JP2000044786A - Flame-retardant thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant thermoplastic resin compsn. excellent in chemical resistance by compounding a resin component contg. (A) a polycarbonate resin and (B) a thermoplastic polyester resin in a specified wt. ratio with (C) a specific polyorganosilsesquioxane compd. SOLUTION: Ingredient A is obtd. by reacting a dihydric or higher phenol compd. with a carbonic diester (e.g. phosgene or diphenyl carbonate). Ingredient B is obtd. by polycondensing a dicarboxylic or a higher acid component with a dihydric or a higher alcohol and/or a phenol component by a known method. The compounding ratio by wt. of ingredieint A to ingredient B is (90/10)-(60/40). This resin component in an amt. of 100 pts.wt. is compounded with 1-30 pts.wt. ingredient C. Ingredient C comprises 100-80% R1SiO3/2, 0-20% R22SiO2/2, and 0-20% R23SiO1/2. Here, R1 is a 1-10C monovalent hydrocarbon group; and R2 is a 1-16C alkyl group modified with a reactive group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant thermoplastic resin composition. More specifically, a thermoplastic resin composition which is flame-retarded by adding a specific polyorganosilsesquioxane compound to a polycarbonate resin and a thermoplastic polyester resin in a specific ratio, and further has excellent chemical resistance Belongs to the technical field of manufacturing and using products.

[0002]

2. Description of the Related Art Polycarbonate resins have the highest impact resistance among engineering plastics and are also known as resins having good thermal deformation resistance. By utilizing these characteristics, they can be used in various fields such as electric and electronics. However, they have drawbacks such as solvent resistance and molding fluidity. On the other hand, polyethylene terephthalate-based resin has solvent resistance,
Various resin compositions have been disclosed for the purpose of improving the drawbacks of polycarbonate resins because of their excellent molding fluidity. For example, JP-B-36-14035, JP-B-39-20434, JP-B-55-94350, JP-B-58-13588, JP-B-5-87540, JP-A-59-176345, JP-A-62-48760. JP-A-62-48761, JP-A-3-140359,
JP-A-4-85360 is exemplified. In particular, in order to secure fire safety, UL-945V (US Underwriters Laboratory) In many cases, a high degree of flame retardancy is required so as to conform to the standard), and therefore, flame retardant resin compositions are being developed and studied by various methods. In recent years, with increasing interest in environmental issues mainly in Europe, various uses of halogen-free flame retardants such as phosphorus-based flame retardants have been studied. However, when flame retardation is carried out using a phosphoric ester compound such as a phosphorus-based flame retardant, red phosphorus, etc., odors are generated during extrusion and molding, and mechanical and thermal properties are adversely affected. For this reason, silicon-based flame retardants are now attracting attention. A resin composition flame-retarded using a silicon-based compound is disclosed in
No. 93363 describes a resin composition in which a modified polyorganosiloxane is blended in a synthetic resin, and JP-A-53-27645 discloses a flame-retardant resin composition in which a polyorganosiloxane and polytetrafluoroethylene are blended in a polycarbonate resin. 49-54411, JP-A-51-45
No. 160 and the like. Also, JP-A-6-1925
No. 56, JP-A-7-157641, JP-A-7-157
JP-A-642 and JP-A-8-157618 disclose resin compositions in which polyorganosilsesquioxane particles are blended with a polycarbonate resin and a polyester resin, respectively. Organosilsesquioxane particles were added, and no mention was made of flame retardancy.

[0003]

In the field where such a flame-retardant resin composition is used (for example, in the application of electric / electronic parts), chemical resistance is required in addition to excellent flame retardancy. ing. In particular, when used in OA equipment, etc., they are exposed to various chemicals such as hydraulic oil used in molding processing and electronic equipment assembling processing, household detergents used in housing cleaning, and insecticides. There are problems such as cause. However, in a resin composition comprising a polycarbonate-based resin and a thermoplastic polyester-based resin or a polycarbonate-based resin and an organosilicon-based compound, the chemical resistance is somewhat improved as compared with the polycarbonate-based resin, but is exposed to OA equipment. Resistance to various chemicals is not sufficient. When polycarbonate resin or polycarbonate resin and polyester resin are made flame retardant by organosilicon compound, the flame retardancy is somewhat improved, but the level of flame retardancy required for electric and electronic parts applications However, a flame-retardant thermoplastic resin composition having excellent chemical resistance has not been obtained.

[0004] The present invention has been made to solve the above problems, and an object of the present invention is to provide a flame-retardant thermoplastic resin composition having excellent chemical resistance.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a resin composition comprising a polycarbonate resin and a thermoplastic polyester resin in a specific ratio is converted to a specific polyorganosilsesquioxane compound. It has been found that by using such a resin composition, a resin composition having surprisingly excellent chemical resistance and flame retardancy can be obtained.
That is, the flame-retardant thermoplastic resin composition of the present invention comprises (A)
100 parts by weight of a resin containing a polycarbonate resin and (B) a thermoplastic polyester resin in a weight ratio of 90/10 to 60/40, and (C) a resin represented by the following general formula (1):
Polyorganosilsesquioxane compounds 1 to 30 in which the units represented by (2) and (3) are constituted in the following proportions:
The present invention relates to a flame-retardant thermoplastic resin composition containing parts by weight.

