ES2304151T3 - COMPOSITION OF POLYCARBONATE RESIN. - Google Patents

Abstract

Resin composition comprising: (A) from 1 to 99 parts by weight of a polycarbonate resin having an average molecular weight in viscosity of 10,000 to 100,000 and (B) from 1 to 99 parts by weight of a styrene resin, selected from the group consisting of ABS resin (acrylonitrile / butadiene / styrene copolymer), AES resin (acrylonitrile / ethylene / propylene / styrene copolymer), ACS resin (acrylonitrile / chlorinated polyethylene / styrene copolymer) and AAS resin (copolymer of acrylonitrile / acrylic / styrene elastomer) (C) a phosphoric ester compound with an acid number of 1 or less, in an amount of 1 to 40 parts by weight per 100 combined parts by weight of (A) + (B), and (D) a reinforcing agent in an amount of 1 to 100 parts by weight per 100 parts by weight combined of (A) + (B) + (C), selected from the group consisting of talc, glass fibers, fibers carbon, glass flakes, ground glass, wolastonite, potassium titanate, ca carbonate lcio, barium sulfate and mica.

Description

Polycarbonate resin composition.

Background of the invention

The present application is a request non-provisional US based on, and claiming priority of, Japanese application number HEI 10-366465, which It is incorporated herein by reference.

The present invention relates to a polycarbonate resin composition.

Polycarbonate (PC) resins, or alloys Polymers produced by combining one of these with a resin of styrene, such as an ABS resin (copolymer of acrylonitrile / butadiene / styrene), are widely used in electrical and electronic parts, photocopiers, printers, faxes, personal computers, laptops and others office automation equipment of this type, telephones laptops and other communication equipment of this type, etc.

In recent years, it has been necessary that products are getting smaller and lighter in these applications, and novel molding methods have been tried in a effort to meet these needs. There is also a growing need for resins that can be molded to give more items fine and can be molded more precisely, and that these resins have better resistance to flame and other properties of this type.

The addition of glass fibers, talc, fibers carbon and other reinforcing agents of this type so that it improve stiffness and dimensional stability has been a practice common in the past in an effort to provide more molding Fine and more precise.

The manufacture and use of these resins have soaring in Southeast Asia in recent years years. In these areas, products are usually used and stored in a high humidity environment, and the degradation of physical properties due to the low moisture resistance of the Resin in a product is often a cause for concern. So it is essential that the moisture resistance of the resins used in the aforementioned products.

Generally a resin of polycarbonate (PC) or a polymer alloy comprising a combination of a polycarbonate resin and a styrene resin have a high resistance to moisture. This is particularly true with a flame resistant resin composition or with a resin composition that has been reinforced with an agent of reinforcement such as carbon fibers.

The present applicant has already invented a polycarbonate resin composition that has excellent moisture resistance and good flame resistance, and in the Japanese patent application 10-216487 and the WO 99/11713 has applied for a patent for a polycarbonate resin composition containing (A) from 1 to 99 parts by weight of a polycarbonate resin having a weight average molecular viscosity of 10,000 to 100,000 and (B) from 1 to 99 parts by weight of (B-i) a copolymer whose structural components are (a) a monomer component of aromatic vinyl, (b) a cyanide monomer component of vinyl, and (c) a polymer similar to rubber and / or (B-2) a copolymer whose structural components they are (a) a component of aromatic vinyl monomer and (b) a component of vinyl cyanide monomer, in which the weight molecular weight average of (B-2) above mentioned is from 30,000 to 200,000, and in which the alkali metal content in each case is not more than 1 ppm, and wherein (C) a phosphoric ester compound is added in a amount from 0 to 40 parts by weight per 100 parts by weight combined of the components (A) and (B) mentioned above.

The document JP-A-10158498 discloses combinations of polycarbonate and ABS resin that have good moldability and warpage resistance comprising (A) 30-80% of polycarbonate, (B) 3-20% of a polyester saturated and (C) 3-50% ABS resin and (D) 1-30 parts per 100 parts of resin (phr) of a flame retardant halogen and / or phosphorus and 1-30 parts per 100 parts resin loads fibers

EP-A-0829517 discloses a flame retardant resin composition comprising (A) a polycarbonate resin whose average molecular weight in viscosity is 16,000-29,000, (B) a poly (alkylene terephthalate) resin, (C) a copolymer containing a rubber polymer and at least one selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, acrylic acid, acrylic esters, methacrylic acid, methacrylic esters and maleimide type monomers as components , (D) an organic phosphorus type flame retardant, (E) a fluorocarbon type resin and (F) an halogen-free epoxy compound; containing 1-10 parts by weight of (C), 2-10 parts by weight of (D), 0.05-2 parts by weight of (E) and 0.01-10 parts by weight of ( F) per 100 parts by weight of a resin whose weight ratio of (A) / (B) is
75 / 25-90 / 10.

Documents JP-A-08239565 and JP-A-11241010 unveil bromine-free flame retardant compositions that comprise (A) 70-95% polycarbonate, (B) the 5-30% styrene polymers, (C) the 2-15% phosphate esters, (D) the 0-5% of rubber graft copolymers of type core / shell and (E) 3-25 parts of talc.

The document JP-A-10147701 discloses compositions flame retardants comprising (A) 40-95 parts of a polycarbonate, (B) 5-60 parts of a rubber with graft of styrene and acrylonitrile monomers, (C) 5-20 phr of a phosphate ester, (D) 0.1-10 phr polysiloxane graft copolymer and (E) 5-50 phr of talc.

The document JP-A-09310011 discloses compositions flame retardants comprising (A) polycarbonate, (B) ABS and / or SAN and (C) 1-30 phr phosphate and (D) 0.1-15 phr of ultrafine anhydrous silica.

The document JP-A-07196873 discloses compositions flame retardants comprising (A) 100 parts of a polycarbonate containing resorcinol, (B) 0.5-40 parts of a copolymer containing aromatic vinyl monomers and vinyl cyanides, and elastomeric polymers, (C) 0.5-40 parts of a graft copolymer of polysiloxane and (D) 1-30 phr of a phosphate.

