JPH11181268A - Flame-retardant thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant thermoplastic resin composition having both of excellent chemical property and heat resistance by adding a phosphazene compound to a resin comprising an aromatic polycarbonate-based resin and a thermoplastic polyester-based resin. SOLUTION: This flame-retardant thermoplastic resin composition is obtained by incorporating (C) 1.5-15 pts.wt. phosphazene compound and (D) 0.5-30 pts.wt talc and/or mica to 100 pts.wt. resin composition containing (A) an aromatic polycarbonate-based resin and (B) a thermoplastic polyester-based resin at a weight ratio of (90/10) to (50/50). Impact resistance of the above resin composition is further improved by further adding (E) 1-15 pts.wt. graft copolymer and/or olefinic resin to the above components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant thermoplastic resin composition used for parts in the fields of machinery, automobiles, electricity, electronics and the like, and more particularly to excellent chemical resistance. The present invention relates to a flame-retardant thermoplastic resin composition having both heat resistance and heat resistance.

[0002]

2. Description of the Related Art Polycarbonate resins have high impact resistance,
It is a thermoplastic resin excellent in heat resistance and the like, and is widely used for parts in fields such as machines, automobiles, electricity, and electronics. Above all, aromatic polycarbonate resin is
High glass transition temperature and excellent heat resistance are expected. However, on the other hand, aromatic polycarbonate resins often cannot obtain sufficient fluidity during processing.
Therefore, a relatively high processing temperature of around 300 ° C. is required to process the aromatic polycarbonate resin, and a relatively high injection temperature is required when the aromatic polycarbonate resin is molded by injection molding or the like. Speed and pressure are required.

On the other hand, thermoplastic polyester resins are excellent in mechanical properties, electrical properties, chemical resistance and the like, and show good molding fluidity when heated to a temperature higher than the crystal melting point of the resin itself. Conventionally, they have been widely used as fibers, films, molding materials and the like. Therefore, attempts have been made to improve problems such as fluidity of the polycarbonate-based resin by utilizing the characteristics of the thermoplastic polyester-based resin. For example,
No. 35, JP-B-39-20434, JP-A-5
Japanese Patent Application No. 9-176345 proposes a resin composition in which a thermoplastic polyester resin such as polyethylene terephthalate or polybutylene terephthalate is added to a polycarbonate resin.

By the way, in the case of thermoplastic resin, in order to ensure safety against fire, the resin used is
In many cases, a high degree of flame retardancy is required so as to conform to UL-94 (U.S. Underwriters Laboratory Standard), and various flame retardants have been developed and studied.

In recent years, in particular, with the growing interest in environmental issues mainly in Europe, various uses of a flame retardant such as a phosphorus-based flame retardant containing no halogen have been studied. Examples of the phosphorus-based flame retardant include a phosphazene compound, a phosphate-based compound, and red phosphorus. However, among these phosphorus-based flame retardants, phosphate ester-based compounds,
When flame retardancy is achieved by using red phosphorus, there are problems such as the heat resistance of the flame-retardant resin being greatly reduced and the generation of odor during molding. Phosphazene compounds that do not adversely affect odor are attracting attention.

As a resin composition flame-retarded using a phosphazene compound, for example, Japanese Patent Application Laid-Open No. 54-119544
JP-A-7-29223 discloses a flame-retardant synthetic resin composition in which a specific phosphazene compound is blended with a synthetic resin.
No. 3 discloses a flame-retardant resin composition in which a phosphazene compound and a fluororesin are blended with a polycarbonate-based resin composition.
A thermoplastic resin composition having excellent flame retardancy, in which phosphazene and polytetrafluoroethylene are blended with a polycarbonate resin and a styrene-based graft copolymer, is disclosed.

[0007]

In the field where such a flame-retardant resin composition is used, for example, in the field of application of electric and electronic parts, heat resistance and chemical resistance in addition to excellent flame retardancy are required. Have been. In particular, when used in OA equipment, etc., the resin composition is inferior in chemical resistance because it is exposed to hydraulic oil used in molding processing and electronic equipment assembly processing and household detergent used in housing cleaning. Have problems such as failure or failure.