[0006] (R ¹ SiO _3/2) units 100 to 80% of the - - - - - - - (1), a unit of _{^{(R 2 2 SiO 2/2) ·}} · · · · · · (2) 0 0 to 20%, a unit of (R ² ₃ SiO _1/2 )...... (3) 0 to 20% (wherein, R ¹ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms) And R ¹ may be the same or different, and R ² is a modified alkyl group having 1 to 16 carbon atoms modified with a reactive group selected from an epoxy group, a hydroxyl group, a vinyl group, an acryl group and a methacryl group; The numbers represent 1 to 10 monovalent hydrocarbon groups and hydroxyl groups, and R ² may be the same or different.)

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polycarbonate resin (A) used in the present invention is specifically obtained by reacting a phenol compound having a valency of 2 or more with a carbonic acid diester such as phosgene or diphenyl carbonate. Things.

There are various dihydric phenols, and in particular, 2,2-bis (4-hydroxyphenyl)
Propane (commonly known as bisphenol A) is preferred. Examples of the dihydric phenol other than bisphenol A include bis (4-hydroxyphenyl) methane; bis (4
Bis (4-hydroxyphenyl) naphthylmethane; bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane; bis (3,5-dichloro-4-hydroxyphenyl) 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 (3,5-dichloro-4
-Hydroxyphenyl) propane; 2,2-bis (3,
5-dibromo-4-hydroxyphenyl) propane;
2,2-bis (3-chloro-4-hydroxyphenyl)
Propane; 2,2-bis (3-methyl-4-hydroxyphenyl) propane; 2,2-bis (3-fluoro-4
-Hydroxyphenyl) propane; 1,1-bis (4-
2,2-bis (4-hydroxyphenyl) butane; 1,4-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) pentane; 4-methyl-2, 2-bis (4-hydroxyphenyl) pentane; 2,2-bis (4-hydroxyphenyl) hexane; 4,4-bis (4-hydroxyphenyl) heptane; 2,2-bis (4-hydroxyphenyl) nonane; 1,10-bis (4-hydroxyphenyl) decane; 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane; 2,
2-bis (4-hydroxyphenyl) -1,1,1,
Dihydroxydiarylalkanes such as 3,3,3-hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-
Dichloro-4-hydroxyphenyl) cyclohexane;
Dihydroxydiarylcycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclodecane, bis (4-hydroxyphenyl) sulfone; bis (3,5-
Dimethyl-4-hydroxyphenyl) sulfone; dihydroxydiaryl sulfones such as bis (3-chloro-4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) ether; bis (3,5-dimethyl-
Dihydroxydiaryl ethers such as 4-hydroxyphenyl) ether, 4,4′-dihydroxybenzophenone; 3,3 ′, 5,5′-tetramethyl-4,
Dihydroxydiaryl ketones such as 4'-dihydroxybenzophenone, bis (4-hydroxyphenyl)
Sulfide; bis (3-methyl-4-hydroxyphenyl) sulfide; dihydroxydiaryl sulfides such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, and dihydroxy diaryl sulfoxides such as bis (4-hydroxyphenyl) sulphoxide And dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl, and dihydroxyarylfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene. In addition to dihydric phenols,
Dihydroxybenzenes such as hydroquinone, resorcinol and methylhydroquinone; 1,5-dihydroxynaphthalene; dihydroxynaphthalenes such as 2,6-dihydroxynaphthalene. Each of these dihydric phenols and the like may be used alone or in combination of two or more.

Examples of the carbonic acid diester compound include diaryl carbonates such as diphenyl carbonate and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

In the present invention, the polycarbonate resin as the component (A) may contain a branched polycarbonate, if necessary. Examples of the branching agent used to obtain the branched polycarbonate include, for example,
Phloroglucin, melitic acid, trimellitic acid, trimellitic chloride, trimellitic anhydride, gallic acid, gallic acid n
-Propyl, protocatechuic acid, pyromellitic acid, pyromellitic dianhydride, α-resorcinic acid, β-resorcinic acid,
Resorcinaldehyde, trimethyl chloride, isatin bis (o-cresol), trimethyl trichloride, 4
-Chloroformylphthalic anhydride, benzophenonetetracarboxylic acid; 2,4,4'-trihydroxybenzophenone; 2,2 ', 4,4'-tetrahydroxybenzophenone;2,4,4'-trihydroxyphenylether; 2,2 ', 4,4'-tetrahydroxyphenyl ether; 2,4,4'-trihydroxydiphenyl-
2-propane; 2,2′-bis (2,4-dihydroxy) propane; 2,2 ′, 4,4′-tetrahydroxydiphenylmethane; 2,4,4′-trihydroxydiphenylmethane; 1- [α-methyl -Α- (4′-dihydroxyphenyl) ethyl] -3- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene; 1-
[Α-methyl-α- (4′-dihydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene; α, α ′, α ″ -tris (4- (Hydroxyphenyl) -1,3,5-triisopropylbenzene; 2,6-bis (2-hydroxy-5 ′
-Methylbenzyl) -4-methylphenol; 4,6-
Dimethyl-2,4,6-tris (4'-hydroxyphenyl) -2-heptene; 4,6-dimethyl-2,4,6
-Tris (4'-hydroxyphenyl) -2-heptane; 1,3,5-tris (4'-hydroxyphenyl)
Benzene; 1,1,1-tris (4-hydroxyphenyl) ethane; 2,2-bis [4,4-bis (4′-hydroxyphenyl) cyclohexyl] propane; 2,6-
Bis (2'-hydroxy-5'-isopropylbenzyl) -4-isopropylphenol; bis [2-hydroxy-3- (2'-hydroxy-5'-methylbenzyl) -5-methylphenyl] methane; bis [2 -Hydroxy-3- (2'-hydroxy-5'-isopropylbenzyl) -5-methylphenyl] methane; tetrakis (4-hydroxyphenyl) methane; tris (4-hydroxyphenyl) phenylmethane; 2 ', 4', 7-trihydroxyflavan; 2,4,4-trimethyl-
2 ', 4', 7-trihydroxyflavan; 1,3-bis (2 ', 4'-dihydroxyphenylisopropyl)
Benzene; tris (4'-hydroxyphenyl) -amyl-s-triazine;

