WO2011155287A1 - Polybutylene terephthalate resin composition, metal composite component, and method for producing metal composite component - Google Patents

Abstract

Disclosed are: a polybutylene terephthalate resin composition which is capable of providing a metal composite component by molding even in cases where the mold temperature is 100˚C or less, said metal composite component having excellent flame retardancy and excellent adhesion between a metal component and the polybutylene terephthalate resin composition; and a method for producing a metal composite component. Also disclosed is a metal composite component which has excellent flame retardancy and excellent adhesion between a metal component and a polybutylene terephthalate resin composition. Specifically, a metal composite component is produced by blending a specific amount of a polyethylene terephthalate resin and a specific amount of a phosphorus flame retardant into a polybutylene terephthalate resin.

Description

Polybutylene terephthalate resin composition, metal composite part, and method for producing metal composite part

The present invention provides a metal having excellent adhesion between a metal part and a polybutylene terephthalate resin composition and having excellent flame retardancy when a metal part and a polybutylene terephthalate resin composition are combined to produce a metal composite part. The present invention relates to a polybutylene terephthalate resin composition giving a composite part. The present invention also relates to a method for producing a metal composite part comprising a metal part and a polybutylene terephthalate resin composition, excellent in adhesion between the metal part and the polybutylene terephthalate resin composition, and excellent in flame retardancy. Furthermore, the present invention relates to a metal composite part comprising a metal part and a polybutylene terephthalate resin composition, having excellent adhesion between the metal part and the polybutylene terephthalate resin composition, and excellent in flame retardancy.

Conventionally, metal composite parts manufactured by combining thermoplastic resin and metal parts by molding methods such as insert molding, outsert molding, and hoop molding have been widely used in home appliances, information communication equipment, automobile parts, etc. ing.

Further, among metal composite parts in which a thermoplastic resin and a metal part are combined, for example, a metal composite laminated part in which a thermoplastic resin is laminated on a part of or the entire surface of a metal plate has a functionality such as strength. From the viewpoints of lightness, design, etc., it has been attracting attention as a casing for small information / communication equipment such as mobile phones and notebook personal computers.

The thermoplastic resin used in such metal composite parts is required to have durability against various external stimuli, so mechanical characteristics, heat resistance, electrical characteristics, weather resistance, water resistance, chemical resistance, solvent resistance, etc. It is desired that these various properties are excellent, and from the standpoint of production efficiency, it is desired that they can be melt-molded by a method such as injection molding. For this reason, use of the polybutylene terephthalate resin composition excellent in various physical properties and moldability for metal composite parts has been studied.

However, when a metal composite part is produced by a method such as injection molding using a polybutylene terephthalate resin or a polybutylene terephthalate resin composition, the resin has a higher coefficient of linear expansion than a metal, or a low-temperature metal part. Since the shrinkage after molding differs greatly from the resin at high processing temperature, even if the metal part and the resin are in good contact within the mold, the metal part and the resin are in close contact after molding. There is a problem that the performance decreases. In addition, since polybutylene terephthalate resin has a high processing temperature, the thermoplastic resin on the surface of the metal part rapidly solidifies due to the contact between the molten thermoplastic resin and the low-temperature metal plate in the mold. In this manufacturing method, there is a problem that it is difficult to manufacture a metal composite part having excellent adhesion between the metal part and the polybutylene terephthalate resin composition.

For this reason, when manufacturing a metal composite laminated part using a polybutylene terephthalate resin or a polybutylene terephthalate resin composition, a molding method such as injection molding cannot be applied due to the problem of adhesion between the metal part and the resin. In addition, a complicated operation of laminating a metal part and a molded product of polybutylene terephthalate resin using an adhesive tape or an adhesive is necessary.

Under such circumstances, when a metal composite part is formed from a metal part and a polybutylene terephthalate resin or a polybutylene terephthalate resin composition by a method such as injection molding, a method for improving the adhesion between the metal part and the resin has been developed. It is desired.

As a method for improving the adhesion between a metal part and a resin in a metal composite part using a polybutylene terephthalate resin or a polybutylene terephthalate resin composition, for example, for a metal part made of an aluminum alloy, in the following order: Anodizing treatment, mechanical removal treatment of oxide layer film, etching treatment with acidic aqueous solution, contact treatment with hydrazine, etc. to perform fine etching, finely etched metal parts and polybutylene containing polyethylene terephthalate resin A method of manufacturing a metal composite part by compounding a terephthalate resin composition by injection molding (Patent Document 1), or after immersing a finely etched metal part in an aqueous solution of a water-soluble alcohol, the metal part and the polyethylene terephthalate resin Containing polybutylene terephthalate tree A composition process for producing a metal composite part with composite (Patent Document 2) are known by injection molding.

Also, high flame retardancy is required for metal composite parts used in the case of small information / communication devices such as mobile phones and notebook personal computers.

JP 2006-001216 A JP 2006-027018 A

According to the methods described in Patent Documents 1 and 2, since the polybutylene terephthalate resin composition slightly penetrates into the recesses formed on the surface of the metal part, the adhesion between the metal part and the polybutylene terephthalate resin composition due to the anchor effect. However, the obtained metal composite part is still easily peeled off at the contact surface between the metal part and the polybutylene terephthalate resin composition.

In addition, in the methods described in Patent Documents 1 and 2, in order to sufficiently infiltrate the polybutylene terephthalate resin composition into the recesses formed on the surface of the metal part, a high-temperature molten resin is used in the metal part at a low temperature. In order to prevent rapid solidification of the resin due to contact with the mold, it is necessary to set the mold temperature to a high temperature exceeding 100 ° C.

For this reason, in the methods described in Patent Documents 1 and 2, a generally used mold temperature control device for circulating hot water cannot be used, and a temperature control device using high-boiling oil as a heat medium is used. It is necessary and there are problems in terms of management of the heat medium and equipment costs. In addition, when the mold is at a high temperature, there is a problem in terms of workability at the time of manufacturing the metal composite part.

Furthermore, in Cited Documents 1 and 2, flame retardancy of metal composite parts is not studied, and the problem of flame retardance of metal composite parts using polybutylene terephthalate resin has not yet been solved.

The present inventor has excellent adhesion between a metal part and a polybutylene terephthalate resin composition when a metal composite part is produced by blending a specific amount of polyethylene terephthalate resin and a phosphorus-based flame retardant into the polybutylene terephthalate resin. In addition, it has been found that highly flame-retardant metal composite parts can be produced even at a mold temperature as low as 100 ° C. or less, and the present invention has been completed. Specifically, the present invention provides the following.

(1) One selected from the group consisting of (A) a polybutylene terephthalate resin, (B) a polyethylene terephthalate resin, a phosphinate, a diphosphinate, and a salt of a phosphinic acid condensate of a trimer or more. Including the above (C) phosphorus flame retardant,
The content of the (B) polyethylene terephthalate resin is 10% by mass to 50% by mass with respect to the total mass of the (A) polybutylene terephthalate resin and the (B) polyethylene terephthalate resin,
Metal whose content of said (C) phosphorus flame retardant is 10 mass parts or more and 100 mass parts or less with respect to 100 mass parts of total amounts of said (A) polybutylene terephthalate resin and said (B) polyethylene terephthalate resin. A polybutylene terephthalate resin composition for molding composite parts.

(2) The phosphoric flame retardant (C) is a phosphinate represented by the following general formula (1) and / or a diphosphinate represented by the following general formula (2). A polybutylene terephthalate resin composition for molding metal composite parts as described.

(In the general formulas (1) and (2), R ¹ and R ² are a linear or branched C _1-6 -alkyl group which may contain a phenyl group, hydrogen, and one hydroxyl group. , R ³ is a linear or branched C _1-10 -alkylene group, arylene group, alkylarylene group or arylalkylene group, and M is an alkaline earth metal, alkali metal, Zn, Al, Fe, Boron, m is an integer from 1 to 3, n is an integer from 1 or 3, and x is 1 or 2.)