However, in the flame-retardant resin composition comprising a polycarbonate resin, a thermoplastic polyester resin and a phosphazene compound, it is necessary to increase the amount of the thermoplastic polyester resin in order to obtain excellent chemical resistance. In such a case, a significant decrease in heat resistance is unavoidable. Further, the flame retardancy is reduced with the increase in the amount of the thermoplastic polyester resin, and it is necessary to increase the amount of the phosphazene compound. However, not only the heat resistance is lowered but also excellent chemical resistance cannot be obtained. However, a flame-retardant thermoplastic resin composition having excellent flame retardancy, chemical resistance, and heat resistance has not yet been obtained.

[0009]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a flame-retardant thermoplastic resin composition having both excellent chemical resistance and heat resistance. Is to provide.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that when a resin comprising a specific ratio of a polycarbonate resin and a thermoplastic polyester resin is made flame-retardant by a specific amount of a phosphazene compound, It has been found that by adding specific amounts of talc and mica, a flame-retardant thermoplastic resin composition having surprisingly excellent chemical resistance and heat resistance can be obtained.

That is, the present invention relates to 100 parts by weight of a resin containing (A) an aromatic polycarbonate resin and (B) a thermoplastic polyester resin in a weight ratio (A / B) of 90/10 to 50/50. And (C) a flame retardant thermoplastic resin composition containing 1.5 to 15 parts by weight of a phosphazene compound and (D) 0.5 to 30 parts by weight of talc and / or mica (Claim 1); In addition to the above, at least one kind of a soft resin selected from the group consisting of (E) a graft copolymer and an olefin-based resin is further added to 100 parts by weight of the total amount of (A) and (B). ~
15 parts by weight of the flame-retardant thermoplastic resin composition (Claim 2).

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The aromatic 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 diester such as phosgene or diphenyl carbonate. It is obtained.

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 and bis (4
-Hydroxyphenyl) phenylmethane, 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-
(Hydroxyphenyl) butane, 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-
Dihydroxydiarylsulfones such as dimethyl-4-hydroxyphenyl) sulfone and 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)
Dihydroxydiaryl sulfides such as sulfide, bis (3-methyl-4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, and dihydroxy diaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide And dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl, and dihydroxyarylfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene. In addition to dihydric phenols,
Examples thereof include dihydroxybenzenes such as hydroquinone, resorcinol, and methylhydroquinone, and dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene. 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 aromatic 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 phloroglucin, melitic acid, trimellitic acid, trimellitic acid chloride, trimellitic anhydride, gallic acid, n-propyl gallate, protocatechuic acid, pyromellitic acid, and pyromellitic acid Anhydride, 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'-trihydroxyphenyl ether, 2,2', 4,4'-tetrahydroxyphenyl ether, 2,4 4'-trihydroxydiphenyl-2-p Bread, 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,
-[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 and the like are mentioned.

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

In addition, examples of the aromatic polycarbonate resin as the component (A) include linear aliphatic dicarboxylic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and decanedicarboxylic acid. May be used as a copolymer monomer.

As the terminal terminator at the time of polymerization of the aromatic polycarbonate resin, various known terminators 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 enhance the flame retardancy, a copolymer with a phosphorus compound or a polymer whose terminal is blocked with a phosphorus compound can 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 aromatic polycarbonate resin (A) used in the present invention is preferably 100
00 to 60,000, and more preferably 15,000.
~ 45000, most preferably 18000-35000
It is. When the viscosity average molecular weight is less than 10,000, the strength and heat resistance of the obtained resin composition tend to be insufficient. On the other hand, when the viscosity average molecular weight exceeds 60,000, moldability tends to be insufficient.

Such aromatic polycarbonate resins are used alone or in combination of two or more. When using in combination of two or more,
The combination is not limited. For example, those having different monomer units, different copolymerization molar ratios, and / or different molecular weights are arbitrarily combined.

Next, the thermoplastic polyester resin (B) used in the present invention comprises a divalent or higher valent aromatic carboxylic acid component and a divalent or higher valent alcohol and / or phenol component by a known method. It is a thermoplastic polyester obtained by condensation.

