JPH01170644A - Flame-retardant polyester resin composition and electric component - Google Patents

Abstract

PURPOSE:To obtain the title resin composition obtained by blending a specific amine compound with an amide compound and prevented in stain of mold or joint metal caused when flame-retarded with a halogen based retardant. CONSTITUTION:(A) Thermoplastic polyester resin is blended with (B) 1-25wt.% organic halogen based fire retardant, (C) 0.01-5wt.% compound selected from an amine compound expressed by formula I, amide compound expressed by formula II-IV (R<1>-R<10> are H, 1-35C alkyl, aryl or polyoxyalkylene having >=1 polymerization degree; in each group of R<1>-R<3>, R<4>-R<6>, R<7>-R<8>, R<9>-R<10>, at least one is >=12C alkyl or aryl; X and Y are alkylene or arylene; m and n are 0 or 1) and (D) 0-60wt.% inorganic filler.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a flame retardant polyester resin composition.

More specifically, we are improving mold contamination during molding of polyester resin made flame retardant by blending organic halogen flame retardants, and contamination of contact metals when used in electrical parts with electrical contacts. The present invention relates to a resin composition.

[Conventional technology and its problems]

Thermoplastic polyester resins, such as polyalkylene terephthalate resins, have excellent mechanical properties, electrical properties, moldability, etc., and are therefore used in a wide range of applications as engineering plastics.

At this time, for applications such as electrical parts that require flame retardancy, organic halogen flame retardants or those further blended with flame retardant aids are used to impart flame retardancy.

However, polyester resin compositions containing such flame retardants and flame retardant aids generally contaminate the mold during molding, deteriorating molding efficiency due to cleaning, and furthermore, the polyester resin compositions containing flame retardants and flame retardant aids contaminate the mold during molding. When used in parts such as housings and circuit boards of switches, relays, etc., there is a problem in that the contact metals are contaminated during long-term use and the electrical resistance of the contacts increases significantly. In particular, the latter problem is serious because it significantly impairs the reliability of electrical parts and the like.

On the other hand, methods using flame retardants that do not contain halogens, such as phosphorus compounds and metal hydrates, are effective in solving the above problems, but this method does not provide sufficient flame retardancy. Moreover, since a large amount of flame retardant is required, there is a problem that various physical properties such as mechanical properties are significantly deteriorated.

Thus, there has been a strong desire for an excellent resin composition that has sufficient flame retardancy without impairing the excellent properties of polyester resins, and also does not have the problem of metal contamination as described above.

[Means for solving problems]

In view of such demands, the present inventors have made extensive studies to solve the problem of metal contamination without impairing the excellent properties of flame-retardant polyester resin compositions containing organic halogen flame retardants. As a result, it was discovered that the addition of a specific compound was effective, and the present invention was achieved.

That is, the present invention includes (A) a thermoplastic polyester resin (B) an organic halogen flame retardant (1 to 25% by weight in the composition) (C) an amine compound represented by the following general formula (1), and the following general formula ( 2) 0.01 to 5% by weight of one or more compounds selected from the group consisting of amide compounds shown in (3) and (4) (in the composition) (D) 0 to 5% by weight of an inorganic filler The present invention provides a flame-retardant polyester resin composition comprising 60% by weight (based on the composition), and an electrical component having metal contacts formed by molding the same.

R' -N -R" [wherein R1 to R1G are hydrogen, an alkyl group having 1 to 35 carbon atoms or a substituted alkyl group, an aryl group, a substituent group,
R1-R3, R4-R6, R1-
In each group of R8, R9-R10, at least one is an alkyl group or substituted alkyl group having 12 or more carbon atoms,
It is an aryl group or a substituted aryl group.

Further, X and Y represent an alkylene group, a substituted alkylene group, an arylene group, or a substituted arylene group, and m and n are 0 or 1. ] The thermoplastic polyester used in the present invention is a polyester mainly composed of dicarboxylic acid residues and diol residues or oxycarboxylic acid residues.

Examples of dicarboxylic acids used as raw material monomers for polyester include terephthalic acid, isophthalic acid, 2-methylterephthalic acid, 4-methylterephthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid,
These are bifunctional carboxylic acids such as adipic acid and sebacic acid, or derivatives thereof capable of forming esters, and one or more types thereof can be used. Particularly preferred is terephthalic acid or its lower alcohol ester.