In some cases, the polycarbonate resin as the component (A) includes a polycarbonate part,
A polycarbonate-polyorganosiloxane copolymer comprising a polyorganosiloxane part may be used. At this time, the degree of polymerization of the polyorganosiloxane portion is preferably 5 or more.

In addition, as the polycarbonate resin of the component (A), for example, a linear aliphatic dicarboxylic acid such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid and the like can be used. A copolymer as a polymerization monomer can also be used.

As the terminal terminator at the time of polymerization of the polycarbonate resin, various known terminating agents can be used. Specifically, examples of the monohydric phenol include phenol, p-cresol, pt-butylphenol, pt-octylphenol, p-cumylphenol, bromophenol, tribromophenol, and nonylphenol.

Further, in order to increase the flame retardancy, a copolymer with a phosphorus compound or a polymer whose terminal is blocked with a phosphorus compound may be used. Further, in order to enhance the weather resistance, a copolymer with a dihydric phenol having a benzotriazole group can be used.

The viscosity average molecular weight of the polycarbonate resin (A) used in the present invention is preferably from 10,000 to
60000, more preferably 15,000 to 45
000, most preferably from 18,000 to 35,000. When the viscosity average molecular weight is less than 10,000, the strength and heat resistance of the obtained resin composition are often insufficient.
If the viscosity average molecular weight exceeds 60,000, the moldability is often insufficient.

[0016] Such a polycarbonate resin has the following properties:
Species or a combination of two or more species is used. When two or more kinds are used in combination, the combination is not limited. For example, those having different monomer units, different copolymerization molar ratios, and / or different molecular weights are arbitrarily combined.

The thermoplastic polyester resin (B) used in the present invention is obtained by polycondensation of a divalent or higher carboxylic acid component, a divalent or higher alcohol and / or phenol component by a known method. It is a thermoplastic polyester. Specific examples of the thermoplastic polyester resin include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate.

As the divalent or higher aromatic carboxylic acid component, divalent or higher aromatic carboxylic acids having 8 to 22 carbon atoms and ester-forming derivatives thereof are used. Specific examples of these include phthalic acid such as terephthalic acid and isophthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methaneanthracene dicarboxylic acid,
4′-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, diphenylsulfonedicarboxylic acid, trimesic acid, trimellitic acid,
Examples thereof include carboxylic acids such as pyromellitic acid, and derivatives thereof having an ester forming ability. These are used alone or in combination of two or more. Preferred are terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid. This is because they are excellent in ease of handling, ease of reaction, physical properties of the obtained resin, and the like.

The dihydric or higher alcohol and / or phenol component includes aliphatic compounds having 2 to 15 carbon atoms, alicyclic compounds having 6 to 20 carbon atoms, and aromatic compounds having 6 to 40 carbon atoms, and And compounds having two or more hydroxyl groups therein, as well as ester-forming derivatives thereof. Specific examples of such alcohol and / or phenol components include ethylene glycol, propylene glycol, butanediol, hexanediol,
Decanediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediol, 2,2 '
-Bis (4-hydroxyphenyl) propane, 2,2 '
Compounds such as -bis (4-hydroxycyclohexyl) propane, hydroquinone, glycerin, pentaerythritol, and the like, and derivatives thereof having an ester-forming ability are exemplified. Preferred alcohol and / or phenol components are ethylene glycol, butanediol,
Cyclohexanedimethanol. Ease of handling,
This is because the easiness of the reaction, the physical properties of the obtained resin, and the like are excellent.

(B) The thermoplastic polyester resin includes:
In addition to the acid component and the alcohol and / or phenol component, known copolymerizable components may be copolymerized as long as the desired properties are not impaired. Examples of such copolymerizable components include carboxylic acids such as divalent or higher valent aliphatic carboxylic acids having 4 to 12 carbon atoms, divalent or higher valent alicyclic carboxylic acids having 8 to 15 carbon atoms, and esters thereof. Forming derivatives. Specific examples thereof include adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, maleic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and other dicarboxylic acids, or esters thereof. Derivatives having the same.

Further, oxyacids such as p-oxybenzoic acid and p-hydroxybenzoic acid and their ester-forming derivatives, cyclic esters such as ε-caprolactone, and the like can also be used as the copolymerization component. Furthermore, polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) blocks and / or random copolymers, bisphenol A copolymerized polyethylene oxide addition polymers, propylene oxide addition polymers, tetrahydrofuran addition polymers, polytetraethylene A polymer obtained by partially copolymerizing a polyalkylene glycol unit such as methylene glycol in a polymer chain can also be used. The copolymerization amount of the above components is generally 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less.