As the divalent or higher aromatic carboxylic acid component, a divalent or higher aromatic carboxylic acid having 8 to 22 carbon atoms and an ester-forming derivative 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 may be used alone or in combination of two or more.
Preferred aromatic carboxylic acids 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,
Examples thereof include alicyclic compounds having 6 to 20 carbon atoms, aromatic compounds having 6 to 40 carbon atoms and having two or more hydroxyl groups in a molecule, and 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′-bis (4-hydroxyphenyl) propane, 2,
Compounds such as 2′-bis (4-hydroxycyclohexyl) propane, hydroquinone, glycerin, and pentaerythritol, and derivatives thereof having an ester-forming ability are exemplified. Preferred alcohol and / or phenol components are ethylene glycol, butanediol, cyclohexanedimethanol. This is because the ease of handling, the ease of reaction, the physical properties of the obtained resin, and the like are excellent.

(B) The thermoplastic polyester resin includes:
In addition to the aromatic carboxylic acid component and the alcohol and / or phenol component, known copolymerizable components may be copolymerized within a range that does not impair the properties of the present invention. Examples of such a copolymerizable component include divalent or higher valent aliphatic carboxylic acids having 4 to 12 carbon atoms,
Examples thereof include carboxylic acids such as a divalent or higher valent alicyclic carboxylic acid having 8 to 15 carbon atoms, and ester-forming derivatives thereof. Specific examples of these include adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, maleic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-
Examples thereof include dicarboxylic acids such as cyclohexanedicarboxylic acid, and derivatives thereof capable of forming an ester.

Also, oxyacids such as p-oxybenzoic acid and p-hydroxybenzoic acid, and ester-forming derivatives thereof, and cyclic esters such as ε-caprolactone can be used as the copolymerization component. Furthermore, polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, bisphenol A
A copolymer obtained by partially copolymerizing a polyalkylene glycol unit such as a copolymerized polyethylene oxide addition polymer, a propylene oxide addition polymer, a tetrahydrofuran addition polymer, and polytetramethylene glycol in a polymer chain can also be used. The copolymerization amount of the above components is generally not more than 20% by weight, preferably 15% by weight.
Or less, more preferably 10% by weight or less.

Specific examples of (B) the thermoplastic polyester resin include, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate And the like. Preferred thermoplastic polyester resin contains alkylene terephthalate units, preferably at least 80% by weight,
More preferably, it is a polyalkylene terephthalate having 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:
It is preferably 0.30 to 2.00 d1 / g, more preferably 0.40 to 1.80 d1 / g, and still more preferably 0.50 to 1.60 d1 / g. Logarithmic viscosity is 0.
If it is less than 30 d1 / g, the molded article tends to have insufficient flame retardancy and mechanical strength. On the other hand, if it exceeds 2.00 dl / g, the moldability tends to decrease.

The thermoplastic polyester resins can 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, components having different copolymer components and different molar ratios and / or components having different molecular weights are arbitrarily combined.

In the present invention, the mixing ratio of (A) the aromatic polycarbonate resin and (B) the thermoplastic polyester resin is 90/10 to 50/5 by weight (A / B).
0, preferably in the range of 82/18 to 55/45, and more preferably in the range of 80/20 to 60/40.
If the ratio of (B) the thermoplastic polyester resin in the mixture of (A) the aromatic polycarbonate resin and (B) the thermoplastic polyester resin is less than 10, the resulting molded article has poor chemical resistance. If it exceeds 50, the heat resistance and the like will be reduced, and the balance between the physical properties of flame retardancy and chemical resistance cannot be obtained.

The phosphazene compound used in the present invention is not particularly limited as long as it has a structure in which a phosphorus atom and a nitrogen atom are connected by a double bond.

Embedded image The phosphazene compound which consists of a combination of the repeating unit represented by these is used. Here, R may be a functional group of any chemical structural formula, excluding the halogen compound.
Specifically, an alkyl group, an aryl group, an alkoxy group,
Organic groups such as an aryloxy group, an alkylamino group, and an arylamino group, and inorganic groups such as an amino group are exemplified. These functional groups may be used alone or in combination of two or more. Also,
The repeating unit represented by the above formula may be linked cyclically or may be linked chainwise. Further, the phosphazene compound comprising a combination of the repeating units represented by the above formula may be an oligomer or a polymer.