(3) The polybutylene terephthalate resin composition for molding metal composite parts according to (2), wherein the (C) phosphorus flame retardant is aluminum diethylphosphinate.

(4) Furthermore, it contains (D) a nitrogen-containing flame retardant aid that is a salt of a triazine compound represented by the following general formula (3) and cyanuric acid or isocyanuric acid,
(D) The content of the nitrogen-containing flame retardant auxiliary is 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total amount of the (A) polybutylene terephthalate resin and the (B) polyethylene terephthalate resin. (1) to (3) The polybutylene terephthalate resin composition for forming a metal composite part according to any one of the above.

(In the formula, R ⁴ and R ⁵ are a hydrogen atom, an amino group, an aryl group, or an oxyalkyl group having 1 to 3 carbon atoms, and R ⁴ and R ⁵ may be the same or different.)

(5) The polybutylene terephthalate resin composition for molding metal composite parts according to (4), wherein the (D) nitrogen-containing flame retardant aid is melamine cyanurate.

(6) Further, (E) contains a filler,
(E) The content of the filler is 5 parts by mass or more and 120 parts by mass or less with respect to 100 parts by mass of the total amount of the (A) polybutylene terephthalate resin and the (B) polyethylene terephthalate resin. (5) The polybutylene terephthalate resin composition for forming a metal composite part according to any one of the above.

(7) Further, (F) containing a fluorine-based resin,
(F) Content of fluorine-type resin is 0.1 to 5 mass parts with respect to 100 mass parts of total amounts of said (A) polybutylene terephthalate resin and said (B) polyethylene terephthalate resin. The polybutylene terephthalate resin composition for forming a metal composite part according to any one of 1) to (6).

(8) Further, (G) contains an elastomer,
(G) The content of the elastomer is from 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the total amount of the (A) polybutylene terephthalate resin and the (B) polyethylene terephthalate resin. 7) The polybutylene terephthalate resin composition for forming a metal composite part according to any one of the above.

(9) A metal composite part comprising the polybutylene terephthalate resin composition for molding a metal composite part according to any one of (1) to (8) and a metal part.

(10) The metal composite part according to (9), wherein the metal part has been subjected to surface roughening treatment.

(11) The metal composite part according to (9) or (10), which is a personal computer part, a portable terminal part, or an OA equipment part.

(12) One selected from the group consisting of (A) a polybutylene terephthalate resin, (B) a polyethylene terephthalate resin, a phosphinate, a diphosphinate, and a salt of a trimer or more phosphinic acid condensate Including the above (C) phosphorus flame retardant,
The content of the (B) polyethylene terephthalate resin is 10% by mass to 50% by mass with respect to the total mass of the (A) polybutylene terephthalate resin and the (B) polyethylene terephthalate resin,
Molding material whose content of the (C) phosphorus flame retardant is 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the total amount of the (A) polybutylene terephthalate resin and the (B) polyethylene terephthalate resin A method for manufacturing a metal composite part, in which a metal molding machine is supplied to a mold on which the metal part is placed.

(13) The method for producing a metal composite part according to (12), wherein the molding material is a polybutylene terephthalate resin composition for molding a metal composite part according to any one of (1) to (8).

(14) The method for producing a metal composite part according to (12) or (13), wherein the metal part has been subjected to surface roughening treatment.

(15) The method for producing a metal composite part according to any one of (12) to (14), wherein the temperature of the mold is 100 ° C. or lower.

(16) A metal composite part obtained by the molding method according to any one of (12) to (15).

According to the present invention, a polybutylene terephthalate capable of forming a metal composite part having excellent adhesion between a metal part and a polybutylene terephthalate resin composition and excellent in flame retardancy even at a mold temperature of 100 ° C. or less. A resin composition is provided. Further, according to the present invention, a metal composite part having excellent adhesion between the metal composite part and the polybutylene terephthalate resin composition and excellent in flame retardancy can be produced even at a mold temperature of 100 ° C. or less. A method of manufacturing a metal composite part is provided. Furthermore, according to the present invention, a metal composite part having excellent adhesion between the metal part and the polybutylene terephthalate resin composition and excellent in flame retardancy is provided.

It is the schematic diagram seen from the upper surface of the test piece used for evaluation of metal adhesiveness in an Example. It is a schematic diagram which shows the evaluation method of the metal adhesiveness in an Example.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. . In addition, although description may be abbreviate | omitted suitably about the location where description overlaps, the summary of invention is not limited.

Hereinafter, the metal composite part molding material, the metal composite part manufacturing method, and the metal composite part will be described in order.

[Molding materials for metal composite parts]
First, a molding material for a metal composite part will be described. In the present invention, the molding material used for the production of the metal composite part includes (A) a polybutylene terephthalate resin, (B) a polyethylene terephthalate resin, and (C) a phosphorus flame retardant. Blended with one or more components selected from the group consisting of a flame retardant aid, (E) filler, (F) tetrafluoroethylene polymer, (G) elastomer, and (H) other additives It is.

The molding material of the metal composite part used in the present invention is not particularly limited as long as it contains a predetermined amount of the components (A) to (H). Specific examples of the form of the molding material of the metal composite part include (i) pellets, flakes, or powders of a polybutylene terephthalate resin composition obtained by melt-kneading all components contained in the molding material, and (ii) (A) polybutylene terephthalate resin, or (A) polybutylene terephthalate resin composition pellets, flakes or powder comprising polybutylene terephthalate resin and a desired component, and (B) polyethylene terephthalate resin or (B) polyethylene A pellet, flake, or powder mixture of (B) polyethylene terephthalate resin composition comprising a terephthalate resin and a desired component may be mentioned.

In the specification and claims of the present application, a material in which all components in the molding material are integrated by a method such as melt-kneading or melt molding is referred to as “polybutylene terephthalate resin composition”, and molding is performed. A material in which at least one component in the material is not integrated with other components is referred to as a “polybutylene terephthalate resin mixture”.

Among these forms, it is easy to uniformly mix each component in the molding material, and it is easy to mold a homogeneous metal composite part. (I) It is obtained by melt-kneading all the components contained in the molding material. Pellets, flakes or powders of the resulting polybutylene terephthalate resin composition are preferred. Further, when the molding material is a polybutylene terephthalate resin composition obtained by melting and kneading all the components, the shape is preferably a pellet because of excellent operability during molding.

(A) polybutylene terephthalate resin, (B) polyethylene terephthalate resin, and (C) phosphorus flame retardant, (D) nitrogen-containing flame retardant aid, (E) filler, (F) tetrafluoroethylene polymer, ( A method for obtaining a polybutylene terephthalate resin composition by blending one or more components selected from the group consisting of G) an elastomer and (H) other additives and melt-kneading these components is conventionally known. What is necessary is just to follow the manufacturing method of a resin composition. A suitable method for producing a polybutylene terephthalate resin composition by melt kneading includes a method using a melt kneading apparatus such as a single-screw or twin-screw extruder.

Hereinafter, (A) polybutylene terephthalate resin, (B) polyethylene terephthalate resin, (C) phosphorus-based flame retardant, (D) nitrogen-containing flame retardant aid, (E) filler, which are components of molding materials for metal composite parts , (F) tetrafluoroethylene polymer, (G) elastomer, and (H) other additives will be described in order.