(B) The thermoplastic polyester resin contains an alkylene terephthalate unit, preferably 80% by weight.
The polyalkylene terephthalate is more preferably 85% by weight or more, most preferably 90% by weight or more. This is because the obtained composition has an excellent balance of physical properties (eg, moldability, mechanical properties).

(B) The logarithmic viscosity (IV) of the thermoplastic polyester resin measured at 25 ° C. in a phenol / tetrachloroethane = 1/1 (weight ratio) mixed solvent is as follows:
Preferably it is 0.30 to 2.00 dl / g or more, preferably 0.40 to 1.80 dl / g, and more preferably 0.50 to 1.60 dl / g. Logarithmic viscosity is 0.
If it is less than 30, the flame retardancy and mechanical strength of the molded product are often insufficient, and if it exceeds 2.00 dl / g, the moldability tends to be reduced.

The thermoplastic polyester resin (B) may be used alone or in combination of two or more.
When two or more kinds are used in combination, the combination is not limited. For example, those having different copolymer components and different molar ratios and / or those having different molecular weights are arbitrarily combined.

In the present invention, the mixing ratio of (A) the polycarbonate resin and (B) the thermoplastic polyester resin is 90/10 to 60/40 by weight, preferably 87/13 to 63/63. / 37, more preferably 8
It is in the range of 5/15 to 65/35. When the weight ratio of (B) the thermoplastic polyester resin in the mixture of (A) the polycarbonate resin and (B) the thermoplastic polyester resin exceeds 90/10, the chemical resistance of the obtained molded product becomes poor. If it is insufficient, and if it is less than 60/40, the heat resistance and the like will be reduced, and the balance of physical properties between flame retardancy and chemical resistance cannot be obtained. The (C) polyorganosilsesquioxane compound used in the present invention has the following general formulas (1), (2),
(3) (R ¹ SiO _3/2) units 100 to 80% of - - - - - - - (1), the unit of _{^{(R 2 2 SiO 2/2) ·}} · · · · · · (2) 0 ２０20%, (R ² ₃ SiO _1/2 )... (3) The unit represented by the formula (3): 0 to 20%. An organosilicon compound having a stitch structure, wherein R ¹ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ¹ may be the same or different;
R ² has 1 to 1 carbon atoms modified with a reactive group selected from an epoxy group, a hydroxyl group, a vinyl group, an acryl group and a methacryl group.
It represents 16 modified alkyl groups, monovalent hydrocarbon groups having 1 to 10 carbon atoms, and hydroxyl groups, and R ² may be the same or different.

The carbon number used as R ¹ and R ² is 1 to 1
Examples of the 0 monovalent hydrocarbon group include an alkyl group such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and t-butyl, and an aryl group such as phenyl, tolyl and xylyl. , Β-phenylethyl, β-phenylpropyl and the like, and 50% or more of R ¹ is a methyl group and / or
Alternatively, a phenyl group is preferred from the viewpoint of flame retardancy.
An epoxy group, a hydroxyl group, a vinyl group used as R ² ,
Examples of the modified alkyl group having 1 to 16 carbon atoms modified with a reactive group selected from an acryl group and a methacryl group include the following.

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

Embedded image The polyorganosilsesquioxane compound (C) used in the present invention has an organosilsesquioxane unit represented by the general formula (1) in an amount of 100 to 80% by weight, preferably 95 to 85% by weight, and more preferably 80 to 85% by weight. %, The effect of flame retardation cannot be obtained. The molecular weight of the (C) polyorganosilsesquioxane compound used in the present invention is not particularly limited as long as it satisfies the claims of the present invention, but preferably has a number average molecular weight of 1,000 or more, more preferably a number average molecular weight. Is preferably a polymer in the range of 2,000 to 100,000,000 from the viewpoint of effectively improving flame retardancy and chemical resistance. (C) used in the present invention
A method for producing a polyorganosilsesquioxane compound,
It is industrially known and may be manufactured by various known methods. For example, alkoxysilanes such as methyltrialkoxysilane, dimethyldialkoxysilane, trimethylalkoxysilane, phenyltrialkoxysilane, diphenyldialkoxysilane, triphenylalkoxysilane, and methylphenyldialkoxysilane, and represented by the following general formula (4) Dehydration condensation reaction followed by hydrolysis of chlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, triphenylchlorosilane, methylphenyldichlorosilane, and dimethylphenylchlorosilane. It can be produced by any method such as by a subsequent dehydration condensation reaction. R ³ _a R ⁴ _b Si (—OR ⁴ ) _4-n ..... (4) (wherein, R ³ is a reactive group selected from an epoxy group, a hydroxyl group, a vinyl group, an acrylic group, and a methacryl group) in indicates denatured number 1 to 16 modified alkyl group having a carbon, R ³ may be the same or different, R ⁴ denotes a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴ is the same In the formula, n represents an integer of 1, 2, 3, a represents an integer of 1, 2, b represents an integer of 0, 1, and n = a + b.) The polyorganosilsesquioxane compound (C) used in the present invention may be used alone or in combination of two or more. When two or more kinds are used in combination, the combination is not limited. For example, as long as the claims of the present invention are satisfied, those having different polymerization components and different molar ratios and / or those having different molecular weights are arbitrarily combined. The shape of the polyorganosilsesquioxane compound (C) used in the present invention is not particularly limited, and any shape such as oil, gum, varnish, powder, and pellet can be used. .

