JP2002332401A - Polycarbonate-styrene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate-styrene resin composition having excellent flame retardance and causing almost no mold deposits. SOLUTION: This resin composition is composed of a cagelike silsesquioxane represented by the following general formula (A) or a partially cleaved structure of a cagelike silsesquioxane represented by the following general formula (B) [RSiO3/2 ]n (A) (RSiO3/2 )n-m (O1/2 H)2+m (B) [in the general formula (A) and general formula (B), Rs denote each any one kind of hydrogen atom, a 1-20C saturated hydrocarbon group, a 2-20C alkenyl group, a 7-20C aralkyl group, a 6-20C aryl group and a 1-10 Si silicon atom-containing group and a plurality of Rs may be the same or different; n is an integer of 6-14; and m is 0 or 1] and a polycarbonate-styrene resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cage silsesquioxane containing a specific component and a polycarbonate-styrene resin composition using the same. More specifically, a cage-like silsesquioxane or a partially-cleaved cage-like silsesquioxane having an effect of improving the flame retardancy of a polycarbonate-styrene resin, and a polycarbonate-styrene resin composition to which the cage-like silsesquioxane is added. It is about.

[0002]

2. Description of the Related Art Polycarbonate resins are lighter and more excellent in impact resistance than metals or glass, and are therefore used in a wide variety of fields including automobile parts, home appliance parts, and OA equipment parts. ing. On the other hand, thinning and weight reduction of molded products in the above fields manufactured using thermoplastic resins,
The demand for better appearance is increasing. Therefore, attempts have been made to improve the fluidity of a thermoplastic resin used for producing a molded article in the above field, improve the moldability, and obtain a thin, lightweight molded article. As a method for improving the moldability of polycarbonate, alloying with a styrene resin having excellent moldability such as acrylonitrile-butadiene-styrene (ABS) is generally used. However, in this method, although the moldability is improved, there is a problem that the flame retardancy is reduced.

As a method for improving the flame retardancy of a polycarbonate-styrene resin, it is known to add a halogen-based, phosphorus-based, inorganic-based or a mixture thereof to the resin. However, in recent years, demands for fire safety have been particularly noticed, and at the same time, technical development of a flame retardant-containing polycarbonate resin composition having no environmental problem has been strongly desired. In other words, a new flame retardant which does not contain halogens and phosphorus and has no environmental problems, has a high flame retardant effect and high recyclability, and does not reduce the practical performance such as the mechanical properties of the resin composition is desired. I have. As a flame retardant that may meet such demands, a method of using an organosilicon compound as a flame retardant has been proposed at present. In the case of an alloy such as polycarbonate / ABS, etc. obtained by kneading a styrene resin such as ABS containing a styrene and a rubber component, the required flame retardancy cannot be obtained.

[0004]

SUMMARY OF THE INVENTION In view of such circumstances, the present invention provides a mold deposit (mold) which is excellent in environmental safety and free of the above-mentioned problems, that is, has excellent flame retardancy. It is an object of the present invention to provide a polycarbonate-styrene resin composition with less contamination.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies on organosilicon compounds having excellent environmental safety in order to solve the above problems. As a result, among the many organosilicon-based compounds, the cage-shaped silsesquioxane compound and the partially-cleaved structure of the cage-shaped silsesquioxane provide excellent moldability improvement and flame retardancy to the polycarbonate-styrene resin. It shows that it has good properties and exhibits excellent characteristics that there is little mold deposit,
The present invention has been completed.

That is, the present invention provides: (1) a cage silsesquioxane represented by the following general formula (A) or a partially cleaved structure of a cage silsesquioxane represented by the following general formula (B) Body and polycarbonate
A resin composition composed of a styrene resin. [RSiO _3/2 ] _n (A) (RSiO _3/2 ) _nm (O _1/2 H) _{2 + m} (B) [In the above general formulas (A) and (B), R
Is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a silicon atom having 1 to 10 silicon atoms Represents any one of the contained groups, and a plurality of Rs may be the same or different. n is 6 to 1
And m is 0 or 1. ]

(2) The polycarbonate-styrene resin described in (1) is a component of a copolymer of (a) a polycarbonate resin and (b) an aromatic vinyl monomer and a vinyl cyanide monomer. And at least one or more of (c) an aromatic vinyl monomer component, a vinyl cyanide monomer component, and an alkyl (meth) acrylate monomer are a rubbery polymer And a graft copolymer obtained by graft-polymerizing the above. (3) The composition of the polycarbonate-styrene resin described in (2) is (a) 90 to 10% by weight, (b) 1 to 5% by weight.
0% by weight and (c) 1 to 50% by weight.