[(A) Polybutylene terephthalate resin]
The (A) polybutylene terephthalate resin used in the present invention comprises a dicarboxylic acid component containing at least terephthalic acid or an ester-forming derivative thereof (C _1-6 alkyl ester, acid halide, etc.) and an alkylene having at least 4 carbon atoms. A polybutylene terephthalate resin obtained by polycondensation with a glycol component containing glycol (1,4-butanediol) or an ester-forming derivative thereof (acetylated product, etc.). The polybutylene terephthalate resin is not limited to a homopolybutylene terephthalate resin, and may be a copolymer containing 60 mol% or more (particularly 75 mol% or more and 95 mol% or less) of a butylene terephthalate unit.

The amount of terminal carboxyl group of (A) polybutylene terephthalate resin used in the present invention is not particularly limited as long as the object of the present invention is not impaired. The terminal carboxyl group amount of the (A) polybutylene terephthalate resin used in the present invention is preferably 30 meq / kg or less, and more preferably 25 meq / kg or less. When using a polybutylene terephthalate resin having an amount of terminal carboxysil group in such a range, the resulting metal composite part is less susceptible to strength reduction due to hydrolysis in a moist heat environment.

The intrinsic viscosity of the (A) polybutylene terephthalate resin used in the present invention is not particularly limited as long as the object of the present invention is not impaired. (A) The intrinsic viscosity (IV) of the polybutylene terephthalate resin is preferably 0.60 dL / g or more and 1.2 dL / g or less. More preferably, it is 0.65 dL / g or more and 0.9 dL / g or less. When a polybutylene terephthalate resin having an intrinsic viscosity in such a range is used, the resulting polybutylene terephthalate resin composition has particularly excellent moldability. The intrinsic viscosity can be adjusted by blending polybutylene terephthalate resins having different intrinsic viscosities. For example, a polybutylene terephthalate resin having an intrinsic viscosity of 0.9 dL / g is prepared by blending a polybutylene terephthalate resin having an intrinsic viscosity of 1.0 dL / g and a polybutylene terephthalate resin having an intrinsic viscosity of 0.7 dL / g. Can do. (A) The intrinsic viscosity (IV) of the polybutylene terephthalate resin can be measured, for example, in o-chlorophenol at a temperature of 35 ° C.

In the polybutylene terephthalate resin (A) used in the present invention, examples of dicarboxylic acid components (comonomer components) other than terephthalic acid and its ester-forming derivatives include, for example, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4 C _8-14 aromatic dicarboxylic acids such as 4,4'-dicarboxydiphenyl ether; C _4-16 alkanedicarboxylic acids such as succinic acid, adipic acid, azelaic acid and sebacic acid; C _5-10 such as cyclohexanedicarboxylic acid And cycloalkane dicarboxylic acids of the above; ester-forming derivatives of these dicarboxylic acid components (C _1-6 alkyl ester derivatives, acid halides, etc.). These dicarboxylic acid components can be used alone or in combination of two or more.

Among these dicarboxylic acid components, C _8-12 aromatic dicarboxylic acids such as isophthalic acid, and C _6-12 alkanedicarboxylic acids such as adipic acid, azelaic acid, and sebacic acid are more preferable.

In the (A) polybutylene terephthalate resin used in the present invention, examples of glycol components (comonomer components) other than 1,4-butanediol include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexa C _2-10 alkylene glycol such as methylene glycol, neopentyl glycol, 1,3-octanediol; polyoxyalkylene glycol such as diethylene glycol, triethylene glycol and dipropylene glycol; fat such as cyclohexanedimethanol and hydrogenated bisphenol A Cyclic diols; aromatic diols such as bisphenol A and 4,4′-dihydroxybiphenyl; ethylene oxide 2-mole adducts of bisphenol A; Such as alkylene oxide 3 moles adduct, alkylene oxide adducts of C _2-4 of bisphenol A; or ester-forming derivatives of these glycols (acetylated, etc.). These glycol components can be used alone or in combination of two or more.

Among these glycol components, C _2-6 alkylene glycol such as ethylene glycol and trimethylene glycol, polyoxyalkylene glycol such as diethylene glycol, and alicyclic diol such as cyclohexanedimethanol are more preferable.

Examples of the comonomer component that can be used in addition to the dicarboxylic acid component and the glycol component include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-carboxy-4′-hydroxybiphenyl, and the like. Aromatic hydroxycarboxylic acids; aliphatic hydroxycarboxylic acids such as glycolic acid and hydroxycaproic acid; C _3-12 lactones such as propiolactone, butyrolactone, valerolactone, caprolactone (ε-caprolactone, etc.); esters of these comonomer components And forming derivatives (C _1-6 alkyl ester derivatives, acid halides, acetylated compounds, etc.).

Any of the polybutylene terephthalate copolymers obtained by copolymerizing the comonomer components described above can be suitably used as the (A) polybutylene terephthalate resin. Moreover, you may use combining a homopolybutylene terephthalate polymer and a polybutylene terephthalate copolymer as (A) polybutylene terephthalate resin.

[(B) Polyethylene terephthalate resin]
The (B) polyethylene terephthalate resin used in the present invention comprises terephthalic acid or an ester-forming derivative thereof (C _1-6 alkyl ester, acid halide, etc.) and ethylene glycol or an ester-forming derivative thereof (acetylated product, etc.). A polyester resin obtained by polycondensation according to a known method.

In the present invention, in the metal composite part, one cause of the effect of improving the adhesion between the metal part and the polybutylene terephthalate resin composition is by blending (B) polyethylene terephthalate resin with (A) polybutylene terephthalate resin. It is presumed that the fluidity of the polybutylene terephthalate resin composition at the time of molding is improved, and the shrinkage rate is reduced due to the decrease in the crystallization rate.

In other words, by improving the fluidity of the polybutylene terephthalate resin composition, the resin composition easily penetrates into the fine recesses on the surface of the metal part, and solidifies in the recesses after cooling due to a decrease in shrinkage rate. It is presumed that the adhesiveness between the metal part and the polybutylene terephthalate resin composition is improved by making it difficult for the obtained resin to be easily detached from the recess.

(B) The polyethylene terephthalate resin may be modified by copolymerizing a small amount of a modifying component that gives other repeating units of a terephthaloyl unit and an ethylenedioxy unit within a range not impairing the object of the present invention. (B) The amount of other repeating units of the terephthaloyl unit and the ethylenedioxy unit contained in the polyethylene terephthalate resin is preferably less than 4 mol% in all repeating units of the (B) polyethylene terephthalate resin, and more preferably 3 mol% or less. Preferably, 2 mol% or less is particularly preferable.

Suitable compounds as dicarboxylic acids or ester-forming derivatives thereof contained in the modifying component include C _8-14 fragrances such as isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-dicarboxydiphenyl ether. Dicarboxylic acids; C _4-16 alkane dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid; C _5-10 cycloalkane dicarboxylic acids such as cyclohexane dicarboxylic acid; ester formation of these dicarboxylic acid components And derivatives (C _1-6 alkyl ester derivatives, acid halides, etc.). These dicarboxylic acids can be used alone or in combination of two or more.

The glycol component contained in the modifying component, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butylene glycol, hexamethylene glycol, neopentyl glycol, and 1,3-octanediol _{C 2- 10} alkylene glycols; polyoxyalkylene glycols such as diethylene glycol, triethylene glycol and dipropylene glycol; cycloaliphatic diols such as cyclohexanedimethanol and hydrogenated bisphenol A; aromatics such as bisphenol A and 4,4′-dihydroxybiphenyl diols, ethylene oxide 2 mol adduct of bisphenol a, propylene oxide 3 mol adduct of bisphenol a, alkylene oxide adducts of C _2-4 of bisphenol a; or which Ester-forming derivatives of the glycol (acetylated, etc.). These glycol components can be used alone or in combination of two or more.