The amount of the polyorganosilsesquioxane compound (C) used in the present invention is from 1 to 30 parts by weight based on 100 parts by weight of the total amount of the (A) polycarbonate resin and (B) the thermoplastic polyester resin. The amount is preferably 1.5 to 25 parts by weight, more preferably 2 to 20 parts by weight. If the amount is less than 1 part by weight, the effects of flame retardancy and chemical resistance cannot be sufficiently obtained, and if it exceeds 30 parts by weight, the appearance and surface properties of the molded article tend to be adversely affected.

In the present invention, a rubber elastic body may be used in order to increase the impact strength, toughness, etc. of the obtained molded article within a range not impairing the properties (flame retardancy, chemical resistance) of the present invention. Good. As the rubber elastic body, it is preferable to add one or more soft resins selected from a graft polymer and / or an olefin resin. The rubber elastic body preferably has a glass transition temperature of 0 ° C. or lower, more preferably −20 ° C. or lower, because the impact strength of the obtained resin is improved.

Among the rubber elastic bodies, the graft rubber is a rubber obtained by graft copolymerizing a vinyl monomer with a rubber-like elastic body.

As the rubbery elastic body, polybutadiene,
Examples include diene rubbers such as styrene-butadiene rubber, acrylonitrile-butadiene rubber, alkyl (meth) acrylate-butadiene rubber, acrylic rubber, ethylene-propylene rubber, and siloxane rubber.

The vinyl-based monomer is an aromatic vinyl-based compound, a vinyl cyanide-based compound, an alkyl (meth) acrylate, or any other vinyl-based compound that can be graft-polymerized to a rubber-like elastic material.

As the aromatic vinyl compound, styrene,
o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, chlorostyrene, bromostyrene, vinyltoluene, and the like.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.

Examples of the alkyl (meth) acrylate include butyl acrylate, butyl methacrylate, ethyl acrylate, ethyl methacrylate, methyl acrylate, and methyl methacrylate.

Other vinyl compounds include unsaturated acids such as acrylic acid and methacrylic acid, glycidyl (meth) acrylate such as glycidyl acrylate and glycidyl methacrylate, vinyl acetate, maleic anhydride, and N-phenylmaleimide. And the like.

There is no particular limitation on the copolymerization ratio at the time of copolymerizing the rubber-like elastic body and the vinyl compound, but a preferable ratio for further increasing the impact strength is 10/9 by weight.
0 to 90/10, and further 30/70 to 80/20. If the weight ratio of the rubber-like elastic body is less than 10, the effect of improving the impact resistance is reduced. If it exceeds 90, the compatibility between the resins (A) and (B) tends to decrease.

Among the rubber elastic bodies, the olefin resin is
In addition to polyolefins in a narrow sense, polydienes, mixtures of two or more thereof, copolymers of olefin monomers and two or more diene monomers, and one or more other vinyl monomers copolymerizable with olefin monomers and olefins Is used as a broad concept including the following copolymers. For example, ethylene, propylene, 1-
Butene, 1-pentene, isobutene, butadiene, isoprene, chloropyrene, phenylpropadiene, cyclopentadiene, 1,5-norbornadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,
A polymer selected from one or a combination of two or more of monomers such as 5-cyclooctadiene, 1,3-cyclooctadiene, α, ω-non-conjugated dienes;
Alternatively, a copolymer, a mixture of one kind of these polymers, and a mixture of two or more copolymers may be used. Among these, polyethylene, polypropylene,
And the like are preferably used because the chemical resistance of the obtained composition is improved.

Further, these olefin components and (meth)
Acrylic acid, alkyl (meth) acrylate,
It may be a copolymer of a vinyl monomer copolymerizable with an olefin such as glycidyl (meth) acrylate, vinyl acetate, maleic anhydride, N-phenylmaleimide, carbon monoxide, and the like. Specific examples of these copolymers include ethylene / ethyl acrylate copolymer, ethylene / butyl acrylate / carbon monoxide terpolymer, ethylene / glycidyl methacrylate copolymer, ethylene / glycidyl methacrylate / vinyl acetate copolymer , Ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-acrylic acid copolymer, ethylene
Maleic anhydride copolymer, ethylene / maleic anhydride /
N-phenylmaleimide copolymer, and the like.

The method for polymerizing these polyolefin resins is not particularly limited, and can be polymerized by various methods. As long as it is polyethylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and the like can be obtained by a polymerization method, and any of them can be preferably used.

Further, the flame-retardant thermoplastic resin composition of the present invention contains a fluorine-based resin and a resin of the present invention in order not to impair the properties (chemical resistance and heat resistance) of the present invention in order to enhance the flame retardancy. Silicones other than the (C) polyorganosilsesquioxane compound used in (1) can be used. The fluorine-based resin is a resin having a fluorine atom in the resin. Specifically, polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer, and the like can be given. Further, if necessary, the monomer used in the production of the fluororesin and the copolymerizable monomer may be used in combination with the monomer to be polymerized, as long as the physical properties such as flame retardancy of the obtained molded article are not impaired. The obtained copolymer may be used. These fluorinated resins are 1
They may be used alone or in combination of two or more.

The molecular weight of the fluororesin is from 1,000,000 to 20
Preferably 100,000, more preferably 2-100
100,000. The method for producing these fluororesins can be obtained by a generally known method such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization.