The document EP-A-0758003 discloses a composition of polycarbonate resin that has a surface appearance improved and an elevated module comprising (A) 99-40 parts by weight of a PC composition and (B) 1-60 parts by weight of an inorganic filler, as well as (C) 1-30 parts by weight of an ester compound of phosphoric acid with respect to a total of 100 parts by weight of the components (A) and (B).

Problems that the invention is intended to solve

The present invention provides a polycarbonate resin composition that has a strength superior to moisture, good flame resistance and resistance remarkably superior mechanics.

Means used to solve the problems above mentioned

The inventors came to the present invention as a result of various investigations aimed at resolving  previous problems

Specifically, the present invention is (1) a resin composition that contains:

(A) from 1 to 99 parts by weight of a resin of polycarbonate having an average molecular weight in viscosity of 10,000 to 100,000 and

(B) from 1 to 99 parts by weight of a resin of styrene,

and that also contains:

(C) a phosphoric ester compound with a acid number of 1 or less, in an amount of 1 to 40 parts in weight per 100 parts by weight combined of (A) + (B), and

(D) a reinforcing agent in an amount of 1 to 100 parts by weight per 100 parts by weight combined of (A) + (B) + (C).

As a result of the thorough investigation aimed at further enhancing the impact resistance of the  resin composition (1) mentioned above without reducing its flame resistance, the inventors perfected the present invention of the following preferred aspects upon discovering that the aforementioned problems can also be solved adding a specific amount of the following (E) copolymer of compound rubber graft to the resin composition (1) previously mentioned.

Examples of preferred aspects include the following.

(2) The resin composition provided in (1) above, which also contains (E) a graft-based copolymer of compound rubber produced by grafting a vinyl monomer into a compound rubber containing a polyorganosiloxane and a poly ((meth) alkyl acrylate), in an amount of 0 to 20 parts by weight per 100 parts by weight combined of (A) + (B) + (C).

(3) The resin composition provided in (2) above, which contains (E) in an amount of 1 to 10 parts in weight.

(4) The resin composition provided in any of (1) to (3) above, in which the amount of metal Alkaline contained in (B) is 1 ppm by weight or less.

(5) The resin composition provided in any of (1) to (3) above, in which the amount of metal Alkaline contained in (B) is 0.5 ppm by weight or less.

(6) The resin composition provided in any of (1) to (3) above, in which the amount of metal Alkaline contained in (B) is 0.1 ppm by weight or less.

(7) The resin composition provided in any of (1) to (6) above, in which the alkali metal Content in (B) is sodium and / or potassium.

(8) The resin composition provided in any of (1) to (7) above, in which (B) is one or more resin types selected from the group consisting of HIPS (high impact polystyrene), ABS resin (copolymer of acrylonitrile / butadiene / styrene), AES resin (copolymer of acrylonitrile / ethylene / propylene / styrene), ACS resin (copolymer of acrylonitrile / chlorinated polyethylene / styrene) and AAS resin (Acrylonitrile / acrylic elastomer / stretch copolymer).

(9) The resin composition provided in any of (1) to (8) above, in which the molecular weight Average viscosity of (A) is 10,000 to 40,000.

(10) The resin composition provided in any of (1) to (9) above, in which (C) is contained in an amount of 3 to 30 parts by weight.

(11) The resin composition provided in any of (1) to (9) above, in which (C) is contained in an amount of 5 to 20 parts by weight.

(12) The resin composition provided in any of (1) to (11) above, which also contains

(F) a compound-based stabilizer epoxy in an amount of 0.01 to 10 parts by weight per 100 Combined parts by weight of (A) + (B).

(13) The resin composition provided in (12)  above, in which (F) is contained in an amount of 0.1 to 0.5 parts by weight.

(14) The resin composition provided in (12) or (13) above, in which the compound-based stabilizer epoxy (F) is carboxylate of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane.

(15) The resin composition provided in any of (1) to (14) above, in which the resin of Polycarbonate (A) is manufactured by polymerization in molten.

(16) The resin composition provided in any of (1) to (15) above, in which the agent of reinforcement (D) is at least one type of agent selected from the group consisting of talc, glass fibers, carbon fibers, flakes glass, ground glass, wolastonite, potassium titanate, calcium carbonate, barium sulfate and mica.

(17) The resin composition provided in any of (1) to (16) above, which also contains (G) of 0.01 to 3 parts by weight of a fluorinated polyolefin.

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Detailed description of the invention

The polycarbonate resin (A) used in the The present invention is an aromatic polycarbonate prepared by a melt process or known phosgene process. Polycarbonate resins such as this are described, for example, in Japanese patent applications open for consultation by the public 63-215763 and 2-124.934. Examples of diphenol used as a starting material include 2,2-bis (4-hydroxyphenyl) propane  (known as bisphenol A); 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) propane; 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (4-hydroxyphenyl) decane; 1,4-bis (4-hydroxyphenyl) propane; 1,1- (hydroxyphenyl) cyclododecane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclododecane;  4,4-dihydroxydiphenyl ether; 4,4-thiodiphenol; 4,4-dihydroxy-3,3-dichlorodiphenyl ether and 4,4-dihydroxy-2,5-dihydroxyphenyl  ether. Examples of precursor substances used to introduce the Carbonate include phosgene and diphenyl carbonate.

The lower limit for molecular weight average viscosity (Mv) of the polycarbonate resin (A) in the  present invention is 10,000, 21,000 being preferred and being Even better 22,000. The upper limit is 100,000, 40,000 being preferred from a practical point of view. Here the average molecular weight in viscosity (Mv) is determined by measuring the intrinsic viscosity [η] at 20 ° C in methylene chloride, and calculating the average molecular weight in viscosity from the Mark-Houwink viscosity formula:

[Mathematical formula 1]

[\ eta] = K (Mv)

(where K = 1.23 x 10 ^ [ileg.]}, And a = 0.83).

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The styrene resin (B) used herein invention is a component composed of (B-1) a graft copolymer containing styrene and / or (B-2) a styrene polymer.