Examples of the hydroxycarboxylic acid component contained in the modified component include aromatic hydroxycarboxylic acids such as 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-carboxy-4′-hydroxybiphenyl; Aliphatic hydroxycarboxylic acids such as glycolic acid and hydroxycaproic acid; or ester-forming derivatives of these hydroxycarboxylic acids (C _1-6 alkyl ester derivatives, acid halides, acetylates, etc.). These hydroxycarboxylic acid components can be used alone or in combination of two or more.

Examples of the lactone component contained in the modifying component include C _3-12 lactones such as propiolactone, butyrolactone, valerolactone, and caprolactone (eg, ε-caprolactone). These lactone components can be used alone or in combination of two or more.

The amount of the (B) polyethylene terephthalate resin used in the molding material of the metal composite part is preferably 10% by mass or more and 50% by mass or less with respect to the total mass of the (A) polybutylene terephthalate resin and the (B) polyethylene terephthalate resin. 15 mass% or more and 45 mass% or less is more preferable, and 20 mass parts or more and 45 mass% or less are especially preferable. (B) When the amount of polyethylene terephthalate resin used is too large, the mold releasability during molding of the metal composite part is impaired, or the mechanical properties and chemical resistance of the resulting metal composite part are impaired. If the amount used is too small, the desired effect of improving adhesion may not be obtained.

[(C) Phosphorus flame retardant]
In the present invention, the molding material for the metal composite part contains (C) a phosphorus-based flame retardant in addition to (A) polybutylene terephthalate resin and (B) polyethylene terephthalate resin. In the present invention, as the phosphorus flame retardant (C), one or more selected from phosphinates, diphosphinates, and salts of phosphinic acid condensates of trimers or more are preferable, and are used in the present invention (C). Among the phosphorus-based flame retardants, phosphinate and / or diphosphinate are more preferable.

Examples of the metal that forms a salt of phosphinate, diphosphinate, or a trimer or more phosphinic acid condensate include alkali metals (potassium, sodium, etc.), alkaline earth metals (magnesium, calcium, etc.), transition metals ( Iron, cobalt, nickel, copper, etc.), periodic table group 12 metal (zinc, etc.), periodic table group 13 metal (aluminum, etc.) and the like. The said metal salt may contain 1 type of these metals, and may contain it in combination of 2 or more types. Of the metals, alkaline earth metals (magnesium, calcium, etc.) and periodic table group 13 metals (aluminum, etc.) are preferred.

The valence of the metal forming the salt is not particularly limited, preferably 1 or more and 4 or less, more preferably 2 or more and 4 or less, and particularly preferably 2 or 3.

In the present invention, the phosphinate used as the phosphorus flame retardant (C) is preferably a compound represented by the following general formula (1), and the diphosphinate is preferably a compound represented by the formula (2).

In the above general formulas (1) and (2), R ¹ and R ² are a linear or branched C _1-6 -alkyl group which may contain a phenyl group, hydrogen, and one hydroxyl group. . R ¹ and R ² are preferably both ethyl groups.
R ³ is a linear or branched C _1-10 -alkylene group, arylene group, alkylarylene group or arylalkylene group.
M is an alkaline earth metal, alkali metal, Zn, Al, Fe, or boron. Among these, Al is preferable.
m is an integer of 1 to 3, n is an integer of 1 or 3, and x is 1 or 2.

Specific examples of phosphinates that can be suitably used in the present invention include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, ethylmethylphosphine. Magnesium finate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, methyl-n-propylphosphinic acid Calcium, magnesium methyl-n-propylphosphinate, aluminum methyl-n-propylphosphinate, zinc methyl-n-propylphosphinate, etc. And the like.

Specific examples of diphosphinate that can be suitably used in the present invention include methandi (methylphosphinic acid) calcium, methandi (methylphosphinic acid) magnesium, methandi (methylphosphinic acid) aluminum, methandi (methylphosphinic acid). Examples thereof include zinc, benzene-1,4- (dimethylphosphinic acid) calcium, and benzene-1,4- (dimethylphosphinic acid) magnesium.

Among the above phosphinates and / or diphosphinates, it is particularly preferable to use aluminum diethylphosphinate.

The amount of the (C) phosphorus flame retardant used in the present invention is preferably 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the total amount of (A) polybutylene terephthalate resin and (B) polyethylene terephthalate resin. The amount is more preferably no less than 80 parts by mass and particularly preferably no less than 15 parts by mass and no greater than 60 parts by mass. (C) If the amount of phosphorus-based flame retardant used is too large, mechanical properties and moldability may be impaired, and if the amount used is too small, good flame retardancy may not be obtained. .

[(D) Nitrogen-containing flame retardant aid]
In the present invention, the molding material for the metal composite part contains (D) a nitrogen-containing flame retardant auxiliary agent in addition to (A) polybutylene terephthalate resin, (B) polyethylene terephthalate resin, and (C) phosphorus flame retardant. Is preferred. The type of (D) nitrogen-containing flame retardant aid is not limited as long as the object of the present invention is not impaired, and various (D) nitrogen-containing flame retardant aids conventionally used as flame retardants for thermoplastic resins. Can be selected and used.

Examples of the (D) nitrogen-containing flame retardant aid preferably used in the present invention include a salt of a triazine compound and cyanuric acid or isocyanuric acid, a double salt of a nitrogen compound containing an amino group and polyphosphoric acid Etc. These (D) nitrogen-containing flame retardant aids can be used in combination of two or more.

As the (D) nitrogen-containing flame retardant aid used in the present invention, (C) a salt of a triazine compound and cyanuric acid or isocyanuric acid because of excellent flame retardancy when combined with a phosphorus flame retardant, And / or the double salt of the nitrogen compound containing an amino group and polyphosphoric acid is more preferable.

As a salt of the triazine compound and cyanuric acid or isocyanuric acid, a salt of a triazine compound represented by the following general formula (3) and cyanuric acid or isocyanuric acid is exemplified as a preferable example.

In the formula, R ⁴ and R ⁵ are a hydrogen atom, an amino group, an aryl group, or a C _1-3 oxyalkyl group, and R ⁴ and R ⁵ may be the same or different.

As the nitrogen-containing flame retardant aid (D) used in the present invention, melamine cyanurate is particularly preferable among the salts of the triazine compound represented by the general formula (3) and cyanuric acid or isocyanuric acid.

Further, the nitrogen compound containing an amino group contained in a double salt of a nitrogen compound containing an amino group and polyphosphoric acid has at least one amino group and a heterocyclic ring having at least one nitrogen atom as a ring hetero atom. The compound is included, and the heterocycle may have other heteroatoms such as sulfur and oxygen in addition to nitrogen. Such nitrogen-containing heterocycles are 5- or 6-membered unsaturated having a plurality of nitrogen atoms such as imidazole, thiadiazole, thiadiazoline, furazane, triazole, thiadiazine, pyrazine, pyrimidine, pyridazine, triazine, and purine as ring constituent atoms. Nitrogen-containing heterocycles and the like are included. Of these nitrogen-containing rings, 5- or 6-membered unsaturated nitrogen-containing rings having a plurality of nitrogen atoms as ring constituent atoms are preferred, and triazoles and triazines are particularly preferred. Of the double salts of nitrogen compounds containing amino groups and polyphosphoric acid, melam polyphosphate is preferred.

The amount of the (D) nitrogen-containing flame retardant aid used in the molding material of the metal composite part is 1 part by mass or more with respect to 100 parts by mass of the total amount of (A) polybutylene terephthalate resin and (B) polyethylene terephthalate resin. 50 mass parts or less are preferable, 1 mass part or more and 40 mass parts or less are more preferable, and 1 mass part or more and 30 mass parts or less are especially preferable. By using the (D) nitrogen-containing flame retardant aid together with the (C) flame retardant in such an amount, a metal composite part having excellent flame retardancy can be obtained.