Examples of other monomer diols include ethylene glycone peprobylene glyconohetrimethylene glycol, tetramethylene glycol, neopentyl glyconohebutenediol, hydroquinone, dihydroxyphenynohenaphthalenediol, dihydroxydiphenyl ether/L'%2 .Glycols such as 2'-bis(4-hydroxyphenyl)propane and polyalkylene glycol, or derivatives thereof capable of forming esters, and 1
You may use a species or a mixture of two or more kinds.

Examples of oxycarboxylic acids include oxybenzoic acid, oxynaphthoic acid, and derivatives thereof capable of forming esters.

Any polyester produced by polycondensation using each of these components as a monomer component can be effectively used as the thermoplastic polyester of the present invention, either alone or in a mixture of two or more, but polyalkylene terephthalate is preferred, and polyalkylene terephthalate is particularly preferred. Preferred are polybutylene terephthalate,
Or a copolymer mainly composed of this.

Further, the flame retardant used in the present invention may be any organic halogen compound generally used in thermoplastic polyester, but aromatic bromine compounds are particularly preferred.
Specific examples include low molecular weight bromine compounds such as 5-10 bromine substituted compounds of diphenyl ether, monomers of aromatic carbonates or epoxy compounds derived from bisphenol A etc., brominated products of these polymers, polystyrene oligomers, etc. These include brominated compounds, brominated cyanuric acid ester compounds, and the like.

These flame retardants may be used alone or in combination of two or more. The amount of flame retardant to be added is preferably as small as possible, since increasing the amount will reduce the mechanical properties of the composition, but generally it is 1 to 25% by weight, and 2 to 25% by weight based on the total amount of the composition. 20% by weight is particularly preferred. In the present invention, the flame retardant is preferably used together with a flame retardant aid.

The flame retardant aid used here includes metal oxides and hydroxides such as antimony dioxide, antimony halides, aluminum hydroxide, and magnesium hydroxide. The amount of the flame retardant aid added is 0 to 15% by weight, preferably 1 to 10% by weight, based on the total amount of the composition.

For thermoplastic polyester resin, flame retardants such as those mentioned above,
Alternatively, blending this together with a flame retardant aid is an effective means for imparting flame retardancy, but such a composition has the problem of metal contamination as mentioned above, and is especially difficult to use when exposed to electricity.・It is essential when used as electronic device parts.

On the other hand, the specific amine compound or amide compound which is component (C) of the composition of the present invention is extremely effective in reducing metal contamination caused by this flame retardant.

In the present invention, the amine compound blended for this purpose is represented by the following general formula (1).

[In the formula, R1, 12, 13 represent hydrogen, an alkyl group or substituted alkyl group having 1 to 35 carbon atoms, an aryl group, a substituted aryl group, a polyoxyalkylene group or substituted polyoxyalkylene group with a degree of polymerization of 1 or more, Although they may be the same or different, at least one of these endogenous groups is an alkyl group or substituted alkyl group, an aryl group, or a substituted aryl group having 12 or more carbon atoms.

Moreover, R1, R2, and R3 may further have an amino group, an amide group, etc. therein. ] In the present invention, any amine compound that conforms to general formula (1) can be used, but aromatic amines are preferred, and two or more of R1 to R3 are aryl-substituted alkyl groups, aryl or substituted aryl groups, such as evaporate, diphenylamine, phenyl-β-naphthylamine, 4,4°-bis-(4-α,α′-dimethylbenzyl)diphenylamine, and the like.

Further, in the present invention, as the amide compound, those represented by the following general formulas (2), (3) and (4) are used.

[In the formula, R4 to RIG represent hydrogen, an alkyl group or substituted alkyl group having 1 to 35 carbon atoms, an aryl group, a substituted aryl group, a polyoxyalkylene group or substituted polyoxyalkylene group with a degree of polymerization of 1 or more, and each is the same and may be different, but R4~R'', R''y, Rs,
In each group of R9 to RIG, at least one is an alkyl group or substituted alkyl group, an aryl group, or a substituted aryl group having 12 or more carbon atoms. Moreover, R4-R10 may further have an amino group, an amide group, etc. therein.

Further, x and y represent an alkylene group, a substituted alkylene group, an arylene group, or a substituted arylene group, and m and n are 0 or 1. ] In the present invention, any amide compound compatible with the general formulas (2) to (4) can be used, but aromatic amide compounds are preferable, and more preferably aromatic amide compounds are used.
) and has an aromatic ring in two or more of R4-R6, and a compound represented by general formula (3) or (4) and having at least one aromatic ring in the compound. be. The latter is particularly preferred.