The graft copolymer containing styrene (B-1) is obtained by grafting (a) a component of aromatic vinyl monomer, or, as needed, a mixture of this and (b) a copolymerizable vinyl monomer component, to (c) a rubber-like polymer.

Examples of the vinyl monomer component aromatic (a) include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, monochlorostyrene, dichloro-styrene, monobromo-styrene, dibromo-styrene, fluorostyrene, p-tert-butyl styrene, ethylstyrene and  Vinylnaphthalene They can be used alone or in combinations of two or More types Α-methylstyrene is preferred.

Examples of the copolymerizable vinyl monomer (b) include acrylonitrile, methacrylonitrile, acrylic acid, acid methacrylic and other α- and carboxylic acids β-unsaturated of that type; (meth) methyl acrylate, (meth) ethyl acrylate, (meth) propyl acrylate, (meth) butyl acrylate, (meth) 2-ethyl acrylate, methacrylate 2-ethylhexyl and other α- carboxylic esters and β-unsaturates of that type; anhydride maleic, itaconic anhydride and other carboxylic anhydrides α- and β-unsaturated of that type; maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-o-chlorophenylmaleimide and others α- and carboxylic imide compounds β-unsaturated of that type. Can be used alone or in combinations of two or more types. No limitations particular about the reason in their composition, which It can be selected as dictated by the application.

Examples of the rubber-like polymer (c) they include diene rubbers such as polybutadiene, polyisoprene, random and block copolymers of styrene and butadiene, versions hydrogenated from the above block copolymers, copolymers acrylonitrile / butadiene, and copolymers of butadiene / isoprene; random and block copolymers of ethylene and propylene; copolymers of ethylene and α-olefins; copolymers of ethylene and an unsaturated carboxylic ester, such as ethylene / methacrylate and ethylene / butyl acrylate; copolymers of a acrylic ester and butadiene, such as an acrylate copolymer of butyl and butadiene or other acrylic elastomer of that type; copolymers of ethylene and a vinyl ester of a fatty acid, such as ethylene / vinyl acetate; terpolymers of ethylene / propylene / unconjugated diene, such as a copolymer of ethylene / propylene / hexadiene; copolymers of butylene and isoprene; Y chlorinated polyethylene. They can be used alone or as a combination of Two or more types. Preferred rubber-like polymers are ethylene / propylene / diene unconjugated terpolymers, rubbers diene and acrylic elastomers, being particularly favorable polybutadiene and copolymers of styrene and butadiene.

There are no particular restrictions restrictions on the compositional reasons of (a), (b) and (c) above mentioned, which must be selected as dictated by the application.

It is preferable that the graft polymer containing styrene (Bi) is HIPS (high impact polystyrene), an ABS resin (acrylonitrile / butadiene / styrene copolymer), an AES resin (acrylonitrile / ethylene / propylene copolymer
leno / styrene), an ACS resin (acrylonitrile / chlorinated polyethylene / styrene copolymer) or an AAS resin (acrylonitrile copolymer / acrylic / styrene elastomer).

The graft copolymer containing styrene (B-2) is obtained using a known method of polymerization of (a) a vinyl monomer component aromatic, or, as needed, a mixture of this and (b) a copolymerizable vinyl monomer compound. (B-2) serves to improve moldability (fluidity) of the resin.

The same substances can be used as the listed above as a vinyl monomer component aromatic (a), and the use of styrene or α-methylstyrene.

The same substances can also be used as those listed above as vinyl monomer copolymerizable (b). They can be used alone or in combinations of two or more types There are no particular limitations on the reason in Composition thereof, which can be selected as it comes dictated by the application. Here, there are no particular limitations about the ratio in composition of (a) / (b), but in the component (B-2) it is preferable that (a) represents 50 to 95% by weight, and preferably 65 to 92% by weight, and that (b) represent 5 to 50% by weight, and preferably 8 to 38% in weight. Preferred examples of the styrene polymer of (B-2) include a styrene resin and a resin SAN (styrene / acrylonitrile copolymer).

In the present invention, the upper limit for the weight average molecular weight (Mw) of the polymer of styrene (B-2) should be 200,000, with preference 110,000 and the lower limit is 30,000.

There are no particular limitations on the method to make the copolymer that serves as component (B), and can any usual known method, such as polymerization, be used in bulk, melt polymerization, suspension polymerization in mass, suspension polymerization or emulsion polymerization. It is also possible to combine copolymerized resins separately. The use of bulk polymerization, polymerization in melt or bulk suspension polymerization.

The alkali metal content of the component (B) in the present invention must be 1 ppm by weight or less, and preferably 0.5 ppm by weight or less, and even more preferably 0.1 ppm by weight or less. In addition, of metals Total alkaline, sodium and / or potassium content in the component (B) must be 1 ppm by weight or less, and preferably 0.5 ppm by weight or less, and even more preferably 0.1 ppm by weight or less.

The component (C) in the present invention is a  composed of phosphoric ester and serves as a flame retardant. It is important that this phosphoric ester has an acid number of 1 or less, with 0.5 or less being preferred, 0.2 or even better smaller and 0.1 or less being even better. It is particularly favorable that this acid number is infinitely close to zero given that the resin composition of the present invention will have a enhanced hydrolysis resistance.

Examples of phosphoric ester compounds include compounds expressed by the following formula (I).

one

Wherein R 1, R 2, R 3 and R 4 are each independently a hydrogen atom or a group organic, excluding the case of R 1 = R 2 = R 3 = R 4 = H. X is a divalent or higher organic group, p is 0 or 1, q is an integer of at least 1, such as an integer of 30 or less, and r is an integer of at least O. However, Other phosphoric ester compounds may also be used.