The silicone other than the (C) polyorganosilsesquioxane compound used in the present invention is (C)
A polyorganosiloxane in a broad sense other than a polyorganosilsesquioxane compound, such as a diorganosiloxane compound such as dimethylsiloxane or phenylmethylsiloxane, or a triorganosylhemioxane such as trimethylsilhemioxane or triphenylsilhemioxane. Oxane compounds, copolymers obtained by polymerizing these, polydimethylsiloxane, polyphenylmethylsiloxane, and the like. When it is an organopolysiloxane,
Also useful are modified silicones whose molecular terminals have been substituted by epoxy groups, hydroxyl groups, carboxyl groups, mercapto groups, amino groups, ethers, and the like.

Among them, a polymer having a number average molecular weight of 200 or more, more preferably a number average molecular weight in the range of 1,000 to 5,000,000 is preferable because flame retardancy can be further enhanced. The shape of the silicone is not particularly limited, and any shape such as an oil, a gum, a varnish, a powder, and a pellet can be used.

The addition amount of the fluorine resin and the silicone is
There is no limitation as long as the properties (chemical resistance, heat resistance, etc.) of the present invention are not impaired, but 0.01 to 100 parts by weight of the total amount of (A) the polycarbonate resin and (B) the thermoplastic polyester resin. 10 to 10 parts by weight, more preferably 0.03 to 8 parts by weight, particularly preferably
It is 0.05 to 6 parts by weight. If the addition amount is less than 0.01, the effect of improving the flame retardancy is small, and if it exceeds 10 parts by weight, the moldability and the like are undesirably reduced.

Further, the flame-retardant thermoplastic resin composition of the present invention may be combined with a reinforcing filler to form a reinforcing material. By adding a reinforcing filler, it is possible to further improve heat resistance, mechanical strength and the like. Specific examples of the reinforcing filler include, for example, fibrous fillers such as glass fiber, carbon fiber, potassium titanate fiber, glass beads, glass flakes, talc, mica, kaolin, wollastonite, smectite, diatomaceous earth, and carbonic acid. calcium,
Examples thereof include calcium sulfate and barium sulfate. Particularly preferred as reinforcing fillers are silicate compounds and / or
Or a fibrous reinforcing agent.

As the silicate compound, the chemical composition is S
Compounds having a shape such as powder, granules, needles, and plates containing iO2 units, such as talc, mica, magnesium silicate, aluminum silicate, calcium silicate, wollastonite, kaolin, diatomaceous earth, and smectite. And it may be natural or synthetic. Of these, talc, mica and smectite are preferred. There is no particular limitation on the average diameter of the silicate compound [the particle diameter when converted to a circle obtained by image processing of a micrograph], but a preferable average diameter is 0.01.
To 100 μm, more preferably 0.1 to 50 μm.
μm, and more preferably 0.3 to 40 μm. If the average particle size is less than 0.01 μm, the effect of improving the strength is not sufficient, and if it exceeds 100 μm, the toughness tends to decrease.

Further, the silicate compound may be treated with a surface treating agent such as a silane coupling agent or a titanate coupling agent. Examples of the silane coupling agent include epoxy silane, amino silane, and vinyl silane. Examples of the titanate coupling agent include monoalkoxy type, chelate type, and coordinate type.

The method of treating the silicate compound with the surface treating agent is not particularly limited, and can be carried out by a usual method. For example, the surface treatment agent can be added to the layered silicate and stirred or mixed in a solution or while heating.

[0054] Examples of the fibrous reinforcing agent include glass fiber and carbon fiber. When a fibrous reinforcing agent is used, it is preferable to use chopped strand glass fibers treated with a sizing agent from the viewpoint of workability. Further, in order to enhance the adhesiveness between the resin and the fibrous reinforcing agent, it is preferable that the surface of the fibrous reinforcing agent is treated with a coupling agent, and a material using a binder may be used. Examples of the coupling agent include the same compounds as described above.

When glass fiber is used for the reinforcing filler,
The diameter is preferably about 1 to 20 μm and the length is about 0.01 to 50 mm. If the fiber length is too short, the reinforcing effect is not sufficient, and if it is too long, the surface properties, extrusion processability, and moldability of the molded product are undesirably deteriorated.

The reinforcing filler can be used alone or in combination of two or more. When two or more kinds are used in combination, there is no particular limitation, but a preferred combination is selected from kaolin, smectite and glass fiber.
More than one reinforcing filler.

The amount of the reinforcing filler to be added is not limited as long as the properties (chemical resistance and the like) of the present invention are not impaired, but the total amount of (A) the polycarbonate resin and (B) the thermoplastic polyester resin is 100 parts by weight. 0.5 to 100
It is preferably 1 part by weight, more preferably 1 to 60 parts by weight, particularly preferably 2 to 40 parts by weight. If the amount is less than 0.5 part by weight, the effect of improving mechanical strength is small, and if it exceeds 100 parts by weight, properties such as workability and impact resistance tend to be impaired.

The flame-retardant resin composition of the present invention may further contain any other thermoplastic or thermosetting resin within the range not impairing the present invention, such as a liquid crystal polyester resin, a polyester ester elastomer resin, and a polyester ether. Elastomer resins, polyolefin resins, polyamide resins, polystyrene resins, polyphenylene sulfide resins, polyphenylene ether resins, polyacetal resins, polysulfone resins, and the like may be added alone or in combination of two or more.

