorb moisture, held, and then molded in a cylinder at a temperature of 250 to 320 ° C., thereby forming a polycarbonate resin molded product. Can be obtained.

Next, the silicone-modified polyarylate resin of the present invention will be described in detail. The silicone-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 following structural formula (D). Structural formula (C):

Embedded image In the above formula, R, R ¹ , Q, d and a are the same as described above. E is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, at least 50% of which 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. Structural formula (D):

Embedded image In the above formula, R ² , D, E and b are the same as described above.

In the silicone-modified polyarylate resin of the present invention, the copolymerization ratio of the structural unit represented by the structural formula (C) to the structural unit represented by the structural formula (D) is 0.1 to 10:
0 mol%: 99.9 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 is not particularly limited, but the weight average molecular weight is 5,000.
It is preferably in the range of 0 to 300,000.

The silicone-modified polyarylate resin of the present invention comprises the above-mentioned constitutional unit. Depending on the purpose of use, the antioxidant such as Teflon powder and other organic resins, sodium sulfite and hydrosulfite, and the like. 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 silicone-modified polyarylate resin of the present invention comprises, for example, an organic resin modifier of the present invention,
General formula:

Embedded image (Wherein R ² , D and b are as defined above) and a polycondensation reaction of an aromatic dicarboxylic acid with a dihydric phenol compound represented by the formula (I). As a reaction method, a usual melt polymerization method, interfacial polymerization method, solution polymerization method, or the like is used.

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.

The aromatic dicarboxylic acids 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, during the production of the silicone-modified polyarylate resin of the present invention, a part of the aromatic dicarboxylic acid may be replaced with another dicarboxylic acid as long as the properties are not practically impaired. Examples of such dicarboxylic acids include alicyclic or aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, adipic acid, sebacic acid and glutaric acid, and halides thereof. Further, this type of dicarboxylic acid is preferably 50 mol% or less, more preferably 20 mol% or less, based on all dicarboxylic acids.

When the silicone-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 the organic resin modifier of the present invention are required. Accordingly, polymerization may be performed at a high temperature under reduced pressure using a catalyst such as a Lewis acid. When the silicone-modified polyarylate resin of the present invention is produced by an interfacial polymerization method, a solution obtained by dissolving terephthalic acid and isophthalic acid as acid halides in an organic solvent which is incompatible with water, A solution in which a dihydric phenol compound is dissolved in an aqueous alkali solution and a solution in which the organic resin modifier of the present invention is suspended in an aqueous alkali solution may be mixed and stirred.

The silicone-modified polyarylate resin of the present invention as described above is dissolved in an organic solvent such as dichloromethane, and then cast on the surface of various substrates to obtain releasability, water repellency and oil repellency. An excellent high hardness coating film can be obtained. Therefore, it is suitably used as a coating agent. Further, the silicone-modified polyarylate resin of the present invention has good moldability, and the obtained molded article is excellent in mold release properties, water repellency, oil repellency, and mechanical properties. A molded article is obtained by heating and melting the polyarylate resin, followed by molding and cooling and solidification. As a molding method, a method generally applied to a method for molding a polyarylate resin can be used, and particularly, an injection molding method is suitably used. That is, after sufficiently drying the silicone-modified polyarylate resin pellets, the pellets are put into a hopper of an injection molding machine so as not to absorb moisture, and then kept at a temperature of 25%.
A polyarylate resin molded article can be obtained by molding in a cylinder at 0 to 320 ° C.

[0028]

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

[0029]

[Reference Example 1] In a reaction vessel, the formula:

Embedded image 29.6 g (0.1 mol) of diethyltetramethylcyclotetrasiloxane represented by the formula:
0.4 g of carbon particles carrying 5% of platinum metal was charged and heated to 60 ° C. While stirring these, the formula:

Embedded image A mixture of 35.6 g (0.2 mol) of p-hydroxyphenyldimethylvinylsilane represented by the formula and 46 g of toluene was added dropwise. After the completion of the dropwise addition, the mixture was heated under reflux for 2 hours. Then, the mixture was cooled and filtered, and volatile components were distilled off under reduced pressure to obtain 58 g of a viscous liquid. The yield was 89%. This viscous liquid is subjected to Fourier transform infrared spectroscopy (hereinafter referred to as FT-I
R), ¹³ C-nuclear magnetic resonance spectrum analysis (hereinafter, ¹³ C-
NMR) and ²⁹ Si-nuclear magnetic resonance spectroscopy (hereinafter referred to as ²⁹ Si-NMR) confirmed that the silicone was a cyclic p-hydroxyphenyl group-containing silicone represented by the following formula.

Embedded image (In the formula, the ratio between x = 1 and x = 0 was 1: 1.)