Examples of organic groups in the aforementioned formula (I) include alkyl groups, cycloalkyl groups and aryl groups. Examples of substituents in the case of substitution include alkyl groups, alkoxy groups, alkylthio groups, halogens, aryl groups, aryloxy groups, arylthio groups and halogenated aryl groups. Groups in which these substituents are combined (such as arylalkoxyalkyl groups) and groups in which these substituents are combined by binding with oxygen atoms, sulfur atoms, nitrogen atoms or the like (such as arylsulfonaryl groups) may also be used as substituents . "Dihydric or higher organic group" refers to a dihydric or higher group produced by removing one or more of the hydrogen atoms attached to carbon atoms from the aforementioned organic groups. Examples include groups derived from polynuclear phenols, such as bisphenols, and alkylene groups, and preferably phenylene (substituted) groups. The relative positions of the two or more free valences are not important. Particularly favorable examples include hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane, dihydroxydiphenyl, p, p'-dihydroxydiphenylsulfone, bisphenol A, bisphenol S and dihydroxynaphthalene.

Specific examples of ester compounds Phosphoric include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl, triphenyl phosphate, tricresyl phosphate, cresylphenyl phosphate, octyldiphenyl phosphate, diisopropylphenyl, tris (chloroethyl) phosphate, tris (dichloropropyl), tris phosphate (chloropropyl), phosphate of bis (2,3-dibromopropyl) -2,3-dichloropropyl, tris (2,3-dibromopropyl) phosphate, phosphate bis (chloropropyl) monooctyl, tetraphenyldiphosphate bisphenol A, bisphenol A tetraxyldiphosphate, tetraphenylphosphate of hydroquinone, hydroquinone tetracresyldiphosphate, Hydroquinone tetraxyldiphosphate, a bisphenol A bisphosphate in which from R 1 to R 4 are each an alkoxy, such as methoxy, ethoxy or propoxy, and preferably a phenoxy (substituted), such as methylphenoxy (substituted), or bisphosphate hydroquinone, resorcinol bisphosphate, triphosphate trioxybenzene The use of triphenyl phosphate and various bisphosphates.

The upper limit for the amount by which use the component (C) mentioned above is 40 parts in weight, and preferably 30 parts by weight, and even more preferably 20 parts by weight, and the lower limit is 1 part by weight, and preferably 3 parts by weight, and even more preferably 5 parts by weight, per 100 parts by weight combined from (A) + (B). The effect of the present invention is not will perform completely if the quantity of component (C) is lower than the lower limit mentioned above, and the heat resistance will be affected if the limit is exceeded above mentioned above.

There are no particular limitations on the agent reinforcement (D) used in the present invention, provided that confer the required functions to a molded wall article fine, such as stiffness, dimensional stability and strength mechanical, but examples include talc, mica, glass fibers, glass flakes, ground glass, carbon fibers, arcid fibers, silica, glass beads, glass balls, silica balls, fibers Metallic, metallic powder, wolastonite, potassium titanate, silicon carbide, calcium carbonate, magnesium carbonate, graphite, barium sulfate, barium sulfate and coal dust. Preferred materials are talc, glass fibers, fiber carbon, glass flakes, ground glass, wolastonite, titanate potassium, calcium carbonate, barium sulfate and mica. The agent of reinforcement used in the present invention can be used alone or as A mixture of two or more types.

The upper limit for the amount by which add the component (D) mentioned above must be 100 parts by weight, and preferably 70 parts by weight, and the limit Bottom should be 1 part by weight, and preferably 4 parts by weight, per 100 parts by weight combined of (A) + (B) + (C). Do not sufficient rigidity and mechanical strength will be obtained if the added amount of component (D) is less than the lower limit previously mentioned, and resistance to impact and fluidity (moldability) will be significantly affected if the upper limit mentioned above.

The component (E) used in the present invention it is a rubber-based graft copolymer produced by the graft copolymerization of one or more types of monomer of vinyl in a compound rubber that has a structure in which a polyorganosiloxane rubber component and a component of poly ((meth) alkyl acrylate rubber) are composed interweaving each other.

A rubber based graft copolymer compound such as this can be manufactured, for example, by a method disclosed in Japanese patent applications open to public consultation 64-79257, 7-207137 and 7-207132.

This compound rubber can be manufactured from the more favorable way by emulsion polymerization. In first  instead, a latex of a polyorganosiloxane rubber is prepared, then a monomer is used to synthesize a rubber of (met) alkyl acrylate to impregnate the rubber particles of the polyorganosiloxane rubber latex, after which it polymerizes the monomer to synthesize an alkyl (meth) acrylate.

The organosiloxane rubber component can be prepared, for example, by emulsion polymerization using the following organopolysiloxane and crosslinking agent (I), and a graft crosslinking agent can be used simultaneously (I).

The organosiloxane can be, for example, a linear organosiloxane such as dimethylsiloxane, or any of several cyclic organosiloxanes with 3-member rings or superior, and preferably rings of 3 to 6 members. Examples include hexamethyl-cyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane and octaphenylcyclotetrasiloxane. These organosiloxanes can be used alone or as a mixture of two or more types. The amount in which used is 50% by weight or more, and preferably 70% by weight or more, of the polyorganosiloxane rubber component.

The crosslinking agent (I) can be an agent of tri or tetrafunctional silane crosslinking, such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane or tetrabutoxysilane The use of a crosslinking agent is preferred tetrafunctional, and of these, the use of tetraethoxysilane is particularly favorable. These crosslinking agents can used alone or as a mixture of two or more types. The amount in the one used in the crosslinking agent is preferably 0.1 30% by weight of the polyorganosiloxane rubber component.