Particularly preferred phosphazene compounds are represented by the following general formula (1)

Embedded image (However, R ¹ and R ^{2 each} represent an alkyl group having 1 to 20 carbon atoms or 6 carbon atoms which may be optionally substituted with an alkyl group.)
To 20 aryl groups, which may be the same or different. ) Is a phosphorus compound composed of a combination of repeating units.

Specifically, the following formula (2)

Embedded image (However, R ¹ and R ^{2 each} represent an alkyl group having 1 to 20 carbon atoms or 6 to ² carbon atoms which may be optionally substituted with an alkyl group.
Represents an aryl group of 0, which may be the same or different. A) a phosphorus compound represented by the following general formula (1), wherein the repeating unit of the general formula (1) is 3 and forms a ring structure:

Embedded image (However, R ¹ and R ^{2 each} represent an alkyl group having 1 to 20 carbon atoms or 6 to ² carbon atoms which may be optionally substituted with an alkyl group.
Represents an aryl group of 0, which may be the same or different. ), A phosphorus compound having 4 repeating units of the above general formula (1) to form a ring structure, and three or more repeating units of the above general formula (1) bonded in a chain. Examples of the phosphorus compound include:

The phosphazene compound used in the present invention is
The phosphorus compound represented by the above formula (2), the phosphorus compound represented by the above formula (3), or the phosphorus compound represented by the above general formula (1) in which three or more repeating units are bonded in a chain. The phosphorus compounds mentioned may be used alone, or a mixture of these phosphorus compounds may be used.

In the above formulas (1) to (3), R ¹ and R ² are specifically a methyl group as an alkyl group,
Examples of the group include an ethyl group, a propyl group, and a butyl group. Examples of the aryl group include a phenyl group, an alkyl-substituted phenyl group such as a cresyl group and a propylphenyl group, a naphthyl group, and an alkyl-substituted naphthyl group. Of these, an aryl group is preferably used, and a phenyl group is particularly preferably used. The phosphazene compound in the present invention is particularly preferably a compound represented by the formula (2) and / or the formula (3), and more preferably, in the formulas (2) and (3), R ¹ and R ² are the same. A phenyl group is used.

The content of the (C) phosphazene compound is as follows:
1.5 to 15 parts by weight, preferably 2.0 to 1 part by weight, based on 100 parts by weight of the total of (A) the aromatic polycarbonate resin and (B) the thermoplastic polyester resin.
It is 2 parts by weight, more preferably 2.5 to 10 parts by weight. If the amount is less than 1.5 parts by weight, the flame retardancy is insufficient and
If it exceeds 5 parts by weight, chemical resistance deteriorates, and furthermore, heat resistance,
Moisture and heat resistance decreases.

The talc and / or (D) used in the present invention
Alternatively, mica is generally known as a silicate compound and is not particularly limited, and may be natural or synthesized.

(D) The average diameter of talc and / or mica is not particularly limited, but from the viewpoint of workability and appearance of the obtained molded article, a preferable average diameter is 0.01 to 10%.
0 μm, more preferably 0.1 to 50 μm, even more preferably 0.3 to 40 μm. Here, the average diameter is a particle diameter when converted into a circle obtained by image processing of a micrograph.

Further, (D) talc and / or mica 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, vinyl silane, and the like.
Examples of titanate-based linking agents include monoalkoxy type, chelate type and coordinate type. (D) The method of treating talc and / or mica with a surface treatment agent is not particularly limited, and can be performed by a usual method. For example, it can be carried out by adding the surface treating agent to the layered silicate and stirring or mixing in a solution or while heating.

The amount of (D) talc and / or mica added is (A) an aromatic polycarbonate resin and (B)
0.5 to 30 parts by weight, preferably 0.7 to 100 parts by weight of the total amount of the thermoplastic polyester resin.
It is 5 to 25 parts by weight, more preferably 1 to 20 parts by weight. If the amount is less than 0.5 part by weight, the effect of improving the flame retardancy is small, and if it exceeds 30 parts by weight, the chemical resistance tends to be adversely affected.