(4) The content of the cage silsesquioxane represented by the general formula (A) or the cage silsesquioxane represented by the general formula (B) is partially 0.1% by weight or more and 50% by weight based on the resin composition composed of the resin and the polycarbonate-styrene resin.
The resin composition according to any one of (1) to (3), wherein: (5) Includes the cage silsesquioxane represented by the general formula (A) or the partially-cleaved cage silsesquioxane represented by the general formula (B) (1) to (4).
A molded article comprising the polycarbonate-styrene resin composition according to any one of the above.

The polycarbonate resin (a) used in the present invention is obtained by reacting a phenol compound having a valency of 2 or more with a carbonate bond-forming agent such as diester carbonate such as diphenyl carbonate or phosgene. The divalent or higher phenol compound is a dihydric phenol, for example, 2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A],
Bis (4-hydroxyphenyl) methane; bis (4-hydroxyphenyl) phenylmethane; bis (4-hydroxyphenyl) naphthylmethane; bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane; bis (3,5 -Dimethyl-4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane;
1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane; 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane; 1,2-bis (4-hydroxyphenyl) ethane; 2-methyl -1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (3,5-
Dimethyl-4-hydroxyphenyl) propane; 1-ethyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (3-methyl-4-hydroxyphenyl) propane; 2,2-bis (3 -Fluoro-4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) butane; 1,4-bis (4-hydroxyphenyl) butane; 2 2,2-bis (4-hydroxyphenyl) pentane; 4-methyl-2,2-bis (4-hydroxyphenyl) pentane; 2,2-bis (4-hydroxyphenyl) hexane; 2,2-bis (4- 2,2-bis (4-hydroxyphenyl) nonane; 1,10-bis (4-hydroxyphenyl) decane; 1, - bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane; 2,2
-Bis (4-hydroxyphenyl) -1,1,1,3,
Dihydroxydiaryl realcans such as 3,3-hexafluoropropane; 1,1-bis (4-hydroxyphenyl) cyclohexane; dihydroxydiarylcycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclodecane; bis (4-hydroxyphenyl)
Sulfones; dihydroxydiaryl sulfones such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) ether; dihydroxydiaryl such as bis (3,5-dimethyl-4-hydroxyphenyl) ether Ethers, 4,4
'-Dihydroxybenzophenone;3,3', 5,5
Dihydroxydiaryl ketones such as'-tetramethyl-4,4'-dihydroxybenzophenone;
-Hydroxyphenyl) sulfide; bis (3-methyl-4-hydroxyphenyl) sulfide; bis (3,5
Dihydroxydiaryl sulfides such as -dimethyl-4-hydroxyphenyl) sulfide, dihydroxy diaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide, dihydroxy diphenyls such as 4,4'-dihydroxyphenyl, and 9,9-bis ( And dihydroxyarylfluorenes such as 4-hydroxyphenyl) fluorene. Further, in addition to the dihydric phenol, dihydroxybenzenes such as hydroquinone, resorcinol, and methylhydroquinone; dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene; and 2,6-dihydroxynaphthalene are also included. Among these, 2,2-bis (4-hydroxydiphenyl) propane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (3,5-dimethyl-4-hydroxyphenyl) Methane, 1-phenyl-1,1-bis (4
-Hydroxyphenyl) ethane, 2,2-bis (3,5
-Dimethyl-4-hydroxyphenyl) propane, 1,
1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bis (4-hydroxyphenyl) sulfone, and 4,4′-dihydroxybenzophenone are difficult to mold and process for the polycarbonate resin composition of the present invention. It is also preferable from the viewpoints of flammability, mechanical strength of the obtained molded article, and flame retardancy, and more preferably 2,2-bis (4
-Hydroxydiphenyl) propane, 1,1-bis (4
-Hydroxyphenyl) -3,3,5-trimethylcyclohexane is preferred.

These dihydric phenols and the like may be used alone or in combination of two or more. Further, a polycarbonate-polyorganosiloxane copolymer in which a polyorganosiloxane structure is inserted into a part of the polycarbonate can also be used. In that case, the degree of polymerization of the polyorganosiloxane portion is preferably 5 or more.

As the carbonic acid diester compound, diaryl carbonates such as diphenyl carbonate;
Examples thereof include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate. As the terminal stopper for the polycarbonate part, various known ones can be used. Specifically, examples of the monohydric phenol include phenol, p-cresol, pt-butylphenol, pt-octylphenol, p-cumylphenol, bromophenol, tribromophenol, nonylphenol and the like. In order to further enhance the flame retardancy, a copolymer with a phosphorus-containing compound or a polycarbonate resin end-blocked with a phosphorus-containing compound can be used. To further improve the weather resistance,
A polycarbonate resin end-capped with a dihydric phenol having a benzotriazole group can be used.