The graft crosslinking agent (I) can be a compound that forms units expressed by the following formulas:

[Chemical formula 2]

(I-1) CH 2 = C (R 2) - COO- (CH 2) p -SiR 1 n O (3-n) / 2 }

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[Chemical formula 3]

(I-2) CH 2 = CH-SiR 1 n O (3-n) / 2

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[Chemical formula 4]

(I-3) HS- (CH 2) p -SiR 1 n O (3-n) / 2

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\hbox{entero desde 1  hasta 6).}

(In the above formulas, R1 is a lower alkyl group, such as the methyl group, ethyl group or propyl group, or
a phenyl group, R2 is a hydrogen atom or a methyl group, n is 0, 1 or 2, and p is a number

 \ hbox {integer from 1 to 6).} 

The (meth) acryloyloxysiloxane that can forming units of the formula (I-1) above is advantageous since the graft efficiency is high, allowing form an effectively grafted chain and showing high impact resistence. A methacryloxysiloxane that can form units of the formula (I-1) is particularly favorable. Specific examples of methacryloxy siloxanes include β-methacryloyloxyethyldimethoxysilane, γ-methacryloxyxypropylmethoxydimethylsilane, γ-methacryloxyxypropyl dimethoxymethylsilane, γ-methacryloxyxypropyltrimethylsilane, γ-methacryloxyxypropylethoxydiethylsilane, γ-methacryloxyxypropyldiethoxymethyl silane and δ-methacryloxybutyldiethoxymethylsilane. They can be used alone or as a mixture of two or more types. The amount in which the graft crosslinking agent is used is preferably from 0 to 10% by weight of the rubber component of polyorganosiloxane.

This latex of a rubber component of Polyorganosiloxane can be manufactured using the treated methods, for example, in U.S. Patent Nos. 2,891,920 and 3,294,725. For the practical application of this invention, it is it is preferable that this latex is manufactured, for example, by a method in which a liquid mixture of organosiloxane is subjected, crosslinking agent (I) and, if desired, crosslinking agent from graft (I) to shear mixing with water in the presence of a sulfonic acid emulsifier, such as an acid alkylbenzenesulfonic acid or an alkylsulfonic acid, using a homogenizer, for example. The use of an acid alkylbenzenesulfonic acid is particularly favorable since it works not only as an organosiloxane emulsifier but also as a polymerization initiator. If used simultaneously here a metal salt of an alkylbenzenesulfonic acid, a metal salt of an alkylsulfonic acid, or the like, is effective in maintaining the stable polymer during graft polymerization.

The rubber component of poly ((meth) alkyl acrylate) that constitutes part of the Compound rubber mentioned above can be synthesized using the following (meth) alkyl acrylates, agents of crosslinking (II) and graft crosslinking agents (II).

Examples of alkyl (meth) acrylates include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylate of n-butyl and acrylate 2-ethylhexyl, and alkyl methacrylates such as hexyl methacrylates, methacrylates 2-ethylhexyl and methacrylates of n-lauryl. The use of acrylate n-butyl is particularly favorable.

Examples of the crosslinking agent (II) include ethylene glycol dimethacrylate, dimethacrylate propylene glycol, 1,3-butylene glycol dimethacrylate and 1,4-butylene glycol dimethacrylate.

Examples of the graft crosslinking agent (II) include allyl methacrylate, triallyl cyanurate and triallyl isocyanurate. Allyl methacrylate can also be used as a crosslinking agent. These crosslinking agents and graft crosslinking agents can be used alone or as a Mix of two or more types. The total amount in which they are used these crosslinking agents and graft crosslinking agents it is preferably 0.1 to 20% by weight of the rubber component of poly ((meth) alkyl acrylate).

The polymerization of the rubber component of poly ((meth) alkyl acrylate) is carried out by adding the (meth) alkyl acrylate, crosslinking agent and graft crosslinking mentioned above to a latex of a rubber component of polyorganosiloxane neutralized by addition of an aqueous solution of an alkali such as hydroxide of sodium, potassium hydroxide or sodium carbonate, so that it they impregnate the organosiloxane rubber particles, and then allowing a radical polymerization initiator usual act on the system. As the reaction of polymerization, forms a reticulated network of rubber of poly ((meth) alkyl acrylate) interwoven with the network crosslinked polyorganosiloxane rubber, which provides a Composite rubber latex comprising rubber components of polyorganosiloxane and poly ((meth) alkyl acrylate) substantially inseparable. In the practical application of the In the present invention, it is preferable to use a rubber complex in the that the main skeleton of the rubber component of Polyorganosiloxane has dimethylsiloxane repeat units, and in which the main skeleton of the rubber component of poly ((meth) alkyl acrylate) has repeat units of n-butyl acrylate.

The compound rubber prepared by emulsion polymerization as described above can be subjected to graft copolymerization with a monomer of vinyl. The gel content of this compound rubber as measured by extraction with toluene at 90 ° C for 12 hours it is preferably 80% by weight or greater.

To get a good balance between flame resistance, impact resistance, appearance, etc., the proportion in which the rubber component of polyorganosiloxane and the rubber component of poly ((meth) alkyl acrylate) of the compound rubber above mentioned must be 3 to 90% by weight of the first with respect to 10 to 97% by weight of the latter, and in addition, the Average particle size of the rubber complex should be 0.08 to 0.6 µm.

Examples of vinyl monomers that can undergo graft polymerization in compound rubber Above mentioned include aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyl toluene; methacrylic esters such as methyl methacrylate and 2-ethylhexyl methacrylate; acrylic esters such as methyl acrylate, ethyl acrylate and acrylate butyl; and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. They can be used alone or as a mixture of two or More types Methyl methacrylate is a vinyl monomer particularly favorable. The amount in which the monomer is used Vinyl is preferably 5 to 70% by weight with respect to 30 to 95% by weight of the rubber compound previously mentioned.

The compound rubber graft copolymer (E) can be separated and recovered by pouring a copolymer latex from compound rubber graft prepared by adding the monomer of Vinyl mentioned above to composite rubber latex mentioned above and carrying out a polymerization by single or multi-phase radicals in hot water that contains a dissolved metal salt such as calcium chloride or magnesium sulfate, to precipitate and coagulate the copolymer wanted.

A commercial is also available compound rubber graft copolymer (E) such as this, by example, as Mitsubishi Rayon's Metablen S-2001 Co., Ltd.

Component (E) is used in an amount whose upper limit is 20 parts by weight, and preferably 10 parts by weight, and even more preferably 6 parts by weight, per 100 parts by weight combined of (A) + (B) + (C). Will be sacrificed the moldability if this upper limit is exceeded.