[0030]

Example 1 In a reaction vessel, 114 g of 2,2-bis (4-hydroxyphenyl) propane, 23.1 g of the p-hydroxyphenyl group-containing silicone obtained in Reference Example 1, 126 g of diphenyl carbonate, 100 g of toluene and 0 g of lithium hydrogen were used. Then, the mixture was heated and stirred under a nitrogen atmosphere to reflux the solvent for 30 minutes. Then, the pressure was gradually reduced to a gentle vacuum (100 to 50 mmHg), and the temperature was gradually increased. As a result, phenol was distilled off at 160 to 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, and the temperature was lowered to 29 mmHg.
The reaction was carried out at 0 ° C. for 2 hours. After cooling, methylene chloride
The reaction polymer was reprecipitated using isopropanol. The precipitate was filtered and dried to obtain a white powdery resin. NMR analysis of the obtained resin revealed that it was a silicone-modified polycarbonate resin comprising the structural units represented by the following structural formulas (A-1) and (B-1). The copolymerization ratio (A-
1) :( B-1) was approximately 7:93 in mol%. The weight average molecular weight of the obtained resin was measured by gel permeation chromatography (GPC) and found to be 23,000. Structural formula (A-1):

Embedded image (In the formula, the ratio between the case where x = 1 and the case where x = 0 is 1: 1.) Structural formula (B-1):

Embedded image The obtained silicone-modified polycarbonate resin was dissolved in methylene chloride to prepare a solution having a concentration of 10%. This was applied to an aluminum plate and dried at a temperature of 120 ° C. to obtain a transparent coating film. The contact angle of this coating film with water was measured with a contact angle meter. The pencil hardness is determined by JIS K
It was measured according to the method specified in 5400. The results are shown in Table 1. 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.

[0031]

[Comparative Example 1] In Example 1, instead of the hydroxyphenyl group-containing silicone obtained in Reference Example 1, a compound represented by the following formula:

Embedded image A white resin was obtained in the same manner as in Example 1 except that 47 g of a linear hydroxyphenyl group-containing dimethylpolysiloxane represented by the following formula was used, and the blending amount of diphenyl carbonate (126 g) was changed to 123.7 g. NMR analysis of the obtained resin revealed that it was a silicone-modified polycarbonate resin comprising the structural units represented by the following structural formulas (A-2) and (B-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 1 using the 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 1. The results are shown in Table 1.

[0032]

[Table 1]

[0033]

Example 2 In a reaction vessel, 2.85 g (0.0125 mol) of 2,2-bis (4-hydroxyphenyl) propane,
8.15 g (0.0125 mol) of the p-hydroxyphenyl group-containing silicone obtained in Reference Example 1 and 2.0 g of sodium hydroxide were added, and these were dissolved in 150 ml of water. While vigorously mixing this solution with a homomixer,
2.54 g of terephthaloyl dichloride (0.012
5 mol) and 2.54 g (0.012) of isophthaloyl dichloride
(5 mol) in 75 ml of chloroform was added dropwise. After completion of the dropwise addition, the mixture was stirred for 1 hour. Next, a large amount of acetone was added thereto, and the polymer was separated by filtration, washed with water and acetone, and dried to obtain a white powdery resin. When the obtained resin was analyzed by FT-IR and NMR, it was found to be a silicone-modified polyarylate resin comprising structural units represented by the following structural formulas (C-1) and (D-1). . The copolymerization ratio (C-1) :( D-1) of these constituent units is about 50:50 by mol%.
Met. The weight average molecular weight of the obtained resin was determined by GPC.
Was 45,000. Structural formula (C-1):

Embedded image (In the formula, the ratio between the case where x = 1 and the case where x = 0 is 1: 1 and the ratio between the case where the phthalate ester portion is m-position and the case where the phthalate ester portion is p-position is 1: 1. Structural formula (D-1):

Embedded image (The ratio of the m-position to the p-position of the phthalic acid ester portion was 1: 1.) The obtained silicone-modified polyarylate resin was dissolved in chloroform to prepare a 10% by weight solution. . This was cast on a glass plate and dried at 100 ° C. for 10 minutes to obtain a colorless and transparent film. The pencil hardness of this film was 2H, and the contact angle with water was 102 degrees.

[0034]

Example 3 In a reaction vessel, 2.85 g (0.0125 mol) of 2,2-bis (4-hydroxyphenyl) propane was added.
formula:

Embedded image 8.8 a hydroxyphenyl group-containing silicone represented by the formula:
3 g (0.0124 mol) and sodium hydroxide 2.0
g were dissolved in 150 ml of water. While vigorously mixing this solution with a homomixer, 2.54 g (0.0125 mol) of terephthaloyl dichloride and 2.54 g (0.0125 mol) of isophthaloyl dichloride were added thereto.
A solution dissolved in 5 ml of chloroform was added dropwise. After completion of the dropwise addition, the mixture was stirred for 1 hour. Subsequently, a large amount of acetone was added thereto, and the polymer was separated by filtration, washed with water and acetone, and dried to obtain a white powdery resin. The obtained resin is F
Analysis by T-IR and NMR revealed that the resin was a silicone-modified polyarylate resin comprising structural units represented by the following structural formulas (C-2) and (D-2). Copolymerization ratio of these constituent units (C-2):
(D-2) was about 50:50 by mol%. The weight average molecular weight of the obtained resin was measured by GPC and found to be 45,000. Structural formula (C-2):