The vinyl monomer which is a component of the copolymer containing (b) an aromatic vinyl monomer and a vinyl cyanide monomer as a component of the copolymer is styrene, α -Aromatic vinyl monomers such as methylstyrene and paramethylstyrene; alkyl (meth) acrylates such as methyl methacrylate, methyl acrylate, butyl acrylate and ethyl acrylate; (meth) acrylic acids such as acrylic acid and methacrylic acid; Α, β-unsaturated carboxylic acids such as maleic acid; maleimide monomers such as N-phenylmaleimide, N-methylmaleimide and N-cyclohexylmaleimide; and glycidyl group-containing monomers such as glycidyl methacrylate. Preferably, aromatic vinyl monomer, alkyl (meth) acrylates, maleimide A monomer, more preferably, styrene, N- phenylmaleimide, butyl acrylate. These vinyl monomers may be used alone or
More than one species can be used in combination.

Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and acrylonitrile is preferred. In the copolymer (b) of the present invention containing an aromatic vinyl monomer and a vinyl cyanide monomer as constituent components of the copolymer, butyl acrylate occupying the copolymer as a vinyl monomer Should be 0.5 to 80% by weight, preferably 0.5 to 60% by weight, and more preferably 1 to 40% by weight.
% By weight. If the amount is less than 0.5% by weight, high fluidity cannot be obtained, and the effect of improving impact resistance is small. On the other hand, when the content exceeds 80% by weight, heat resistance is significantly reduced.

Next, the composition and production method of the graft copolymer (c) of the present invention will be described. The graft copolymer (c) can be obtained by graft-polymerizing a vinyl monomer capable of being graft-polymerized onto a rubbery polymer, and may contain a vinyl polymer which is simultaneously polymerized in the polymerization process. Absent. Examples of the rubbery polymer used in the present invention include conjugated diene rubbers such as polybutadiene, polyisoprene, polychloroprene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene rubber, ethyl acrylate, and acrylic. Acrylic rubbers such as butyl acid are preferred, but conjugated diene rubbers such as polybutadiene, butadiene-styrene copolymer and butadiene-acrylonitrile copolymer are preferred. These can be used in combination of two or more. The content of the rubbery polymer in the graft copolymer (c) of the present invention is 3 to 80% by weight, preferably 5 to 70% by weight. If it is less than 3% by weight, impact resistance cannot be obtained, and if it exceeds 80% by weight, the fluidity and gloss during molding are reduced, which is not preferable.

Examples of the vinyl monomer that can be graft-polymerized on the rubbery polymer include aromatic vinyl monomers such as styrene, α-methylstyrene and paramethylstyrene, methyl methacrylate, methyl acrylate, butyl acrylate, and the like.
Alkyl (meth) acrylate monomers such as ethyl acrylate; (meth) acrylic acids such as acrylic acid and methacrylic acid; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; α and β such as maleic anhydride
Maleimide monomers such as unsaturated carboxylic acids, N-phenylmaleimide, N-methylmaleimide and N-cyclohexylmaleimide; and glycidyl group-containing monomers such as glycidyl methacrylate. Monomers, alkyl (meth) acrylates, vinyl cyanide monomers and maleimide monomers, more preferably styrene, acrylonitrile, N-phenylmaleimide, and butyl acrylate. These vinyl monomers can be used alone or in combination of two or more.

The vinyl polymer which can be contained in the graft copolymer (c) of the present invention includes aromatic vinyl monomers such as styrene, α-methylstyrene, paramethylstyrene and the like.
Alkyl (meth) acrylates such as methyl methacrylate, methyl acrylate, butyl acrylate, and ethyl acrylate; (meth) acrylic acids such as acrylic acid and methacrylic acid; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; maleic anhydride; Maleimide monomers such as α, β-unsaturated carboxylic acid, N-phenylmaleimide, N-methylmaleimide and N-cyclohexylmaleimide; and glycidyl group-containing monomers such as glycidyl methacrylate. It is an aromatic vinyl monomer, an alkyl (meth) acrylate, a vinyl cyanide monomer, or a maleimide monomer, and is more preferably a polymer composed of styrene, acrylonitrile, N-phenylmaleimide, and butyl acrylate. . These vinyl monomers can be used alone or in combination of two or more, or can be used after copolymerization.

As a specific example of the graft copolymer (c) of the present invention, high impact polystyrene resin (HIP
S), acrylonitrile-butadiene-styrene (AB
S) Resins and the like. The method for producing the graft copolymer (c) of the present invention is not particularly limited, but an emulsion graft polymerization system in which a vinyl monomer is graft-polymerized to a rubbery polymer latex produced by emulsion polymerization, and A two-stage polymerization method combining graft polymerization with solution polymerization or suspension polymerization is exemplified. These can be any of a continuous type, a batch type, and a semi-batch type. In addition, a graft copolymer having a high rubber content is prepared in advance by the above method, and then a thermoplastic resin containing a vinyl monomer as a main component used in the graft polymerization produced by bulk polymerization, emulsion polymerization or suspension polymerization is blended. To obtain the desired rubber content.