A stabilizer can also be added to base of epoxy compound that serves as component (F) in the present invention in an effort to enhance resistance to hydrolysis. Carboxylate of 3,4-epoxycyclohexyl-methyl-3 ', 4'-epoxycyclohexane  like this stabilizer based on epoxy compound. This Stabilizer is available as Daicel Seroxide 2021P Chemical Industries, or as R-51 by Asahi Denka Kogyo The amount added must not exceed 10 parts in weight, and preferably 0.5 parts by weight, and the lower limit it is 0.01 parts by weight, and preferably 0.1 parts in weight, per 100 parts by weight combined of (A) + (B). I dont know you will get mechanical resistance if the upper limit is exceeded above, but no increase in resistance to hydrolysis below the lower limit mentioned above. The epoxy compound stabilizer is not limited to the previous structure.

A polyolefin can be added additionally fluorinated serving as component (G) to the resin composition of the present invention as an anti-drip agent. Advantageously polytetrafluoroethylene can be used. Polytetrafluoroethylene is a white solid, and is commercially available or can be manufactured by a known method. For example, it can be obtained using a free radical catalyst (such as sodium peroxydisulfate, potassium or ammonium) to polymerize tetrafluoroethylene in a medium aqueous at a pressure of 689.5 kPA at 6894.8 kPA and a temperature of 0 to 200 ° C, and preferably 20 to 100 ° C. In the patent American Brubaker, number 2,393,967 are announced Details of this procedure.

Although not essential, it is preferable to use a resin in the form of relatively large particles, such as particles with an average size of 0.3 to 0.7 mm (mainly of 0.5 mm) This is better than usual polytetrafluoroethylene powder which has a particle size of 0.05 to 0.5 mm. The reason why that a substance like this with a particle size relatively large is particularly favorable is because it it will more easily disperse in a polymer and show a tendency to join polymers together and create a fiber material. A favorable polytetrafluoroethylene as this is called type 3 by ASTM, and is currently available as Teflon 6 from E.I. du Pont de Nemours. It is also available as Teflon 30J from Mitsui Dupont Fluorochemical. The upper limit for the quantity in which the fluorinated polyolefin (G) is contained must be 3.0 parts by weight, and preferably 1.0 part by weight, and the lower limit should be 0.01 parts by weight, and preferably 0.05 parts by weight, per 100 parts by weight combined of (A) + (B).

A polysiloxane or the like can be used as flame retardant and a drip agent, preferably in an amount of 0.1 to 20 parts by weight per 100 parts by weight combined from (A) + (B).

In addition to the various components treated previously, other additives commonly used in the mixing and molding of resins to the resin composition of the present invention as indicated by the application provided, provided that its properties are not visible engaged. Examples of these additives include pigments, dyes, heat resistant agents, stabilizers (antioxidants), weathering agents (UV absorbers), lubricants, separating agents, crystal nucleation, plasticizers, fluidity improvers and antistatic agents.

Examples of stabilizers include phosphorus-based stabilizers available from various manufacturers of stabilizers as antioxidants. Examples Specific include triphenyl phosphite, diphenylnonyl phosphite,  phosphite of tris (2,4-di-t-butylphenyl), trisnonylphenyl phosphite, diphenylisooctyl phosphite, phosphite 2,2'-methylenebis (4,6-di-t-butylphenyl) octyl, diphenylisodecyl phosphite, phosphite diphenylmono (tridecyl), fluorophosphite 2,2'-ethylenebis (4,6-di-t-butylphenol), phenyldiisodecyl phosphite, phenyldi phosphite (tridecyl), tris (2-ethylhexyl) phosphite, phosphite tris (isodecyl), tris phosphite (tridecyl), dibutyl hydrogen phosphite, trilauryl trithiophosphite, phosphonite of tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene,  (C 12 -C 15) alkyl phosphite of 4,4'-isopropylidenediphenol, ditridecyl phosphite 4,4'-butylidenbis (3-methyl-6-t-butylphenyl),  diphosphite of bis (2,4-di-t-butylphenyl) pentaerythritol,  diphosphite of bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol,  bis (nonylphenyl) pentaerythritol diphosphite, diphosphite of distearyl-pentaerythritol, diphosphite of phenyl bisphenol A and pentaerythritol, diphosphite tetraphenyldipropylene glycol, 1,1,3-tris (2-methyl-4-di-tridecyl phosphite-5-t-butylphenyl) butane  and 2-oxide of 3,4,5,6-dibenzo-1,2-oxaphosphane.

Examples of commercial products include Adekastab PEP-36, PEP-24, PEP-4C and PEP-8 (all brands trademarks of Asahi Denka Kogyo), Irgafos 168 (trademark of Ciba-Geigy), Sandstab P-EPQ (brand trademark of Sandoz), Chelex L (trademark of Sakai Chemical Industries), 3P2S (trademark of Ihara Chemical Industries), Mark 329K and Mark P (both trademarks of Asahi Denka Kogyo) and Weston 618 (trademark of Sanko Kagaku).

Examples of other stabilizers include antioxidants based on hindered phenol, stabilizers based on Epoxy compound and sulfur-based stabilizers. Examples of  Phenol-based antioxidants include propionate n-octadecyl-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl), 2,6-di-t-butyl-4-hydroxymethylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol)  and propionate of pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl).  Examples of epoxy compound based stabilizers include epoxidized soybean oil, epoxidized flax seed oil, phenyl glycidyl ether, allyl glycidyl ether and carboxylate 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane.

There are no particular limitations on the amount in which these stabilizers are added, but a amount from 0.0001 to 5 parts by weight per 100 parts by weight Combined of (A) + (B) is preferable.

Examples of separation agents include methylphenylsilicone oil and other separating agents based of this type of silicon, pentaerythritol tetraestearate, glycerol monostearate, montanic acid wax, poly-α-olefins and others ester-based separating agents or separating agents a Olefin base of this type. There are no particular limitations on the amount in which these separating agents are added, but an amount of 0.0001 to 5 parts by weight per 100 parts in Combined weight of (A) + (B) is preferable.