For example, N,N'-hexamethylenebis(3,5-dyl-t-phthyl-4-hydroxy-hydroxynamamide)
,N,N”-bis[3-(3,5-di)butyl-4
-hydroxyphenyl)propionyl]hydrazine, and the like.

In the present invention, these amine compounds and amide compounds are added so that the composition contains 0.01 to 5% by weight. If the amount is less than 0.01% by weight, sufficient metal contamination resistance effect cannot be obtained, and if the amount is more than 5% by weight, it is not only uneconomical but also the metal contamination resistance effect reaches saturation, and conversely, the physical properties deteriorate. etc. cannot be ignored, which is not desirable. From the viewpoints of metal stain resistance improvement effect, physical properties, and economic efficiency, it is preferably used in an amount of 0.01 to 1% by weight.

Next, an inorganic filler is added to the composition of the present invention, if necessary. - The inorganic fillers used are usually used to improve mechanical and physical properties such as strength, rigidity, hardness, heat resistance, deformation resistance, and electrical properties of thermoplastic polyester. It is a well-known inorganic filler that can be added in any shape depending on the purpose, such as fibrous, plate, powder, etc.

Examples include glass fiber, glass foil, milled glass fiber, glass beads, asbestos, talc, clay, kaolin, silica, alumina, potassium titanate fiber, carbon fiber, graphite fiber, various mica, wollastonite, calcium silicate. , graphite, other inorganic acid salts such as carbonates and sulfates, metal fibers, metal foils,
Metal powder, etc. Two or more of these may be used depending on the purpose.

Particularly important and most effective in the present invention are glass fibers and mixed fillers of glass fibers and other inorganic fillers.

Such an inorganic filler may be used as it is, but in order to further enhance its effects such as mechanical strength, it is preferable to treat the surface with a surface treatment agent or a coupling agent, or to add these at the same time.

As the surface treatment agent or coupling agent for the inorganic filler used here, there are used known functional compounds conventionally used for this purpose, such as epoxy compounds, isocyanate compounds, silane compounds, and titanate compounds.

In the present invention, the amount of the inorganic filler used is 0 to 60% by weight, preferably 5 to 50% by weight based on the total amount of the composition.
It is. The amount of the functional compound surface treatment agent used in combination is 0 to 10% by weight, preferably 0.05 to 5% by weight, based on the inorganic filler.

Further, the composition of the present invention may further contain a known thermoplastic resin in combination. For example, polyethylene,
Ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, polypropylene, ethylene-propylene copolymer, polyamide, polyacetal, polystyrene, styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, styrene- butadiene-acrylic acid or its ester) copolymer, styrene-acrylonitrile copolymer, polycarbonate,
Polyurethane, fluororesin, polyphenylene oxide, polyphenylene sulfide, polybutadiene, halogenated polyolefin, polyhalogenated vinyl, butyl rubber, multilayer graft copolymers mainly composed of polyacrylate, etc. can be blended in any ratio depending on the purpose. It is.

The composition of the present invention may further include conventionally known additives, such as lubricants, nucleating agents, mold release agents, antistatic agents, other surfactants, plasticizers, and colorants, in order to impart desired properties depending on the purpose. Of course, it is also possible to add a heat-resistant stabilizer, an ultraviolet light stabilizer, and the like.

The composition of the present invention can be easily prepared using known equipment and methods commonly used for conventional resin composition preparation methods. For example, l) a method of mixing each component and then kneading and extruding it using an extruder to prepare pellets, and then molding; 1i) - first preparing pellets with different compositions, mixing a predetermined amount of the pellets and molding; method for obtaining a molded product with the desired composition after molding, 1ii) applying one or two of each component to a molding machine;
Any method of directly preparing the above ingredients can be used. Further, it is a preferable method to mix and add a part of the resin component as a fine powder with other components in order to uniformly blend these components.

The flame-retardant polyester resin composition of the present invention can be processed into various molded products that require flame retardancy, and its effects are particularly remarkable when applied to electrical parts having metal contacts.

〔Example〕

EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

The characteristics shown in the examples below are measured as follows.

1) Method for evaluating metal contamination After thoroughly drying the pellets prepared in the Examples and Comparative Examples, 20 g of the pellets were placed in a silver piece (15 mm x 2 mm x
0.2 mm) or a copper piece with measuring contacts made of 10% silver and 90% gold alloy, sealed in a glass tube,
After heating at 0° C. for 240 hours, the electrical resistance value of the metal piece was measured using a milliohmmeter.