In the present invention, an emulsion grafting method in which a vinyl monomer is continuously added to a rubbery polymer produced by emulsion polymerization together with an initiator, a molecular weight regulator and the like is preferable. The pH at the time of polymerization is not particularly limited, but is preferably around neutral (pH 7 to 9) from the viewpoint of the graft reaction. The average particle size of the obtained graft copolymer is 0.1 to 1.5 μm.
m is preferable, and 0.15 to 0.8 μm is more preferable.
And particularly preferably 0.2 to 0.6 μm.
If it is less than 0.1 μm, the effect of improving the impact resistance of the resin composition will be insufficient, and if it exceeds 1.5 μm, the fluidity and appearance of the molded product will be poor. In the present invention, a composite rubber-based graft copolymer may be used. A composite rubber having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are alternately entangled and combined and integrated, A composite rubber-based graft copolymer obtained by graft polymerization of one or more vinyl monomers.
Rubber polymers which can be produced by the method described in JP-A-4-79257 are preferably used.

The method for producing the composite rubber-based graft copolymer is not particularly limited, but an emulsion graft polymerization method in which a vinyl monomer is graft-polymerized to a latex-like rubbery polymer produced by emulsion polymerization, and And a two-stage polymerization method in which emulsion graft polymerization is combined with solution polymerization or suspension polymerization. These can be any of a continuous type, a batch type, and a semi-batch type. In addition, a graft copolymer having a high rubber content is prepared in advance by the above method, and then a thermoplastic resin containing a vinyl monomer as a main component used in the graft polymerization produced by bulk polymerization, emulsion polymerization or suspension polymerization is blended. It is also possible to keep.

Next, the cage silsesquioxane used in the present invention and its partially cleaved structure will be described. Whereas the silica is represented by the general formula [SiO _2], silsesquioxane is a compound represented by [R 'SiO _3/2]. Silsesquioxane is usually R ′ Six ₃ (R ′ =
A hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, etc., X = halogen, alkoxy group, etc.) A polysiloxane synthesized by hydrolysis-polycondensation of a compound. Is an amorphous structure,
Ladder-like structure, cage-like (completely condensed cage-like) structure or its partially-cleaved structure (structure in which one silicon atom is missing from a cage-like structure, or structure in which a silicon-oxygen bond is partially broken in a cage-like structure), etc. It has been known.

The present inventors have studied in detail the effect of adding various silsesquioxane compounds to a polycarbonate resin. As a result, among various silsesquioxane compounds, cage silsesquioxanes, that is, cage silsesquioxane represented by the above general formula (A), or cage silsesquioxane represented by the above general formula (B) Polycarbonate resin that gives a molded article with excellent moldability (or melt flowability) and excellent flame retardancy when a partially cleaved structure of fibrous silsesquioxane is added to a polycarbonate resin at a specific ratio. The present inventors have found that a composition can be obtained and completed the present invention. [RSiO _3/2 ] _n (A) (RSiO _3/2 ) _nm (O _1/2 H) _{2 + m} (B) [In the above general formulas (A) and (B), R
Is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, an aryl group having 7 to 20 carbon atoms, and a silicon atom having 1 to 10 silicon atoms In the containing group, a plurality of Rs may be the same or different. n is an integer of 6 to 14, and m is 0 or 1. ]

Examples of the cage silsesquioxane represented by the general formula (A) used in the present invention include [RSi
O _3/2] type represented by the chemical formula ₆ (the following general formula _{(1)), [RSiO 3/2} ] type represented by ₈ of formula (the following formula _{(2)), [RSiO 3} /2 The type represented by the chemical formula ( ₁₀ ) (the following general formula (3)), [RSiO
_3/2 ] ₁₂ (general formula (4) below), and [RSiO _3/2 ] ₁₄ (general formula (5)).

[0023]

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[0024]

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The above-mentioned general formula (A) of the present invention [RSi
The value of n in the cage silsesquioxane represented by O _3/2 ] _n is an integer of 6 to 14, preferably 8, 10 or 12, and particularly preferably 8 or 8,10. , 12. In the present invention,
The above-mentioned general formula (B) [RSiO _3/2 ], which is obtained by partial cleavage of a silicon-oxygen bond in a cage silsesquioxane.
_{nm (O 1/2 H) 2 +} m (n is an integer from 6 to 14,
m is 0 or 1. )), A partially-cleaved cage-like silsesquioxane structure may also be used. For example, a trisilanol compound [R
The type represented by the chemical formula of SiO _3/2 ] ₇ (O _1/2 H) ₃ (the following general formula (6)), [RSiO _3/2 ] ₈ (O _1/2 H)
) The type represented by the chemical formula ₂ (the following general formula (7)), the type represented by the chemical formula [RSiO _3/2 ] ₈ (O _1/2 H) ₂ (the following general formula (8)), etc. No.
In the following general formulas (6), (7) and (8), the silanol group and R bonded to the same silicon atom may have their positions exchanged with each other.