In the present invention it can be used as UV absorber any commonly used UV absorber in PC resin compositions. Examples include absorbents of UV based on benzotriazole, UV absorbers based on benzophenone and salicylate-based UV absorbers. Examples of absorbents UV based benzotriazole include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) -benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-amylphenyl) -benzotriazole, 2- (2'-hydroxy-3'-dodecyl-5'-methylphenyl) -benzotriazole, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) benzotriazole Y 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol).  A benzotriazole-based UV absorber is available as UV531 of American Cyanamid. A UV absorber based on Benzophenone is available as UV531 from Cyanamid. Examples of UV absorbers based on salicylate include salicylate phenyl, p-t-butylphenyl salicylate and salicylate of p-octylphenyl.

There are no particular limitations on the amount in which these UV absorbers are added, but a amount from 0.0001 to 5 parts by weight per 100 parts by weight Combined of (A) + (B) is preferable.

An improvement agent for the  miscibility to the thermoplastic resin composition to which refers to the present invention.

Miscibility enhancement agents include copolymers produced by grafting a polycarbonate into a copolymer of acrylonitrile / styrene, and copolymers produced by grafting a polystyrene resin in a polycarbonate. For example, Modiper CH430, L430D and L150D are available from Nippon Oil & Fats. Poly (methyl methacrylate) (PMMA) can also be used as miscibility improvement agent. No limitations particular about the amount in which these agents are added miscibility improvement, but an amount of 0.1 to 30 parts in weight per 100 parts by weight combined of (A) + (B) is preferable.

There are no particular limitations on the method for manufacturing the resin composition of the present invention and any usual method can be used satisfactorily. Without However, a melt mixing method is generally preferred. It is possible to use a small amount of solvent, but It is generally not necessary. Examples of the devices used in the Manufacturing include an extruder press, Banbury mixer, roller and kneader These devices can be operated continuous or discontinuous way. There are no particular limitations about the order in which the components are mixed.

The present invention will now be described with more detail by way of embodiments, but the present invention is not limited to, nor by, these examples of realization.

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Examples of realization

Listed below are the various substances used in the embodiments and comparatives

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Component (A): polycarbonate (PC)

Lexan 141 (trademark of GE Plastics Japan; a bisphenol A polycarbonate; intrinsic viscosity measured at 20 ° C in methylene chloride is 0.50 dl / g, and Mv \ approx 23,000 (calculated value))

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Component (B): resin styrene

ABS-1: Suntac ABS resin AT-07 (trademark of Mitsui Chemical)

ABS-2: ABS resin UX050 (brand commercial of Ube Sycon)

SAN: SAN resin SR05B (trademark of Ube Sycon)

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Component (C): ester compound phosphoric

FR-2: bisphenol A diphosphate, CR741 (trademark of Daihachi Chemical), acid number of 0.64

FR-3: bisphenol A diphosphate, CR741S (trademark of Daihachi Chemical), acid number of 0.63

FR-1: (comparative component): bisphenol diphosphate A, CR741 (trademark of Daihachi Chemical), acid number of 1.6

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Component (D): agent reinforcement

Talc: LMS-200 {trademark from Fuji Talc Industries)

Glass fibers: FT116 (trademark of Asahi Fiberglass)

Carbon fibers: HTA-C6-SRS (trademark of Toho Rayon)

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Component (E): copolymer of rubber based graft compound

Metablen S-2001 (trademark from Mitsubishi Rayon)

Acrylic rubber (comparative component): Paraloid EX2315 (trademark of Kureha Chemical Industry)

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Component (F): stabilizer a compound base epoxy

Carboxylate 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane  (Seroxide 2021P, trademark of Daicel Chemical Industries)

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Component (G): polyolefin fluoridated

Polytetrafluoroethylene (PTFE): Teflon 30J (brand  Commercial of Mitsui Dupont Fluorochemical)

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Embodiment Examples 1 to 24 and comparative examples 1 to eleven

The various components shown were extruded in tables 2 to 5 from a double extruder press spindle at a spindle speed of 200 rpm and a temperature of cylinder from 270 to 280 ° C, and the extrudate was cut in granules

The granules thus manufactured were used to mold a test piece with an injection molding machine of 80 tons manufactured by Toyo Kikai Kinzoku. The conditions of molding comprised a cylinder temperature of 240 ° C and a molding temperature of 60 ° C.

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(1) Izod impact resistance

Izod impact resistance was measured with a 1/8 inch notch according to ASTM D256.

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(2) Tensile strength and elongation by traction

Measured according to ASTM D638.

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(3) Flexural strength and flexural modulus

Measured according to ASTM D790.

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(4) Fusion Index (MI)

Measured at 260 ° C and a load of 5 kg according to the ASTM D1238.

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(5) Load deformation temperature

Measured according to ASTM D648, using a test piece with a thickness of 1/4 inches and a load of 18.6 kg / cm2.

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(6) Flame resistance test

Tests were performed according to UL 94 / V0 method, VI or VII. Five samples with a thickness of 1/16 inch according to the method described in Underwriters Laboratories, Inc., Bulletin 94, "Combustion Tests for Materials Classification "(referred to herein below document UL-94). Using this test method, you evaluated the sample material to see if it had a degree UL-94 V-0, V-I or V-II based on the results of five samples. The criteria for the various degrees of V in the method UL-94 is summarized below.

V-0: The average time of flame maintenance after removing the ignition flame is from 10 seconds or less, and none of the samples drop flames particulates that light absorbent cotton.

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V-I: The average time of flame maintenance after removing ignition flames is 30 seconds or less, and none of the samples drop flames particulates that light absorbent cotton.

V-II: The average time of flame maintenance after removing ignition flames is 30 seconds or less, and the samples drop flames particulates that light absorbent cotton.

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(7) Moisture resistance test

A test piece was left in an oven at high temperature and high humidity (80 ° C, 98% RH), after which it was measured tensile strength in the same way as previously.

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(8) Component alkali metal quantification (B)

The sample was calcined and dissolved in pure water, and quantification was performed using ICP and absorption methods atomic. The quantification results are given in the table 1 below.

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(9) Measurement of the acid number of the component (C)

Measured by the method provided to continuation.