The resin composition of the present invention is selected from the group consisting of (E) a graft copolymer and an olefin resin in order to further improve the impact strength, toughness, chemical resistance and the like of the obtained molded article. It is preferable to use at least one kind of soft resin. As the soft resin, those having a glass transition temperature of 0 ° C. or lower, more preferably −20 ° C. or lower are preferable because the impact strength of the obtained resin is improved.

Of the component (E), the graft copolymer is a rubber obtained by graft copolymerizing a vinyl monomer with a rubber-like elastic material. Examples of the rubbery elastic body include diene rubbers such as polybutadiene, styrene-butadiene rubber, acrylonitrile-butadiene rubber, alkyl (meth) acrylate-butadiene rubber, acrylic rubber, ethylene-propylene rubber, and siloxane rubber. These are used alone or in combination of two or more. In addition, vinyl monomers include aromatic vinyl compounds, vinyl cyanide compounds, alkyl (meth) acrylates, and other vinyl compounds that can be graft-polymerized to rubber-like elastic materials. Are used alone or in combination of two or more.

The aromatic vinyl compound includes:
Styrene, o-methylstyrene, m-methylstyrene,
Examples thereof include p-methylstyrene, α-methylstyrene, chlorostyrene, bromostyrene, vinyltoluene and the like, and these are used alone or in combination of two or more. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and these may be used alone or in combination of two or more. Furthermore, examples of the alkyl (meth) acrylate include butyl acrylate, butyl methacrylate, ethyl acrylate, ethyl methacrylate, methyl acrylate, methyl methacrylate, and the like. These may be used alone or in combination of two or more. Also,
As the other vinyl compounds, acrylic acid, unsaturated acids such as methacrylic acid, glycidyl acrylate,
Glycidyl (meth) acrylate such as glycidyl methacrylate, vinyl acetate, maleic anhydride, N-
Phenylmaleimide and the like are used, and these are used alone or in combination of two or more.

The copolymerization ratio at the time of copolymerizing the rubber-like elastic material and the vinyl monomer is not particularly limited, but a preferable ratio for further increasing the impact strength is a weight ratio (rubber-like elastic material / 10/90 to 90/10 with vinyl monomer),
Furthermore, it is 30/70 to 80/20. When the proportion 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 with the components (A) and (B) tends to decrease.

Among the components (E), the term “olefin resin” means, in addition to polyolefin in a narrow sense, a polydiene, a mixture of two or more thereof, and a copolymer of two or more olefin monomers and diene monomers. It is used as a broad concept including a coalescence, a copolymer comprising at least one other vinyl monomer copolymerizable with an olefin monomer and an olefin, and the like. For example, ethylene, propylene, 1-butene, 1-pentene, isobutene, butadiene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 1,5-norbornadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene , 1,5-
Cyclooctadiene, 1,3-cyclooctadiene,
Homopolymers or copolymers selected from one or a combination of two or more of monomers such as α, ω-non-conjugated dienes, and two of these homopolymers and copolymers A mixture composed of the above is mentioned. Among these, polyethylene, polypropylene and the like are preferably used because the resulting resin composition has improved chemical resistance. In addition, these olefin components, (meth) acrylic acid, alkyl (meth) acrylate, glycidyl (meth) acrylate, vinyl acetate, maleic anhydride, N
A copolymer with another monomer copolymerizable with an olefin such as phenylmaleimide or carbon monoxide may be used.
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 An acrylic acid copolymer, an ethylene / maleic anhydride copolymer, an ethylene / maleic anhydride / N-phenylmaleimide copolymer and the like can be mentioned. Among these polyolefin-based resins, preferred specific examples from the viewpoint of compatibility with the component (A) and the component (B) and heat resistance include ethylene-ethyl acrylate copolymer, ethylene-glycidyl methacrylate copolymer, ethylene -An acrylic acid copolymer is mentioned. The method for polymerizing these polyolefin resins is not particularly limited, and can be polymerized by various methods. If polyethylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, depending on the polymerization method,
Although linear low-density polyethylene and the like can be obtained, any of them can be preferably used.