[(E) Filler]
In the present invention, the molding material of the metal composite part is added to (A) polybutylene terephthalate resin, (B) polyethylene terephthalate resin, and (C) phosphorus-based flame retardant for the purpose of improving the mechanical properties of the metal composite part. (E) a filler is preferably included. The type of filler (E) used in the present invention is not particularly limited as long as the object of the present invention is not impaired, and various fillers conventionally used as fillers for polymer materials can be used. Either inorganic fillers or organic fillers can be used. In addition, the shape of the filler (E) used in the present invention is not limited as long as the object of the present invention is not hindered, and any of a fibrous filler, a granular filler, and a plate-like filler can be suitably used. .

Suitable fibrous fillers used in the present invention include, for example, glass fiber, asbestos fiber, silica fiber, silica-alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, Furthermore, inorganic fibrous materials, such as metal fibrous materials, such as stainless steel, aluminum, titanium, copper, and brass, are mentioned.

Examples of suitable granular fillers used in the present invention include carbon black, graphite, silica, quartz powder, glass beads, milled glass fiber, glass balloon, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, Silicates such as diatomaceous earth, wollastonite, iron oxide, titanium oxide, zinc oxide, antimony trioxide, oxides of metals such as alumina, carbonates of metals such as calcium carbonate and magnesium carbonate, calcium sulfate and barium sulfate Examples thereof include metal sulfates, other ferrites, silicon carbide, silicon nitride, boron nitride, various metal powders and the like. Suitable plate-like fillers include mica, glass flakes, various metal foils and the like.

Among these (E) fillers, it is particularly preferable to use glass fibers because of excellent balance between cost and physical properties of the obtained metal composite part.

As the glass fiber, any known glass fiber is preferably used, and the glass fiber diameter, the cross-sectional shape such as a cylinder, a bowl-shaped cross section, an oval cross section, or the length or glass used for manufacturing chopped strands, rovings, etc. It does not depend on the cutting method. In the present invention, the type of glass used as a raw material for the glass fiber is not particularly limited, but E glass or corrosion resistant glass containing a zirconium element in the composition is preferably used in terms of quality.

In addition, for the purpose of improving the interfacial characteristics between the (E) filler and the resin matrix comprising (A) a polybutylene terephthalate resin and (B) a polyethylene terephthalate resin, the surface is treated with an organic treatment agent such as a silane compound or an epoxy compound. Treated fillers are preferably used. As the silane compound and epoxy compound used for such a filler, any known one can be preferably used, and does not depend on the type of silane compound or epoxy compound used for the surface treatment of the filler in the present invention.

The amount of (E) filler used in the present invention is preferably 5 parts by mass or more and 120 parts by mass or less with respect to 100 parts by mass of the total amount of (A) polybutylene terephthalate resin and (B) polyethylene terephthalate, and 10 parts by mass. The amount is more preferably 100 parts by mass or less, and particularly preferably 15 parts by mass or more and 80 parts by mass or less. (E) When there is too much usage-amount of a filler, the fluidity | liquidity of the resin composition at the time of shaping | molding may be impaired.

[(F) Fluororesin]
In the present invention, the molding material of the metal composite part preferably contains (F) a fluorine resin in addition to (A) polybutylene terephthalate resin, (B) polyethylene terephthalate resin, and (C) phosphorus flame retardant. . (F) By using a fluorine-type resin, dripping of the molten resin when a polybutylene terephthalate resin composition touches a flame is suppressed, and the metal composite component which is more excellent in a flame retardance can be obtained.

Suitable (F) fluorine-based resins include tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, perfluoroalkyl vinyl ether and other fluorine-containing monomers alone or copolymers, and the fluorine-containing monomers Examples thereof include copolymers with copolymerizable monomers such as ethylene, propylene and (meth) acrylate. These (F) fluorine resins can be used alone or in combination of two or more.

Examples of such (F) fluorine-based resins include homopolymers such as polytetrafluoroethylene, polychlorotrifluoroethylene, and polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymers, and tetrafluoroethylene. -Copolymers such as perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, etc. are exemplified. The (F) fluorine-based resin may be a (meth) acrylate resin such as methyl methacrylate / butyl acrylate copolymer, a polyester resin such as polyethylene terephthalate, or a polyamide resin such as polyamide 6. You may use as a mixture with resin.

The amount of the (F) fluorine-based resin used in the present invention is preferably 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total amount of (A) polybutylene terephthalate resin and (B) polyethylene terephthalate resin. 0.2 parts by mass or more and 1.5 parts by mass or less is particularly preferable.

[(G) Elastomer]
In the present invention, the molding material for the metal composite part preferably contains (G) an elastomer in addition to (A) polybutylene terephthalate resin and (B) polyethylene terephthalate resin. (G) By using an elastomer, the adhesion between the metal part and the polybutylene terephthalate resin composition is particularly excellent.

Suitable (G) elastomers that can be used in the present invention include polyester elastomers, olefin elastomers, polyvinyl acetate, fluororesins, urethane elastomers, amide elastomers, acrylate elastomers, styrene elastomers, fluorine elastomers, and butadiene. Based elastomers and the like. Furthermore, a core-shell type polymer composed of a core portion made of a rubber-like crosslinked body such as butyl acrylate and a shell portion of a glassy polymer such as methyl acrylate is also used. These elastomers may be modified by known methods such as introduction of reactive groups such as epoxy groups, isocyanate groups, and amino groups, crosslinking, and grafting.

The amount of the (G) elastomer used in the present invention is not particularly limited as long as the object of the present invention is not impaired. The amount of the elastomer (G) used is preferably 1 part by mass or more and 100 parts by mass or less, preferably 3 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total amount of (A) polybutylene terephthalate resin and (B) polyethylene terephthalate resin. Is more preferably 5 parts by mass or more and 30 parts by mass or less. (G) By making the usage-amount of an elastomer into this range, the adhesiveness of a metal component and a polybutylene terephthalate resin composition can be made especially excellent.

(G) Elastomers preferably used in the present invention are olefin elastomers, styrene elastomers, core shell elastomers, and polyester elastomers. Hereinafter, the olefin elastomer, the styrene elastomer, the core shell elastomer, and the polyester elastomer will be described in order.

<Olefin-based elastomer>
Preferred as the olefin-based elastomer is a copolymer containing ethylene and / or propylene as components, and specifically includes an ethylene-propylene copolymer, an ethylene-butene copolymer, an ethylene-octene copolymer, an ethylene- Examples include, but are not limited to, propylene-butene copolymers, ethylene-propylene-diene copolymers, ethylene-ethyl acrylate copolymers, ethylene-vinyl acetate copolymers, ethylene-glycidyl methacrylate copolymers. It is not a thing. Further, among the olefin elastomers, (I) an ethylene-unsaturated carboxylic acid alkyl ester copolymer or (II) an olefin copolymer comprising an α-olefin and an α, β-unsaturated glycidyl ester, A graft copolymer in which one or two or more polymers or copolymers composed of repeating units represented by the following general formula (4) are chemically bonded in a branched or crosslinked structure can also be used. (Where R ⁶ is hydrogen or a lower alkyl group, X is —COOCH ₃ , —COOC ₂ H ₅ , —COOC ₄ H ₉ , —COOCH ₂ CH (C ₂ H ₅ ) C ₄ H ₉ , —C ₆ H ₅ , Represents one or more groups selected from —CN)

<Styrene elastomer>
As the styrene-based elastomer used as the elastomer (G) in the present invention, a block copolymer composed of a polystyrene block and an elastomer block having a polyolefin structure is preferably used. Specific examples of styrene-based elastomers include styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene / propylene-styrene block copolymer (SEPS), and styrene-ethylene / butylene-styrene block copolymer (SEBS). And styrene-ethylene / ethylene / propylene-styrene block copolymer (SEEPS).