Further, in order to make the flame-retardant resin composition of the present invention higher in performance, an antioxidant such as a phenolic antioxidant and a thioether antioxidant, and a heat stabilizer such as a phosphorus stabilizer are used. It is preferable to use one or more agents, etc. in combination. Further, if necessary, usually well-known, lubricants, release agents, plasticizers, non-phosphorus-based flame retardants, flame retardant aids such as zinc borate, ultraviolet absorbers, light stabilizers, pigments,
Dyes, antistatic agents, conductivity-imparting agents, dispersants, compatibilizers,
One or more additives such as antibacterial agents can be used in combination.

The method for producing the composition of the present invention is not particularly limited. For example, it can be manufactured by a method of melting and kneading with a melt kneading machine such as a single-screw or twin-screw extruder after drying the above components, other additives, resins, and the like as necessary. . Also, when the compounding agent is a liquid,
It can also be manufactured by adding the mixture to a twin-screw extruder using a liquid supply pump or the like.

The method of molding the flame-retardant thermoplastic resin composition produced by the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, for example, injection molding, blow molding, extrusion molding, and the like. Molding, vacuum molding, press molding, calender molding, foam molding, etc. can be applied.

The flame-retardant thermoplastic resin composition of the present invention is suitably used for various uses. Preferred applications include
Injection molded products such as home appliances, OA equipment parts, and automobile parts, blow molded products, extruded molded products, foam molded products, and the like.

[0063]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. In the following, “parts” means parts by weight and “%” means% by weight, unless otherwise specified.

The evaluation of the resin composition was performed by the following method. Evaluation method After drying the obtained pellets at 100 ° C. for 5 hours, 35 t
Using an injection molding machine, a 2.9 mm thick bar (width 12.7 mm, length 127 mm) and ASTM No. 1 dumbbell were obtained at a cylinder temperature of 280 ° C. and a mold temperature of 50 ° C., and the following evaluation was performed. Flame retardancy: 2.9 according to UL-945V standard
The bar was evaluated for flame retardancy. Chemical resistance: The following chemicals were applied to a bar of ASTM No. 1 dumbbell (thickness: 3.2 mm) to which a strain of 1.0% was applied, treated at 80 ° C. for 24 hours, and then subjected to a tensile test (ASTM D638). According to the above, evaluation was made based on the retention (%) of tensile elongation at break. Retention of tensile elongation at break (%) = (tensile elongation at break after treatment / tensile elongation at break before treatment) × 100 Chemical: Pericoat S6 (release agent from Chukyo Kasei Kogyo Co., Ltd.): Organophosphorus pesticide ( Permethrin 7.0% aqueous solution): Eflux (a vaporizable rust inhibitor manufactured by Chukyo Kasei Kogyo Co., Ltd.) Example 1 Production of polyorganosilsesquioxane compound (C-1) 200 ml of methyltridichlorosilane in a flask The solution was gradually added to 600 ml of ion-exchanged water at 15 to 20 ° C. while stirring. After completion of the addition, the mixture was gradually heated to 120 ° C. while removing water under reduced pressure, and reacted for 4 hours. The obtained reaction product was cooled and then ground in a mortar to obtain a polyorganosilsesquioxane compound (C-1). Varia
As a result of measuring an NMR spectrum using an XL-300 apparatus manufactured by n Company, the constitutional ratio of the structural units represented by the general formulas (1), (2) and (3) was 98: 2: 0.

70 parts by weight of a bisphenol A type polycarbonate resin (A-1) having a viscosity average molecular weight of about 22,000, 30 parts by weight of a polyethylene terephthalate resin (B-1) having a logarithmic viscosity of about 0.75 dl / g, and polyorganosyl 7 parts by weight of sesquioxane compound (C-1), ADK STAB HP-10 (trade name, manufactured by Asahi Denka) as a phosphorus-based stabilizer
0.3 parts by weight, dry-blended in advance, and then a twin-screw extruder with a vent set to a cylinder temperature of 280 ° C
The resin composition was obtained by supplying to a hopper of [TEX44: trade name of Nippon Steel Works Co., Ltd.] and performing melt extrusion. Table 1 shows the evaluation results of the resin composition. Examples 2 to 8: Resin compositions were obtained in the same manner as in Example 1 except that the amounts of the respective ingredients were changed to those shown in Table 1. Further, the following compounding agents were used. Table 1 shows the evaluation results.

[0066]