[0026]

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The type of R used in the present invention includes a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an araalkyl group having 7 to 20 carbon atoms, and a carbon atom having 7 to 20 carbon atoms. Examples thereof include an aryl group having 6 to 20 and a silicon atom-containing group having 1 to 10 silicon atoms represented by the following general formulas (9) and (10). Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, butyl (n-butyl, i-butyl, t-butyl, sec-butyl), pentyl (n-butyl Pentyl, i-pentyl, neopentyl, cyclopentyl, etc.), hexyl (n-hexyl, i-hexyl, cyclohexyl, etc.), heptyl (n-heptyl,
i-heptyl, etc.), octyl (n-octyl, i-octyl, t-octyl, etc.), nonyl (n-nonyl, i-nonyl, etc.), decyl (n-decyl, i-decyl, etc.), undecyl (n-octyl, etc.) Undecyl, i-undecyl, etc.), dodecyl (n-dodecyl, i-dodecyl, etc.) and the like.

As the alkenyl group having 2 to 20 carbon atoms, any of acyclic alkenyl groups and cyclic alkenyl groups can be used. Examples include vinyl, propenyl, butenyl, pentenyl, hexenyl, cyclohexenyl, cyclohexenylethyl, norbornenylethyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, and the like. Examples of aralkyls having 7 to 20 carbon atoms include benzyl, phenethyl or benzyl or phenethyl which is mono- or multi-substituted with alkyl having 1 to 13 carbon atoms, more preferably 1 to 8 carbon atoms. No. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a phenyl group substituted with an alkyl group having 1 to 14, more preferably 1 to 8 carbon atoms,
Examples include a tolyl group and a xylyl group.

When R in the cage silsesquioxane or its partially cleaved structure used in the present invention is a hydrocarbon group, it is preferable that R is an alkyl or alkenyl group as a main component. These compounds have a large effect of improving the melt fluidity and a large effect of improving the flame retardancy even during combustion. In addition, when one molecule contains a small amount of an aryl group or an araalkyl group as R 1, for example, when one is contained, a good effect is exhibited. The number of carbon atoms in R of the hydrocarbon structure in the above general formulas (A) and (B) is usually 20 or less, but the balance of melt fluidity, flame retardancy and operability at the time of molding. It is preferably 16 or less, particularly preferably 12 or less.
The following are used:

The number of silicon atoms used as R is 1 to 10
As the silicon atom-containing group having a wide range of structures, examples thereof include groups having the following general formula (9) or the following general formula (10). The number of silicon atoms in the silicon atom-containing group is generally in the range of 1 to 10, preferably in the range of 1 to 6, more preferably 1 to 6.
3 range. If the number of silicon atoms is too large, the cage silsesquioxane compound becomes a viscous liquid, which makes handling and purification difficult.

[0031]

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In the general formula (9), n is usually from 1 to 1.
It is an integer in the range of 0, preferably an integer in the range of 1 to 6, more preferably an integer in the range of 1 to 3. Also,
The substituents R ₅ and R ₆ in the general formula (9) are a hydrogen atom or an organic group having 1 to 10, preferably 1 to 6 carbon atoms.

Examples of the organic group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group and a cyclohexyl group; a group containing an unsaturated bond such as a vinyl group and an allyl group;
Alternatively, a substituted alkyl group such as a fluorinated alkyl group such as CF ₃ CH ₂ CH ₂ —, an aryl group such as a phenyl group and a tolyl group, and an araalkyl group such as a benzyl group and a phenethyl group are exemplified.

R ₇ in the above formula (9) is a hydrogen atom or an organic group having 1 to 20, preferably 1 to 12, more preferably 1 to 8 carbon atoms. Examples of the organic group include 1) a methyl group, an ethyl group, a propyl group,
Alkyl groups such as butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, 2-cyclohexyl-ethyl group, octyl group and dodecyl group; 2) alkenyl groups such as vinyl group, allyl group and 2-cyclohexenyl-ethyl group Groups, 3) aryl groups such as phenyl group, tolyl group, and alkyl-substituted phenyl group; 4) araalkyl groups such as benzyl group and phenethyl group; and 5) fluorine-containing groups such as 3,3,3-trifluoro-n-propyl group. Alkyl group or CF ₃
Examples include a partially substituted hydrocarbon group such as a fluorinated ether group such as a CF ₂ CF ₂ OCH ₂ CH ₂ CH ₂ — group. In the general formula (9), the same silicon atom has 2
No two or more hydrogen atoms are linked at the same time.