<Core shell elastomer>
The core-shell elastomer used as the elastomer (G) in the present invention has a multilayer structure composed of a core layer (core portion) and a shell layer covering at least a part of the surface of the core layer. The core layer of the core-shell elastomer is preferably composed of a rubber component (soft component), and acrylic rubber is suitably used as the rubber component. The rubber component used for the core layer preferably has a glass transition temperature (Tg) of less than 0 ° C. (eg −10 ° C. or less), and −20 ° C. or less (eg −180 ° C. or more and −25 ° C. or less). More preferably, it is −30 ° C. or lower (for example, −150 ° C. or higher and −40 ° C. or lower).

The acrylic rubber used as the rubber component is preferably a polymer obtained by polymerizing an acrylic monomer such as alkyl acrylate as a main component. The alkyl acrylate used as the monomer for the acrylic rubber is preferably a C ₁ to C ₁₂ alkyl ester of acrylic acid such as butyl acrylate, and more preferably a C ₂ to C ₆ alkyl ester of acrylic acid.

The acrylic rubber may be a homopolymer of an acrylic monomer or a copolymer. When the acrylic rubber is a copolymer of acrylic monomers, it may be a copolymer of acrylic monomers or a copolymer of an acrylic monomer and another unsaturated bond-containing monomer. When the acrylic rubber is a copolymer, the acrylic rubber may be a copolymer of a crosslinkable monomer.

<Polyester elastomer>
In the present invention, the polyester elastomer used as the elastomer (G) is not particularly limited as long as the flexural modulus is 1000 MPa or less, preferably 700 MPa or less, and various types can be used. Either can be used.

The polyether-type polyester elastomer is a polyester elastomer having an aromatic polyester unit as a hard segment and a polyester composed of a polymer of oxyalkylene glycol and a dicarboxylic acid as a soft segment.

The aromatic polyester unit in the hard segment is a polycondensate of a dicarboxylic acid compound and a dihydroxy compound, a polycondensate of an oxycarboxylic acid compound, or a polycondensate of a dicarboxylic acid compound, a dihydroxy compound, and an oxycarboxylic acid compound. It is a derived unit. Specific examples of the hard segment include units derived from polybutylene terephthalate.

The soft segment is introduced into the polyester elastomer by a compound formed by polycondensation of a polyalkylene ether and a dicarboxylic acid compound. Specific examples of the soft segment include a unit derived from an ester compound of polyoxytetramethylene glycol derived from tetrahydrofuran.

As the polyether type elastomer, a synthesized one or a commercially available one may be used. Examples of commercially available polyether type elastomers include Perprene P-30B, P-70B, p-90B, P-208B manufactured by Toyobo Co., Ltd .; Hytrel 4057, 4767 manufactured by Toray DuPont Co., Ltd. 6347, 7247; Light Flex 655 manufactured by Chicona Corporation.

The polyester type elastomer is a polyester elastomer having an aromatic polyester unit as a hard segment and an amorphous polyester unit as a soft segment. The aromatic polyester unit in the hard segment is the same as that of the polyether type elastomer. Examples of the amorphous polyester unit in the soft segment include a unit derived from a ring-opening polymer of lactone or a polycondensate of an aliphatic dicarboxylic acid and an aliphatic diol.

The polyester type elastomer may be a synthesized one or a commercially available one. Examples of commercially available polyester elastomers include Perprene S-1002 and S-2002 manufactured by Toyobo Co., Ltd.

[(H) Other additives]
In the present invention, the molding material for the metal composite part includes (A) a polybutylene terephthalate resin, (B) a polyethylene terephthalate resin, and (C) a phosphorus-based flame retardant according to the purpose, and (D) a nitrogen-containing flame retardant aid. Other additives such as an agent, (E) filler, (F) fluororesin, and (G) elastomer may be included.

(H) Other additives are not particularly limited as long as the object of the present invention is not impaired, and various additives conventionally used for various resins can be used. (H) Specific examples of other additives include antioxidants, heat stabilizers, ultraviolet absorbers, antistatic agents, dyes, pigments, lubricants, mold release agents, crystallization accelerators, crystal nucleating agents, and the like. Can be mentioned.

As (H) other additives in the present invention, it is particularly preferable to add a phosphorus-based stabilizer for the purpose of improving thermal stability and suppressing transesterification between the polybutylene terephthalate resin and the polyethylene terephthalate resin. The phosphorus stabilizer is not particularly limited as long as it does not impair the object of the present invention, and various known phosphorus-containing compounds used as stabilizers for polymer materials can be used. Examples of the phosphorus stabilizer suitably used in the present invention include phosphate ester compounds, phosphite ester compounds, phosphonate ester compounds, and phosphate metal salt compounds. These phosphorus stabilizers can be used in combination of two or more.

In the present invention, the total content of the components (A) to (G) in the molding material of the metal composite part is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass in the molding material. % Or more is particularly preferable, and 99% by mass or more is most preferable. By setting the total content of the components (A) to (G) within such a range, it is easy to obtain a metal composite part that is particularly excellent in adhesion between the metal part and the polybutylene terephthalate resin composition.

[Production method of metal composite parts]
Next, a method for manufacturing a metal composite part will be described in the order of a metal part and a forming method.

[Metal parts]
The material of the metal part used in the present invention is not particularly limited. For example, a metal such as aluminum, copper, iron, magnesium, nickel, or titanium; an alloy such as aluminum alloy, phosphor bronze, or stainless steel; Etc. Moreover, the material which comprises a metal component is not limited to a metal, What is necessary is just a component which has a metal layer on the surface. Examples of components having a metal layer on the surface include components plated with metals such as nickel, chromium, and gold.

The shape of the metal part is not particularly limited as long as the metal part and the molding material of the metal composite part can be combined, and various shape parts such as a plate shape, a cylindrical shape, and a rod shape can be used. The metal parts used in the present invention include various bosses for screwing, ribs for reinforcement, insertion holes for attaching parts such as gears, and the like necessary for assembling final products such as electric and electronic products. You may have a component. The shape of the portion where the metal part and the molding material of the metal composite part come into contact with each other is not particularly limited, and an arbitrary shape such as a quadrangle, a circle, or an ellipse may be selected. Further, the shape of the surface where the metal part and the molding material of the metal composite part come into contact is not particularly limited, and may be a flat surface or a curved surface. The surface on which the metal part and the molding material of the metal composite part come into contact is not limited to a single plane or curved surface, and may have a convex portion or a concave portion inside the plane or curved surface of the metal plate. The area of the part where the metal part and the molding material of the metal composite part come into contact is not particularly limited.

It is preferable that at least a part of the metal part that is in contact with the molding material of the metal composite part is roughened in advance.

The method of roughening treatment for forming fine irregularities on the surface of the metal part used in the present invention is not particularly limited, and a conventional metal roughening treatment method according to the metal material, shape, required characteristics, etc. Can be selected as appropriate. Examples of the treatment for forming fine irregularities on the metal surface include chemical etching, alumite treatment on aluminum, physical treatment such as liquid honing and sandblasting, and processing by electroless plating. Chemical etching is a method of treating a metal surface with a chemical or the like, and various methods are known depending on the type of metal and the purpose of treatment, and are used in various industrial fields. When chemical etching is performed as a roughening method for metal parts, the chemical etching method is not particularly limited, and any of conventional methods can be selected. Specific examples of the chemical etching method include the methods described in JP-A-10-96088 and JP-A-10-56263, for example.

For example, when the material of the metal part is aluminum or an aluminum alloy, (1) fine etching with an acidic aqueous solution and / or a basic aqueous solution, or (2) after forming an oxide film on the surface of the metal part, the oxide film is removed. Then, a method of treating the surface of the metal part with ammonia, hydrazine, a water-soluble amine compound or the like is preferable. Specifically, those processed by the method described in JP-A-2006-001216 can be used.