By adding the graft polymer and the olefin resin together as the component (E), the various effects described above can be further enhanced.

Component (E) is added in an amount of preferably 1 to 15 parts by weight, based on 100 parts by weight of the total of (A) the polycarbonate resin and (B) the thermoplastic polyester resin.
More preferably, it is 1.5 to 12 parts by weight, most preferably 2 to 10 parts by weight. If it exceeds 15 parts by weight, flame retardant,
It is not preferable because rigidity and heat resistance tend to decrease. If the amount is less than 1 part by weight, the effect of improving the impact strength is small, which is not preferable.

Further, the flame-retardant thermoplastic resin composition of the present invention contains a fluorine-containing resin within a range not impairing the properties (chemical resistance and heat resistance) aimed at by the present invention in order to enhance the flame retardancy. , Silicone and the like can be used.

The fluororesin is a resin having a fluorine atom in the resin, and specifically, polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, tetrafluoroethylene / Xafluoropropylene copolymers and the like can be mentioned. Further, to the extent that physical properties such as flame retardancy of the obtained molded article are not impaired, if necessary, polymerization is carried out by using a monomer used for producing the fluororesin and a copolymerizable monomer in combination. The obtained copolymer may be used. These fluorinated resins are used alone or in combination of two or more. The molecular weight of the fluororesin is preferably from 1,000,000 to 20,000,000, more preferably from 2,000,000 to 10,000,000. As a method for producing these fluororesins, generally known methods such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization can be used.

The silicone is a polyorganosiloxane, such as a diorganosiloxane compound such as dimethylsiloxane and phenylmethylsiloxane; an organosilsesquioxane compound such as methylsilsesquioxane and phenylsilsesquioxane; Silhemioxane, triorganosylhemioxane compounds such as triphenylsilhemioxane, and copolymers obtained by polymerizing these, polydimethylsiloxane,
Examples include organopolysiloxanes such as polyphenylmethylsiloxane, polymethylsilsesquioxane, and polyphenylsilsesquioxane. In the case of an organopolysiloxane, a modified silicone having a molecular terminal substituted by an epoxy group, a hydroxyl group, a carboxyl group, a mercapto group, an amino group, an ether, or the like is also useful.
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 form of the silicone is not particularly limited, and any form such as an oil, a gum, a varnish, a powder, and a pellet can be used.

The amount of the fluorine-based resin and silicone added depends on the properties (chemical resistance, heat resistance, etc.) aimed at by the present invention.
The amount is not limited as long as it is not impaired, but is preferably 0.01 to 10 parts by weight, more preferably 0 to 10 parts by weight, based on 100 parts by weight of the total of (A) the aromatic polycarbonate resin and (B) the thermoplastic polyester resin. 0.03 to 8 parts by weight, particularly preferably 0.05 to 6 parts by weight. The amount added is 0.
If it is less than 01, the effect of improving the flame retardancy is small, and
Exceeding the weight part is undesirable because the moldability and the like are reduced.

Further, the flame-retardant thermoplastic resin composition of the present invention may be used as a reinforcing material by further combining a reinforcing filler. By adding a reinforcing filler, it is possible to further improve heat resistance, mechanical strength, and the like. Specific examples of reinforcing fillers include, for example, glass fibers, carbon fibers, fibrous fillers such as potassium titanate fibers, crow beads, glass flakes, kaolin, wollastonite, smectite, diatomaceous earth, calcium carbonate, calcium sulfate,
Barium sulfate and the like can be mentioned. Particularly preferred as reinforcing fillers are silicate compounds (excluding talc and mica) and / or fibrous reinforcing agents.

Silicate compounds (excluding talc and mica)
), The chemical composition is SiO _TwoPowder containing unit
Compounds with a shape such as shape, grain, needle, plate, etc.
For example, magnesium silicate, aluminum silicate, silica
Calcium acid, wollastonite, kaolin, diatomaceous earth,
Mectite, etc.
It may be something. Among them, kaolin and smectite
Is preferred.