Specific examples of the silicon atom-containing group represented by the general formula (9) include, for example, trimethylsiloxy,
Dimethylphenylsiloxy, diphenylmethylsiloxy, dimethyl-n-hexylsiloxy, dimethylcyclohexylsiloxy, dimethyloctylsiloxy, (CH
₃ ) ₃ SiO [Si (CH ₃ ) ₂ O] _k- (k = 1 to 9), 2-phenyl-2,4,4,4-tetramethylsiloxy, 4,4-diphenyl-2,2,4 -Trimethylsiloxy, 2,4-diphenyl-2,4,4-trimethylsiloxy and the like.

[0036]

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In the above general formula (10), Ra is carbon
A divalent hydrocarbon group of the formulas 1 to 10
Is preferably in the range of 2 to 6, and particularly preferably 2
Or 3. Specific examples of Ra include, for example, -C
H_TwoCH_Two-, -CH_TwoCH_TwoCH_Two-,-(CH_Two)_m
And alkylene groups such as-(m = 4 to 10). Up
R in the general formula (10)_Five, R₆, R₇Is the general formula
R in (9)_Five, R ₆, R₇Is the same as Also,
R₈, R₉Is R_Five, R₆Is the same as n 'is 0
Or an integer in the range of 1 to 9, preferably 0 or
An integer in the range from 1 to 5, particularly preferably 0, 1 or 2
is there.

R in the above general formulas (A), (B) and (1) to (8) may be one kind, which may constitute a cage silsesquioxane or a partially cleaved structure thereof, or two kinds. It may be composed of the above substituents. Further, the above general formula (B)
[RSiO _3/2 ] _nm (O _1/2 H) _{2 + m} A part or all of the OH groups in the cage-like silsesquioxane partially cleaved structure are silicon atoms having 1 to 10 silicon atoms. Containing group,
Preferably, a partially-cleaved cage-like silsesquioxane having a structure substituted by a silicon atom-containing group represented by the general formula (9) can also be used in the present invention.

The cage silsesquioxane of the present invention is described, for example, in Brown et al. Am. Chem. Soc. 196
5, 87, 4313; Polymer Sci. 1
963.1C. 83 and Feher et al. Am. Ch
em. Soc. 1989, 111, 1741 or O
rganometallics 1991, 10, 25
26 and the like. For example, octaphenyloctasilsesquioxane having a structure represented by the general formula (2) is obtained by dissolving phenyltrichlorosilane in benzene, adding an aqueous benzyltrimethylammonium hydroxide solution, and refluxing. Also,
Dodecaphenyldodecasylsesquioxane having a structure represented by the general formula (4) is obtained by converting phenyltrichlorosilane to TH.
It is obtained by dissolving in F, adding an aqueous benzyltrimethylammonium hydroxide solution, and refluxing. Then, cyclohexyltriethoxysilane is dissolved in water / methyl isobutyl ketone, and tetramethylammonium hydroxide is added and reacted to obtain a mixture of silsesquioxane having a structure represented by the general formulas (1) to (3). Is obtained as crystals. Furthermore, the general formula (2)
The octakis (trimethylsiloxy) octasilsesquioxane having the structure represented by the formula is obtained by dissolving tetraethoxysilane in acetone / water, adding tetramethylammonium hydroxide, and reacting the resulting solution to obtain the tetramethyl octasilsesquioxane. It can be obtained by obtaining crystals of the ammonium salt and reacting them with trimethylchlorosilane in a THF solution. The trisilanol compound and the disilanol compound represented by the general formulas (6) to (8), which are partially-cleaved structures of the cage silsesquioxane, are simultaneously produced when the complete condensation type cage silsesquioxane is produced. It can also be synthesized by forming it or by partially cleaving it once from a complete condensation type cage silsesquioxane with trifluoroacid or tetraethylammonium hydroxide. (Feher et al., Chem. Commun., 1
998, 1279)

The structural analysis of the cage silsesquioxane of the present invention was carried out by X-ray structural analysis (Larsson et al., Alkiv.
Kemi 16, 209 (1960)), but identification can be performed simply using an infrared absorption spectrum or NMR (for example, Ingot of Vogt et al.).
rga. Chem. 2,189 (1963)). The cage silsesquioxane or the partially-cleaved cage silsesquioxane used in the present invention may be used alone or as a mixture of two or more. A cage silsesquioxane and a partially cleaved structure of the cage silsesquioxane may be used in combination. Also,
The cage silsesquioxane, the cage silsesquioxane partially-cleaved structure, or a mixture thereof used in the present invention may be used in combination with a silicon-based compound having another structure.