In addition, according to alumite treatment, which is a general surface treatment method applied to aluminum, an aluminum is electrolyzed with an anode using an acid to form a porous of the order of several tens of nanometers to several tens of micrometers. Is possible. Further, not only forming a concave portion on the surface, but conversely, TRI treatment or the like is known as a method for forming a convex portion.

In this way, by using chemical, physical, electrical methods, or a combination thereof, by forming irregularities with a size of several tens of nanometers to several tens of micrometers on the surface of the metal parts, the metal parts And the polybutylene terephthalate resin composition can be made more excellent in adhesion.

[Molding method]
After placing the metal component described above on the mold, the metal composite component of the present invention is manufactured by supplying the molding material of the metal composite component with a molding machine. The molding machine used for the production of the metal composite part is not particularly limited as long as a composite molded body of the metal part and the polybutylene terephthalate resin composition can be formed. Conventionally, a metal such as an injection molding machine, an extrusion molding machine, a compression molding machine, etc. Various molding machines used for molding composite parts can be used. It is preferable to use an injection molding machine in terms of ease of installation of metal parts in a mold, simplicity of equipment, and excellent productivity.

温度 Mold temperature is not particularly limited when molding metal composite parts. In order to improve the adhesion between the metal part and the polybutylene terephthalate resin composition, a high temperature, for example, a temperature exceeding 100 ° C. is preferable. In mass production of metal composite parts, the mold temperature is preferably 100 ° C. or lower, more preferably 50 ° C. or higher and 100 ° C. or lower, because the cooling time is short and the molding cycle can be shortened. When the mold temperature is set to 100 ° C. or lower, the temperature of the mold can be controlled by a temperature control apparatus using hot water as a heating medium, which is generally used as a mold temperature control apparatus. There is an advantage that preparation becomes unnecessary and manufacturing work of the metal composite part is safe.

The molding material of the metal composite part is not particularly limited as long as it contains a predetermined amount of the materials (A) to (H), and any of a polybutylene terephthalate resin mixture and a polybutylene terephthalate resin composition can be used. . Preferable examples of the polybutylene terephthalate resin mixture include (1) (A) a polybutylene terephthalate resin composition obtained by melt-kneading (A) a polybutylene terephthalate resin and a predetermined amount of the components (C) to (H). A mixture of pellets and (B) polyethylene terephthalate resin pellets, (2) (A) polybutylene terephthalate resin pellets, (B) polyethylene terephthalate resin and predetermined amounts of components (C) to (H). The mixture with the pellet of the polyethylene terephthalate resin composition obtained by melt-kneading is mentioned.

As the molding material for the metal composite part used in the present invention, it is more preferable to use a polybutylene terephthalate resin composition because it is easy to produce a homogeneous metal composite part.

[Metal composite parts]
The metal composite part of the present invention obtained by the materials and methods described above is excellent in adhesion between the metal part and the polybutylene terephthalate resin and excellent in flame retardancy. For this reason, the metal composite part of this invention is used suitably, for example as a part of various electrical / electronic products. Examples of suitable electrical / electronic products using metal composite parts obtained by the method of the present invention include mobile phones, digital cameras, personal digital assistants (PDAs), portable game terminals, portable terminals such as electronic book readers, notebooks, etc. OA equipment such as computers such as copy-type personal computers and desktop personal computers, copiers, printers, and facsimiles. The metal composite part of the present invention is particularly suitable as a casing of a mobile terminal, a computer, an OA device, etc., because a metal and a polybutylene terephthalate resin composition are combined to be excellent in strength, lightness, design and the like. Used for.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<Examples 1 to 5 and Comparative Examples 1 to 6>
In Examples 1 to 5 and Comparative Examples 1 to 6, the following materials were used as components of the polybutylene terephthalate resin composition.

[(A) Polybutylene terephthalate resin]
A1: Polybutylene terephthalate resin (made by Wintech Polymer Co., Ltd.) with an intrinsic viscosity of 0.69 dL / g
[(B) Polyethylene terephthalate resin]
B1: Polyethylene terephthalate resin (manufactured by SK Chemical Co., melting point 258 ° C., intrinsic viscosity 0.76 dL / g)
The melting point was measured according to JIS K7121.
[(C) Phosphorus flame retardant]
C1: Aluminum diethylphosphinate (phosphorous flame retardant, manufactured by Clariant, Exolit OP 1230)
[(C ′) flame retardant]
C'1: Phosphate ester (Daihachi Scientific Co., Ltd., PX-200)
C'2: Brominated polycarbonate (brominated flame retardant, manufactured by Teijin Chemicals Ltd., FG-7500)
[(D) Nitrogen-containing flame retardant aid]
D1: Melamine cyanurate (nitrogen-based flame retardant aid, manufactured by DSM, Melapure 50)
[(D ') Flame retardant aid]
D'1: antimony trioxide (antimony compound, manufactured by Nippon Seiko Co., Ltd., PATOX-M)
[(E) Filler]
E1: Glass fiber (manufactured by Nitto Boseki Co., Ltd., CS3J648S)
[(F) Fluororesin]
F1: Tetrafluoroethylene polymer (Mitsui DuPont Fluorochemical Co., Ltd., PTFE850A)
[(G) Elastomer]
G1: Core-shell elastomer (Rohm and Haas Japan KK, Paraloid ELX2311)

The components shown in Table 1 were dry blended in the proportions (parts by mass) shown in Table 1, and using a twin screw extruder (TEX-30α manufactured by Nippon Steel Co., Ltd.), the cylinder temperature was 260 ° C., the discharge rate Pellets of polybutylene terephthalate resin composition were prepared by melt-kneading under conditions of 12 kg / hr and screw rotation speed of 130 rpm. Test pieces were prepared using the pellets obtained in the examples and comparative examples, and tested for adhesion and flame retardancy according to the following methods. Table 1 shows the test results regarding the adhesion and flame retardancy of the polybutylene terephthalate resin compositions of Examples and Comparative Examples.

<Adhesion>
[Test specimen preparation]
Hereinafter, a method for evaluating adhesion will be described with reference to FIGS. 1 and 2. Using an injection molding machine (TR-40VR, manufactured by Sodick Co., Ltd.), setting the mold temperature to 80 ° C. with a temperature control device using hot water as a heating medium, and placing metal parts in the mold, the following Under these conditions, a test piece for evaluating adhesion was injection molded. The metal part used was an aluminum (A1050) plate that was subjected to “NMT treatment by Taisei Plus Co., Ltd.” known as a type of chemical etching and the surface was roughened. The shape of the test piece for adhesion evaluation is as shown in FIG. 1, and the 20 mm × 50 mm × 1.6 mm thick aluminum plate 2 and the polybutylene terephthalate resin composition 1 are 10 mm × 5 mm rectangular contacts. The composite was used via the surface.

[Adhesion evaluation]
First, after removing burrs around the contact surface between the aluminum plate 2 and the polybutylene terephthalate resin composition 1 of the test piece, the test piece is placed in the recess of the test piece fixing jig 4 as shown in FIG. Two aluminum plates were fixed. Subsequently, the pushing jig 3 is lowered at a speed of 1 mm / min to push down the polybutylene terephthalate resin composition 1 to be tested, and the maximum load when the polybutylene terephthalate resin composition 1 and the aluminum plate 2 are peeled off (N ) And observed the mode of destruction. For evaluation of adhesion, Tensilon UTA-50KN manufactured by Orientec Co., Ltd. was used.