Embedded image (In the formula, the ratio of the m-position to the p-position of the phthalate ester portion was 1: 1.) Structural formula (D-2):

Embedded image (The ratio of the m-position to the p-position of the phthalic acid ester portion was 1: 1.) The obtained silicone-modified polyarylate resin was dissolved in chloroform to prepare a 10% by weight solution. . This was cast on a glass plate and dried at 100 ° C. for 10 minutes to form a colorless and transparent film. The pencil hardness of the obtained film was 2H, and the contact angle with water was 101 degrees.

[0035]

The organic resin modifier of the present invention is an organopolysiloxane having two hydroxyphenyl groups in one molecule, and is particularly useful as a modifier for a polycarbonate resin or a modifier for a polyarylate resin. Has advantages. Further, the silicone-modified organic resin of the present invention modified by the organic resin modifier has an advantage that it is useful as a coating agent.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4J029 AA03 AA09 AB01 AC01 AC02 AD01 AE11 BB12A BB12B BB12C BB13A BB13B BE05A BE05B BF14A BF14B BG08X BG20X BG24X BH02 BH04 CB04A01B12 CB05A01 CB05A01 CA08M CA081 CA15M CA152 CA30M CA301 FB01 FB02 GA04 GB02 GB08 LB01 4J038 DD171 DE021 DL051

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, A is a substituted or unsubstituted hydroxyphenyl group, Q is a polydiorganosiloxane chain, and d is A hydroxyphenyl group-containing silicone represented by the formula (1): 2. The substituted or unsubstituted hydroxyphenyl group of A is represented by the formula: (In the formula, R ¹ is an alkyl group, an alkoxy group or a halogen atom having 1 to 4 carbon atoms, a is an integer of 0-4.) The organic resin modifier according to claim 1, which is represented by. 3. The polydiorganosiloxane chain of Q is
Formula: (Wherein, R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, and m is an integer of 1 to 300), or a linear siloxane chain represented by
Formula: (Wherein, R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, n is an integer of 1 to 13, and x is an integer of 0 to n). The organic resin modifier according to claim 1 or 2, which is a cyclic siloxane chain. 4. A silicone-modified organic resin obtained by subjecting the organic resin modifier according to claim 1 and a functional group-containing organic resin monomer to a copolymerization reaction. 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)
5. The silicon according to claim 4, comprising 99.9 to 0 mol%.
Corn-modified polycarbonate resin. Structural formula (A):(In the formula, R is the same species containing no aliphatic unsaturated bond or
Different monovalent hydrocarbon groups,¹Is 1 to 4 carbon atoms
An alkyl group, an alkoxy group or a halogen atom
Q is a polydiorganosiloxane chain;
And d is an integer of 2 to 8. Structural formula (B):(Where R^TwoIs a halogen atom or a group having 1 to 4 carbon atoms.
A monovalent hydrocarbon group, wherein D is a divalent C 1-20 carbon atom,
Hydrocarbon group, -O-, -S-, -CO-, -SO _Two-Or
A group selected from the group consisting of:
is there. ) 6. A coating agent comprising the silicone-modified polycarbonate resin according to claim 5. 7. A structural unit represented by the following structural formula (C):
0.1 to 100 mol% of the structural unit represented by the structural formula (D)
5. The silicon according to claim 4, comprising 99.9 to 0 mol%.
Corn-modified polyarylate resin. Structural formula (C):[Wherein, R is the same or a group containing no aliphatic unsaturated bond or
Different monovalent hydrocarbon groups,¹Is 1 to 4 carbon atoms
An alkyl group, an alkoxy group or a halogen atom
And E is a substituted or unsubstituted divalent group having 1 to 20 carbon atoms.
Is a monovalent hydrocarbon group (provided that at least 50
% Is aromatic. ). Q is polydiorganosiloxane
A is an integer of 0 to 4 and d is an integer of 2 to 8
It is. Structural formula (D):[Wherein, R^TwoIs a halogen atom or a group having 1 to 4 carbon atoms.
A monovalent hydrocarbon group, wherein D is a divalent C 1-20 carbon atom,
Hydrocarbon group, -O-, -S-, -CO-, -SO _Two-Or
A group selected from the group consisting of:
20 substituted or unsubstituted divalent hydrocarbon groups (provided that
However, at least 50% of this E is aromatic. ).
b is an integer of 0-4. ] 8. A coating agent comprising the silicone-modified polyarylate resin according to claim 7.