The above general formula (A) used in the present invention,
(B) The cage-shaped silsesquioxane represented by (1) to (8) or the cage-shaped silsesquioxane partially-cleaved structure is an amorphous polysilsesquioxine having no cage formed. When Sun is used as an additive of the polycarbonate-styrene resin composition, it has little effect on improving melt fluidity during molding and flame retardancy. A cage silsesquioxane represented by the above general formula (A), a cage silsesquioxane represented by the above general formula (B) in a polycarbonate-styrene resin composition, or a partially cleaved structure thereof Is used in an amount of 0.1% by weight or more and 50% by weight or less based on the polycarbonate-styrene resin composition. Preferably, it is used in a range of 0.3% by weight to 30% by weight, more preferably, in a range of 0.6% by weight to 20% by weight, and particularly preferably, in a range of 1.0% by weight to 15% by weight. If the amount is less than the above range, the effect on the melt fluidity and flame retardancy is small. If the amount is larger than the above range, physical properties such as mechanical strength are undesirably reduced.

A fluorine-based resin can be added to the polycarbonate-styrene-based resin composition of the present invention in order to enhance flame retardancy. Examples of the fluorine-based resin include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and a tetrafluoroethylene / hexafluoropropylene copolymer. If necessary, the above-mentioned fluorine-containing monomer and a copolymerizable monomer may be used in combination.
The addition amount of the fluororesin is not limited as long as the melt fluidity of the present invention is not impaired, but the content in the polycarbonate resin composition is preferably from 0.01 to 10% by weight, more preferably from 0.03 to 10% by weight. 8% by weight, particularly preferred from 0.05 to 6% by weight. If it is less than 0.01% by weight, the effect of improving the flame retardancy is small, and if it exceeds 10% by weight, the moldability and the like are undesirably reduced.

Further, the polycarbonate-styrene resin composition of the present invention may be combined with a reinforcing filler as long as the melt fluidity of the present invention is not impaired. Heat resistance, mechanical strength, and the like can be improved by adding a reinforcing filler. Examples of the reinforcing filler include fibrous substances such as glass fiber and carbon fiber, glass beads, glass flake, talc, diatomaceous earth and the like. The method for producing the polycarbonate-styrene resin composition of the present invention is not particularly limited, and may be melt-kneaded using a kneader such as an extruder, a plast mill, a heating roll, a kneader, a Banbury mixer, a solution blend, or a cast. Can be produced. Among them, kneading with an extruder is preferable in terms of productivity.

The polycarbonate-styrene-based resin composition of the present invention has significantly improved melt fluidity as compared with the polycarbonate-styrene-based resin as a base, so that a molded article can be obtained with high productivity by a melt molding method. I can do it.
Further, the molded article obtained by the above method is excellent in flame retardancy and can be used for various applications. That is, according to the present invention, it is possible to industrially advantageously produce molded articles of various polycarbonate-styrene-based resin compositions having excellent flame retardancy, which are useful as automobile parts, home electric appliance parts, OA equipment parts, and the like. Was.

[0045]

Embodiments of the present invention will be described below in detail with reference to Examples and Comparative Examples. The present invention is not limited to these. For the cage silsesquioxane and the partially cleaved structure of the cage silsesquioxane,
U.S.A. manufactured by Hybrid Plastic (product numbers: MS0825, MS0830, MS0865, M
S0810, SO1450) were used after purification. The symbols in parentheses in the column of “silicon compound” in Examples 1 to 7 in Table 1 below are the above-mentioned US Hybrid.
It represents each product number manufactured by Plastic. The physical properties of the obtained cage-like silsesquioxane and the polycarbonate-styrene-based resin containing the cage-like silsesquioxane partially-cleaved structure were evaluated according to the following methods. (1) Evaluation of Mold Deposit (MD) A test specimen of 10 × 25 × 0.2 mm was molded in 1000 shots, and the degree of MD adhesion on the surface of the mold was visually evaluated. (2) Flame retardancy evaluation The flame retardancy was evaluated as follows: 126 mm long, 12.6 mm wide, thickness 1
Using five / 8-inch plate specimens, UL-94
(U.S. Underwriters Laboratory Standards).

[0046]

Example 1 Evaluation of a resin composition was performed by the following method.
72% by weight of polycarbonate (S3000, manufactured by Mitsubishi Engineering-Plastics Co., Ltd.) dried at 120 ° C. for 4 hours; 9% by weight of acrylonitrile-styrene (AS) resin (Styrac AS T88001; manufactured by Asahi Kasei Corporation); acrylonitrile-butadiene-styrene (ABS) 9% by weight of resin (M8801 manufactured by Mitsubishi Rayon Co., Ltd.) and 270
Octaisobutyloctasilsesquioxane (MS0825) purified by sublimation at 1 ° C. and 1 mmHg [In the above formula (2), R = isobutyl group] 10
After premixing the weight%, the mixture was put into a twin-screw extruder (ZSW-15, Technovel) set at 250 ° C. and melted and kneaded to obtain a polycarbonate-styrene resin composition. The obtained resin composition pellets were injected into an injection molding machine (FANUC FAS-
15A) and the cylinder temperature was set to 255/255/2.
55/255 ° C, injection speed 50mm /
Molding was performed in seconds. Table 1 shows the evaluation results of the obtained compositions.