The average diameter of the silicate compound (excluding talc and mica) is not particularly limited, but a preferable average diameter is 0.01 to 100 μm, more preferably 0.1 to 50 μm, and particularly preferably. Is 0.3-40μ
m. 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. Here, the average diameter is a particle diameter when converted into a circle obtained by image processing of a micrograph.

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-based coupling agent include an epoxy-based silane, an amino-based silane, and a vinyl-based silane, and examples of the titanate-based coupling agent include a monoalkoxy-type, a chelate-type, and a 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, it can be carried out by adding the above-mentioned surface treating agent to the layered silicate, and stirring or mixing with heating in the solution as needed.

[0056] 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 fibers are used as the reinforcing filler, the diameter is preferably about 1 to 20 μm and the length is about 0.01 to 50 mm. If the diameter is too small or the fiber length is too short, the effect of reinforcement is not sufficient, and conversely, the diameter is too large,
If the fiber length is too long, the surface properties, extrusion processability, and moldability of the molded product deteriorate, which is not preferable.

The reinforcing fillers can be used alone or in combination of two or more. The combination when two or more kinds are used in combination is not particularly limited, but a preferable combination is two or more kinds of reinforcing fillers selected from kaolin, smectite, and glass fiber.

The amount of the reinforcing filler to be added is not limited as long as the desired properties (chemical resistance and the like) of the present invention are not impaired. However, (A) aromatic polycarbonate resin and (B)
The amount is preferably 0.5 to 100 parts by weight, more preferably 1 to 60 parts by weight, particularly preferably 2 to 40 parts by weight, based on 100 parts by weight of the total amount of the thermoplastic polyester resin. 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 thermoplastic resin composition of the present invention comprises
Still other arbitrary thermoplastic or thermosetting resins within a range not impairing the object of the present invention, such as a liquid crystal polyester resin, a polyester ester elastomer resin, a polyester ether elastomer resin, a polyolefin resin, a polyamide resin, and polystyrene. A resin, a polyphenylene sulfide resin, a polyphenylene ether-based side oil, a polyacetal resin, a polysulfone resin, or the like may be added alone or in combination of two or more.

In order to improve the performance of the flame-retardant resin composition of the present invention, antioxidants such as phenol-based antioxidants and thioether-based antioxidants, heat stabilizers such as phosphorus-based stabilizers, etc. Are preferably used alone or in combination of two or more. Furthermore, if necessary, lubricants, release agents, plasticizers, non-phosphorus-based flame retardants, flame retardant aids, ultraviolet absorbers, light stabilizers, pigments, dyes, antistatic agents, conductive agents Property imparting agent, dispersant,
Additives such as a compatibilizer and an antibacterial agent can be used alone or in combination of two or more.

The method for producing the resin composition of the present invention is not particularly limited. For example, the components (A) to (D),
Further, it can be produced by, for example, a method of drying the component (E), other additives, resins, and the like, if necessary, followed by melt-kneading with a melt-kneading machine such as a single-screw or twin-screw extruder. it can. When the compounding agent is a liquid, it can be manufactured by adding the compounding agent to a twin-screw extruder using a liquid supply pump or the like.

The method of molding the flame-retardant thermoplastic resin composition according to the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, such as injection molding, blow molding, extrusion molding, and the like. Vacuum molding, press molding, calender molding, foam molding and the like can be applied.

The flame-retardant thermoplastic resin composition of the present invention is suitably used for various uses. Preferred applications include
For example, injection molded articles, blow molded articles, extruded molded articles, foam molded articles, etc. of home appliances, OA equipment parts, automobile parts and the like can be mentioned.

[0065]

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 parts by weight unless otherwise specified. The evaluation of the resin composition was performed by the following method.

[Evaluation Method] The obtained resin pellets were
After drying at 0 ° C for 5 hours, using a 35t injection molding machine, the cylinder temperature is 280 ° C, the mold temperature is 70 ° C, and the thickness is 1.6m.
m, 3.2 mm, and 6.4 mm bars (each having a width of 12.7 mm and a length of 127 mm) were evaluated as follows.

[Flame retardancy] The flame retardancy of a 1.6 mm thick bar was evaluated in accordance with the UL-94V standard.