In Comparative Examples 2 and 4, since the metal part and the resin did not adhere to each other, the adhesion could not be evaluated. Moreover, in Comparative Example 6, since the mold release failure occurred when the test piece was created, the adhesion could not be evaluated.

<Flame retardance>
The test piece (0.8 mm thickness) was subjected to UL94 standard vertical combustion test by Underwriters Laboratories.

According to Examples 1 to 5, the content of the polyethylene terephthalate resin in the molding material is 10% by mass or more and 50% by mass or less with respect to the total mass of the polybutylene terephthalate resin and the polyethylene terephthalate resin. When the content of the acid salt is 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the total amount of the polybutylene terephthalate resin and the polyethylene terephthalate resin, the metal parts and the polybutylene terephthalate resin composition It can be seen that a metal composite part excellent in adhesion and flame retardancy can be obtained. In addition, Example 4 shows that when the molding material contains an elastomer, a metal composite part having particularly excellent adhesion between the metal part and the polybutylene terephthalate resin composition can be obtained.

According to Comparative Example 1, if no polyethylene terephthalate resin is added to the polybutylene terephthalate resin, the resulting metal part is inferior in adhesion between the metal part and the polybutylene terephthalate resin composition and flame retardancy. It turns out that it is. Moreover, according to Comparative Example 2, it can be seen that even when only the phosphorus-based flame retardant is added to the polybutylene terephthalate resin, the adhesion between the metal part and the polybutylene terephthalate resin composition is not improved.

According to Comparative Example 3, even when a suitable amount of polyethylene terephthalate resin is used relative to polybutylene terephthalate resin, the amount of phosphorus-based flame retardant used is 100 parts by mass of the total amount of polybutylene terephthalate resin and polyethylene terephthalate resin. On the other hand, when it exceeds 100 mass parts, it turns out that the metal composite component which is excellent in the adhesiveness of a metal component and a polybutylene terephthalate resin composition is not obtained. Further, according to Comparative Example 6, even when a suitable amount of phosphorus-based flame retardant is used for the polybutylene terephthalate resin, the amount of the polyethylene terephthalate resin used is based on the total mass of the polybutylene terephthalate resin and the polyethylene terephthalate resin. If it exceeds 50% by mass, it can be seen that a metal composite part of good quality cannot be obtained due to the problem of releasability.

According to Comparative Examples 4 and 5, with respect to polybutylene terephthalate resin, even when a suitable amount of polyethylene terephthalate resin is used, phosphoric acid ester (flame retardant) is used, or brominated flame retardant and antimony compound (flame retardant) are used. It is understood that a metal composite part having excellent adhesion between the metal part and the polybutylene terephthalate resin composition cannot be obtained when the auxiliary agent is used in combination.

DESCRIPTION OF SYMBOLS 1 Polybutylene terephthalate resin composition 2 Aluminum plate 3 Pushing jig 4 Test piece fixing jig

Claims (16)

1. One or more (A) selected from the group consisting of (A) a polybutylene terephthalate resin, (B) a polyethylene terephthalate resin, a phosphinate, a diphosphinate, and a salt of a trimer or more phosphinic acid condensate. C) a phosphorus flame retardant,
   The content of the (B) polyethylene terephthalate resin is 10% by mass to 50% by mass with respect to the total mass of the (A) polybutylene terephthalate resin and the (B) polyethylene terephthalate resin,
   Metal whose content of said (C) phosphorus flame retardant is 10 mass parts or more and 100 mass parts or less with respect to 100 mass parts of total amounts of said (A) polybutylene terephthalate resin and said (B) polyethylene terephthalate resin. A polybutylene terephthalate resin composition for molding composite parts.
2. The metal according to claim 1, wherein the (C) phosphorus-based flame retardant is a phosphinate represented by the following general formula (1) and / or a diphosphinate represented by the following general formula (2). A polybutylene terephthalate resin composition for molding composite parts.
   

   

   (In the general formulas (1) and (2), R ¹ and R ² are a linear or branched C _1-6 -alkyl group which may contain a phenyl group, hydrogen, and one hydroxyl group. , R ³ is a linear or branched C _1-10 -alkylene group, arylene group, alkylarylene group or arylalkylene group, and M is an alkaline earth metal, alkali metal, Zn, Al, Fe, Boron, m is an integer from 1 to 3, n is an integer from 1 or 3, and x is 1 or 2.)
3. The polybutylene terephthalate resin composition for molding metal composite parts according to claim 2, wherein the (C) phosphorus flame retardant is aluminum diethylphosphinate.
4. Furthermore, it contains a (D) nitrogen-containing flame retardant aid that is a salt of a triazine compound represented by the following general formula (3) and cyanuric acid or isocyanuric acid,
   (D) The content of the nitrogen-containing flame retardant auxiliary is 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total amount of the (A) polybutylene terephthalate resin and the (B) polyethylene terephthalate resin. The polybutylene terephthalate resin composition for molding metal composite parts according to any one of claims 1 to 3.
   

   

   (In the formula, R ⁴ and R ⁵ are a hydrogen atom, an amino group, an aryl group, or an oxyalkyl group having 1 to 3 carbon atoms, and R ⁴ and R ⁵ may be the same or different.)
5. The polybutylene terephthalate resin composition for molding metal composite parts according to claim 4, wherein the (D) nitrogen-containing flame retardant aid is melamine cyanurate.
6. Furthermore, (E) containing a filler,
   (E) The content of the filler is 5 parts by mass or more and 120 parts by mass or less with respect to 100 parts by mass of the total amount of the (A) polybutylene terephthalate resin and the (B) polyethylene terephthalate resin. 5. A polybutylene terephthalate resin composition for molding metal composite parts according to any one of 5 above.
7. Further, (F) contains a fluorine resin,
   (F) Content of fluorine-type resin is 0.1 to 5 mass parts with respect to 100 mass parts of total amounts of said (A) polybutylene terephthalate resin and said (B) polyethylene terephthalate resin, Item 7. A polybutylene terephthalate resin composition for molding a metal composite part according to any one of Items 1 to 6.
8. And (G) an elastomer,
   The content of the elastomer (G) is 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the total amount of the (A) polybutylene terephthalate resin and the (B) polyethylene terephthalate resin. A polybutylene terephthalate resin composition for molding a metal composite part according to any one of the above.
9. A metal composite part comprising the polybutylene terephthalate resin composition for molding a metal composite part according to any one of claims 1 to 8, and a metal part.
10. The metal composite part according to claim 9, wherein the metal part has been subjected to surface roughening treatment.
11. The metal composite part according to claim 9 or 10, which is a personal computer part, a portable terminal part, or an OA equipment part.
12. One or more (A) selected from the group consisting of (A) a polybutylene terephthalate resin, (B) a polyethylene terephthalate resin, a phosphinate, a diphosphinate, and a salt of a trimer or more phosphinic acid condensate. C) a phosphorus flame retardant,
    The content of the (B) polyethylene terephthalate resin is 10% by mass to 50% by mass with respect to the total mass of the (A) polybutylene terephthalate resin and the (B) polyethylene terephthalate resin,
    Molding material whose content of the (C) phosphorus flame retardant is 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the total amount of the (A) polybutylene terephthalate resin and the (B) polyethylene terephthalate resin. A method for manufacturing a metal composite part, in which a metal molding machine is supplied to a mold on which the metal part is placed.
13. The method for producing a metal composite part according to claim 12, wherein the molding material is a polybutylene terephthalate resin composition for molding a metal composite part according to any one of claims 1 to 8.
14. The method for producing a metal composite part according to claim 12 or 13, wherein the metal part has been subjected to a surface roughening treatment.
15. The method for producing a metal composite part according to any one of claims 12 to 14, wherein the temperature of the mold is 100 ° C or lower.
16. A metal composite part obtained by the molding method according to claim 12.

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