[0047]

Examples 2 to 5 A resin composition was obtained in the same manner as in Example 1 except that the cage-like silsesquioxane or the partially-cleaved structure of the cage-like silsesquioxane shown in Table 1 was used. , Was evaluated. Table 1 shows the results.

EXAMPLE 6 The composition ratio of polycarbonate, AS resin, ABS resin and cage silsesquioxane was 74% by weight of polycarbonate, 9.25% by weight of AS resin, and AB, respectively.
A resin composition was obtained and evaluated in the same manner as in Example 1, except that S resin was changed to 9.25% by weight and octaisobutyl-octasilsesquioxane was changed to 7.5% by weight. Table 1 shows the results.

[0048]

Example 7 The composition ratio of polycarbonate, AS resin, ABS resin and cage silsesquioxane was 76% by weight of polycarbonate, 9.5% by weight of AS resin, and ABS, respectively.
A resin composition was obtained and evaluated in the same manner as in Example 1 except that the resin was changed to 9.5% by weight and octaisobutyl-octasilsesquioxane was changed to 5% by weight. Table 1 shows the results.

[0049]

Comparative Example 1 A single polycarbonate-styrene resin composition was evaluated without using a cage silicon compound. Table 1 shows the results.

Comparative Example 2 Methyltriethoxysilane 1 in a glass container
Then, 100 parts of toluene and 80 parts of toluene were added, and 50 parts of a 1% by weight aqueous hydrochloric acid solution was gradually added with stirring to carry out a silane hydrolysis reaction. After the addition was completed, the organic phase was separated, taken out and washed with water, and then toluene as a solvent was distilled off to obtain polymethylsilsesquioxane containing a silanol group. The molecular weight of the obtained polymethylsilsesquioxane is about 5,000.
(GPC measurement, in terms of polystyrene), the silanol group was about 5 mol% (NMR spectrum). Except for the silicon compound, a resin composition was obtained and evaluated in the same manner as in Example 1. Table 1 shows the results.

[0050]

[Table 1]

As is clear from the above, the polycarbonate resin composition to which the specific cage-like silsesquioxane or the cage-like silsesquioxane partially-cleaved structure of the present invention is added has excellent flame retardancy and a mold deposit. Is small.

[0052]

According to the present invention, by adding a specific cage-like silsesquioxane or a partially-cleaved cage-like silsesquioxane structure to a polycarbonate-styrene resin composition, excellent flame retardancy is obtained. A polycarbonate-styrene-based resin composition having a small mold deposit can be obtained.
These are industrially useful.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 83/04 ZAB C08L 83/04 ZAB F term (Reference) 4F071 AA11 AA12 AA13 AA22 AA33 AA34 AA50 AA67 AA76 AA77 AF47 AH07 AH11 AH12 BA01 BB05 4J002 BC06Y BG01Y BG04Y BG10Y BH01Y BN14Z CG00X CG01X CG02X CG04Y CP03W CP06W GN00 GQ00 GS00 GT00

Claims (5)

[Claims] 1. A cage-like silsesquioxane represented by the following general formula (A) or a partially-cleaved cage-like silsesquioxane represented by the following general formula (B): A resin composition composed of a resin. [RSiO _3/2 ] _n (A) (RSiO _3/2 ) _nm (O _1/2 H) _{2 + m} (B) [In the general formula (A) and the general formula (B), R
Is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a silicon atom having 1 to 10 silicon atoms Represents any one of the contained groups, and a plurality of Rs may be the same or different. n is 6 to 1
And m is 0 or 1. ] 2. The polycarbonate-styrene resin according to claim 1, comprising: (a) a polycarbonate resin;
(B) a copolymer containing an aromatic vinyl monomer and a vinyl cyanide monomer as constituent components of the copolymer, (c) an aromatic vinyl monomer component, a vinyl cyanide monomer component, and At least one of the alkyl (meth) acrylate monomers
A resin composition characterized in that one or two or more thereof are composed of a graft copolymer obtained by graft-polymerizing a rubbery polymer. 3. The composition of the polycarbonate-styrene resin according to claim 2, wherein (a) 90 to 10% by weight;
(B) 1 to 50% by weight, and (c) 1 to 50% by weight. 4. The content of the cage silsesquioxane represented by the general formula (A) or the content of the cage silsesquioxane represented by the general formula (B) is partially The resin composition according to any one of claims 1 to 3, wherein the content is 0.1% by weight or more and 50% by weight or less based on the resin composition composed of the polycarbonate-styrene resin. 5. A cage-like silsesquioxane represented by the general formula (A) or a partially-cleaved cage-like silsesquioxane represented by the general formula (B). A molded article comprising the polycarbonate-styrene resin composition according to any one of the above.