[Chemical Resistance] A 3.2 mm-thick bar having a strain of 1.0% was treated with water for 5 minutes.
A diluted aqueous solution of MagicLin (synthetic detergent, trade name of Kao Corporation) or a commercially available hydraulic oil was applied and treated at 23 ° C. × 24 h and 23 ° C. × 240 h, respectively. Was evaluated according to the following criteria. ：: no change in appearance, ×: occurrence of cracks.

[Heat resistance] Using a bar having a thickness of 6.4 mm,
According to ASTM D-648, the deflection temperature under load was measured at a load of 0.45 MPa, and the heat resistance was evaluated.

[Impact Resistance] Using a bar having a thickness of 3.2 mm, the Izod impact strength with a notch was measured in accordance with JIS K7110.

Example 1 The viscosity average molecular weight was about 2200
0 bisphenol A type polycarbonate resin (A-
1) 85 parts, 15 parts of a polyethylene terephthalate resin (B-1) having a logarithmic viscosity of about 0.75 d1 / g, and as a phosphazene compound, in the general formula (1), R ¹ and R ² are phenyl groups; 3 or 4 repeating units
3 parts of a mixture of phosphazene compounds having a cyclic structure (phenoxyphosphazene oligomer SP-134, trade name of Otsuka Chemical Co., Ltd.) (C-1), talc having an average particle size of 3.2 μm (Microace K-1, manufactured by Nippon Talc) Product name)
(D-1) 10 parts, and 0.3 parts of ADK STAB HP-10 (trade name, manufactured by Asahi Denka) as a phosphorus-based stabilizer were dry-blended in advance, and then a twin-screw extruder with a vent set to a cylinder temperature of 280 ° C. (TEX44, trade name, manufactured by Nippon Steel Works, Ltd.) and melt-extruded to obtain a pellet-shaped resin composition. Table 1 shows the evaluation results of the obtained resin compositions.

Examples 2 to 10 and Comparative Examples 1 to 9 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 Tables 1 and 2. In addition, what was described in Table 3 was used as a compounding agent other than the above. The evaluation results are shown in Tables 1 and 2.

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

[Table 3]

As is clear from the results in Tables 1 and 2, in Comparative Examples 1 and 2, the mixing ratio of the polycarbonate resin and the thermoplastic polyester resin was out of the range of the present invention, so that the chemical resistance, heat resistance or Flame retardancy is inferior to the examples. In Comparative Example 3, since a large amount of the phosphazene compound was added, the chemical resistance was reduced, and the heat resistance was further inferior. In Comparative Example 4, since the amount of the phosphazene compound added was smaller than the range of the present invention, the flame retardancy was poor. Comparative Examples 5 and 6 are inferior in flame retardancy because talc and / or mica are not added. In Examples 6 to 10, since the soft resin as the component (E) was added, the impact resistance was planted. In Comparative Examples 7 to 9, the soft resin as the component (E) was used. Due to the large amount added, flame retardancy and heat resistance are poor. As is clear from the above, it is understood that the resin composition of the present invention is excellent in all of flame retardancy, chemical resistance and heat resistance.

[0077]

According to the present invention, an industrially very useful flame-retardant resin composition having excellent chemical resistance and heat resistance can be obtained.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C08L 69/00 67:00 51:04 23:00) (C08K 13/02 3:34 5: 5399)

Claims (2)

[Claims] A weight ratio (A / A / A) of (A) an aromatic polycarbonate resin and (B) a thermoplastic polyester resin.
Resin 1 contained in B) in the range of 90/10 to 50/50
A flame-retardant thermoplastic resin composition comprising: 00 parts by weight, (C) 1.5 to 15 parts by weight of a phosphazene compound, and (D) 0.5 to 30 parts by weight of talc and / or mica. 2. The flame-retardant thermoplastic resin composition according to claim 1, further comprising: (E) at least one soft resin selected from the group consisting of a graft copolymer and an olefin resin;
A flame-retardant thermoplastic resin composition obtained by adding 1 to 15 parts by weight to 100 parts by weight of the total of (B) and (B).