2) Physical property measurement method tensile test Impact strength according to ASTM D-638
Based on ASTM D-256 3) Place the test piece for long-term thermal stability tensile test in an oven, in an air atmosphere,
After heating at 180° C. for 20 days, the tensile strength was measured and the strength retention rate relative to the initial strength was determined.

Examples 1 to 9, Comparative Examples 1 to 4 Flame retardants, flame retardant aids, various fillers, and amine compounds or amide compounds were added and mixed to polybutylene terephthalate with an intrinsic viscosity of 1.0 in the proportions shown in Tables 1 and 2. Then, a pellet-like composition was obtained using an extruder.

Next, using this pellet, perform the metal contamination test,
In addition, test pieces were molded by injection molding, and mechanical properties and long-term thermal stability were evaluated.

The results are shown in Tables 1 and 2.

On the other hand, as a comparative example, pellets containing no amine compound or amide compound were similarly tested and evaluated.

〔Effect of the invention〕

As is clear from the above description and examples (the composition of the present invention in which a specific amine compound or amide compound is further blended with a polyester resin containing an organic halogen flame retardant) Not only does it effectively improve the problem of metal contamination, especially metal contamination that coexists with the mold during molding and during use, but it also improves the thermal stability of the resin.
Deterioration during melt processing or long-term high-temperature use is improved, and there is no loss in mechanical properties such as flame retardancy, various strengths, rigidity, deformation resistance, various chemical and electrical properties, etc. It is particularly suitable for use as electrical parts.

Claims (1)

[Scope of Claims] 1 (A) Thermoplastic polyester resin (B) 1 to 25% by weight of an organic halogen flame retardant (in the composition) (C) An amine compound represented by the following general formula (1), and the following general 0.01 to 5% by weight (in the composition) of one or more compounds selected from the group consisting of amide compounds represented by formulas (2), (3) and (4) (D) Inorganic filler A flame-retardant polyester resin composition comprising 0 to 60% by weight (in the composition). ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( 4) [In the formula, R^1 to R^1^0 are hydrogen, an alkyl group or substituted alkyl group having 1 to 35 carbon atoms, an aryl group, a substituted aryl group, a polyoxyalkylene group with a degree of polymerization of 1 or more, or a substituted polyoxyalkylene group. Indicates an oxyalkylene group, each of which may be the same or different, R^1~R^3, R^4~
In each group of R^6, R^7 to R^8, R^9 to R^1^0, at least one is an alkyl group or substituted alkyl group, an aryl group, or a substituted aryl group having 12 or more carbon atoms. . Further, X and Y represent an alkylene group, a substituted alkylene group, an arylene group, or a substituted arylene group, and m and n are 0 or 1. ] 2 The amine compound represented by the general formula (1) is R^1~
The flame-retardant polyester resin composition according to claim 1, which is an amine having an aromatic ring in two or more of R^3. 3. The flame-retardant polyester according to claim 1, wherein the amide compound is represented by the above general formula (3) or (4) and has at least one aromatic ring in the compound. Resin composition. 4. The flame-retardant polyester resin composition according to any one of claims 1 to 3, wherein the thermoplastic polyester resin is a polybutylene terephthalate resin or a copolyester mainly composed of polybutylene terephthalate resin. 5 (A) Thermoplastic polyester resin (B) Organic halogen flame retardant 1 to 25% by weight (in the composition) (C) An amide compound represented by the following general formula (1), and the following general formula (2), ( 0.01 to 5% by weight (in the composition) of one or more compounds selected from the group consisting of amide compounds shown in 3) and (4) (D) 0 to 60% by weight of an inorganic filler ( An electrical component having metal contacts formed by molding a flame-retardant polyester resin composition. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( 4) [In the formula, R^1 to R^1^0 are hydrogen, an alkyl group or substituted alkyl group having 1 to 35 carbon atoms, an aryl group, a substituted aryl group, a polyoxyalkylene group with a degree of polymerization of 1 or more, or a substituted polyoxyalkylene group. Indicates an oxyalkylene group, each of which may be the same or different, R^1~R^3, R^4~
In each group of R^6, R^7 to R^8, R^9 to R^1^0, at least one is an alkyl group or substituted alkyl group, an aryl group, or a substituted aryl group having 12 or more carbon atoms. . Further, X and Y represent an alkylene group, a substituted alkylene group, an arylene group, or a substituted arylene group, and m and n are 0 or 1. ]