[Table 1] (A) As a polycarbonate resin ・ A bisphenol A type polycarbonate resin having a viscosity average molecular weight of about 28800 (A-2) (B) As a thermoplastic polyester resin ・ A polyethylene terephthalate resin having a logarithmic viscosity of 0.6 dl / g ( B-2)-Polybutylene terephthalate resin having a logarithmic viscosity of 0.85 dl / g (B-3) (C) as a polyorganosilsesquioxane compound-Polyorganosilsesquioxane compound (C-2):
180 ml of phenyltrimethoxysilane, 12 ml of phenylmethyldimethoxysilane, and 19 ml of triphenylethoxysilane were gradually added to 600 ml of water at 20 to 30 ° C. adjusted to pH 4 with hydrochloric acid in a flask while stirring, and after the addition was completed, water was added. 120 gradually while removing under reduced pressure
C. and reacted for 4 hours. After cooling the obtained reaction product, it was pulverized in a mortar to obtain a polyorganosilsesquioxane compound (C-2). XL made by Varian
As a result of measuring an NMR spectrum using a -300 apparatus,
The structural ratio of the structural units represented by the general formulas (1), (2), and (3) was 89: 6: 5. -Polyorganosilsesquioxane compound (C-3):
180 ml of phenyltrimethoxysilane and 43 ml of γ-glycidoxypropylmethyldimethoxysilane were adjusted to pH 6 with hydrochloric acid in a flask.
The mixture was gradually added to 0 ml with stirring, and after completion of the addition, the mixture was gradually heated to 120 ° C. while removing water under reduced pressure, and reacted for 7 hours. The obtained reaction product is cooled and then pulverized in a mortar to obtain a polyorganosilsesquioxane compound (C-3).
I got N using a Varian XL-300 device
As a result of measuring the MR spectrum, the general formula (1),
The weight ratio of the structural units represented by (2) and (3) is 85:
15: 0. -Polyorganosilsesquioxane (C-4): YR-
3370 (manufactured by Toshiba Silicone Co., Ltd., general formula (1),
The weight ratio of the structural units represented by (2) and (3) is 92:
8: 0) Polyorganosilsesquioxane compound (C-5):
100 ml of phenyltrimethoxysilane, 100 ml of phenylmethyldimethoxysilane and 30 ml of triphenylethoxysilane were gradually added to 600 ml of water at 20 to 30 ° C. adjusted to pH 4 with hydrochloric acid in a flask while stirring, and after the addition was completed, water was added. 12 while removing under reduced pressure
The mixture was heated to 0 ° C. and reacted for 4 hours. The obtained reaction product was cooled to obtain a polyorganosilsesquioxane compound (C-
5) was obtained. As a result of measuring an NMR spectrum using an XL-300 apparatus manufactured by Varian, the general formula (1),
The structural ratio of the structural units represented by (2) and (3) is 43:
50: 7. -Polyorganosilsesquioxane compound (C-6):
100 ml of methyltrimethoxysilane and 160 ml of trimethylmethoxysilane are gradually added to 600 ml of water at 20 to 30 ° C. adjusted to pH 4 with hydrochloric acid in a flask while stirring, and after the addition is completed, water is gradually removed while removing water under reduced pressure. C. and heated for 4 hours to obtain a polyorganosilsesquioxane compound (C-6). Vari
As a result of measuring an NMR spectrum using an XL-300 device manufactured by An Corporation, the structural ratio of the structural units represented by the general formulas (1), (2), and (3) was 37: 0: 63. -Polyorganosiloxane compound (C "-1): TSF
451 (manufactured by Toshiba Silicone Co., Ltd.)
Dimethyl silicone oil which is 00 cSt) Polyorganosiloxane compound (C "-2): TSF
4730 (manufactured by Toshiba Silicone Co., Ltd.)
Epoxy-modified dimethyl silicone oil that is 00 cSt) As a component of the rubber elastic body and the reinforcing filler, • Soft resin (D): EXL-2602 (trade name of Kureha Chemical: diene rubber copolymerized with methacrylic acid) • Average particle size Talc (E-1) having a diameter of 10 μm: talcan powder (trade name, manufactured by Hayashi Kasei) ・ Mica having an average particle diameter of 40 μm (E-2): A-41S
(Trade name, manufactured by Mika Yamaguchi Co., Ltd.) Comparative Examples 1 to 10 Example 1 except that the amount of each compounding agent was changed to the amount shown in Table 2.
In the same manner as in the above, a resin composition was obtained. Table 2 shows the evaluation results.

[0067]

[Table 2] In Comparative Examples 1, 2, and 3, the compounding ratio of the polycarbonate-based resin and the thermoplastic polyester resin is outside the scope of the present invention, so that the chemical resistance or the flame retardancy is inferior to those of Examples. In Comparative Examples 4, 5, and 6, the polyorganosilsesquioxane compound was not added or the addition amount was outside the scope of the present invention, so that the chemical resistance and the flame retardancy were poor, or
Molding processability is poor and molding is impossible. Comparative Example 7,
In 8, 9, and 10, the polyorganosilsesquioxane compound is out of the scope of the present invention, and the flame retardancy is poor because the polyorganosiloxane compound is used.

As is clear from the above, the composition of the present invention is excellent in both flame retardancy and chemical resistance.

[0069]

According to the present invention, a resin composition having excellent flame retardancy and excellent chemical resistance can be obtained. These are very useful industrially.

Claims (1)

[Claims] 1. A method according to claim 1, wherein (A) the polycarbonate resin and (B) the thermoplastic polyester resin are 90/10 to 60
100 parts by weight of a resin contained at a weight ratio of / 40;
A flame-retardant resin composition containing 1 to 30 parts by weight of a polyorganosilsesquioxane compound in which units represented by the following general formulas (1), (2) and (3) are constituted in the following proportions. (R ¹ SiO _3/2) units 100 to 80% of - - - - - - - (1), (R ² ₂ SiO _2/2) units 0-20% of - - - - - - - (2) , (R ² ₃ SiO _1/2 ) Unit 0 to 20% of (3) (wherein R ¹ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms; ¹ is a good .R ² be the same or different epoxy group, hydroxyl group, vinyl group, acryl group, a reactive modified number 1 to 16 modified alkyl group having a carbon with a group selected from a methacrylic group, carbon atoms 1 Represents a monovalent hydrocarbon group or a hydroxyl group, and R ² may be the same or different.)