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Method of measuring the acid value of the phosphoric ester

Measured by the following operation.

192 {192} 40 ml of a mixed solution of ethyl alcohol and water using a test tube in a triangular flask of 200 ml.

19 {193} 1 ml of a solution of bromothymol blue by a graduated pipette in this flask triangular and then the assessment was performed with a solution of sodium hydroxide N / 10 until the color changed to green bluish.

19 {194} Approximately 10 g of sample (component (C)) was measured in this triangular flask, using an electronic scale and reading to the first decimal point (sample amount: S ).

\ ding {195} The assessment was performed with a Sodium hydroxide solution N / 10 until the color changed to teal like in \ ding {193} (amount of assessment: TO).

The acid value of the ester was calculated phosphoric from the following formula.

[Mathematical formula 2]

Index of acidity of the ester phosphoric

(KOH mg / g) = (A x F x 5.61) / S

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(Here, A is the amount (ml) of hydroxide of sodium N / 10 necessary for the titration of the sample, F is the title of the sodium hydroxide solution N / 10 and S is the sample amount (g)).

The reagents used in the measurements Previous were the following.

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192 {192} Mixed solution of ethyl alcohol and Water

Ethyl alcohol was mixed (reagent guaranteed) and water subjected to ion exchange in a reason 9: 1 volumetric.

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\ ding {193} Bromothymol blue solution

20 ml of 95% ethyl alcohol was added in volume (guaranteed reagent) to 0.10 g of bromothymol blue, and This was diluted with water and brought to 100 ml.

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\ ding {194} Sodium hydroxide solution N / 10

Standardization of the dissolution title of sodium hydroxide N / 10

Sulfamic acid was dried (conventional reagent) in a vacuum sulfuric acid desiccator, weighed from 0.2 to 0.3 g thereof and placed in a 200 ml triangular flask, then approximately 25 ml of water was added and dissolved, and titration was performed with a solution of Sodium hydroxide N / 10 using a bromothymol blue solution as an indicator The title was calculated from the following formula.

[Mathematical formula 3]

Title = (S x P) / (0.9709 x TO)

(Here, S is the amount (g) of sulfamic acid used, P is the purity (%) of sulfamic acid and A is the amount of  titration (ml) of the sodium hydroxide solution N / 10).

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TABLE 1 Amount of alkali metal in the component B

2

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The various results are provided in the Tables 2 to 5.

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3

4

5

6

7

8

9

10

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Examples of embodiment 1 to 8 are resin compositions of the present invention in which They used various reinforcing agents (D).

In comparison with resin compositions of Comparative Examples 1 and 2, which did not contain reinforcement (D), [the resin compositions of the examples of embodiment 1 to 8] all had a mechanical resistance superior, specifically, tensile strength, elongation by traction, flexural strength and flexural modulus. The comparative examples 3 and 4 contained the reinforcing agent (D) [in an amount] that exceeded the range of the present invention. Molding was impossible in both cases. In the examples of embodiment 5 to 8, the component (B) used in the examples of embodiment 1 to 4 was replaced by a styrene resin whose alkali metal content was 1 ppm by weight or less. There was a notable increase in tensile strength after Aging in all cases.

Embodiments 9 to 12 used a phosphoric ester compound (C) with a higher acid number than that of embodiments 5 to 8, but still inside of the range of the present invention. There was a certain reduction in tensile strength after aging in all cases, but the effect of the present invention was not lost. The comparative examples 5 to 8 used a component (C) that had a acidity index that exceeded the range of the present invention. There was a notable increase in tensile strength after aging in all cases.

In embodiments 13 to 18, examined the effect of adding the compound-based stabilizer epoxy (F). It can be seen that the addition of (F) increased notably the tensile strength after aging.

In embodiments 19 to 24, examined the effect of adding graft copolymer based on compound rubber (E). It can be seen that the addition of (E) notably increases Izod impact resistance. In the comparative examples 9 to 11, an acrylic rubber was used instead of (AND). This is not desirable since although the Izod impact resistance, flame resistance decreases

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Effect of the invention

The present invention provides a polycarbonate resin composition that has excellent moisture resistance, good flame resistance and remarkably superior mechanical resistance.

Claims (6)

1. Resin composition comprising: (A) from 1 to 99 parts by weight of a resin of polycarbonate having an average molecular weight in viscosity of 10,000 to 100,000 and (B) from 1 to 99 parts by weight of a resin of styrene, selected from the group consisting of ABS resin (acrylonitrile / butadiene / styrene copolymer), AES resin (acrylonitrile / ethylene / propylene / styrene copolymer), resin ACS (Acrylonitrile / Chlorinated Polyethylene / Styrene Copolymer) and AAS resin (acrylonitrile / elastomer copolymer acrylic / styrene) (C) a phosphoric ester compound with a acid number of 1 or less, in an amount of 1 to 40 parts in weight per 100 parts by weight combined of (A) + (B), and (D) a reinforcing agent in an amount of 1 to  100 parts by weight per 100 parts by weight combined of (A) + (B) + (C), selected from the group consisting of talc, fibers of glass, carbon fibers, glass flakes, ground glass, wolastonite, potassium titanate, calcium carbonate, sulfate Barium and Mica. 2. Resin composition according to claim 1, which also contains: (E) a rubber based graft copolymer compound produced by grafting a vinyl monomer in a compound rubber containing a polyorganosiloxane and a poly ((meth) alkyl acrylate), in an amount of 0 to 20 parts by weight per 100 parts by weight combined of (A) + (B) + (C). 3. Resin composition according to claim 2, in which (E) is contained in an amount of 1 to 10 parts in weigh. 4. Resin composition according to any of the  claims 1 to 3, wherein the amount of alkali metal contained in (B) is 1 ppm by weight or less. 5. Resin composition according to claim 4, in which the alkali metal contained in (B) is sodium and / or potassium. 6. Resin composition according to any of the  claims 1 to 5, further containing: (F) a compound-based stabilizer epoxy in an amount of 0.01 to 10 parts by weight per 100 Combined parts by weight of (A) + (B).