CN102933655B - The manufacture method of polybutylene terephthalate resin combination, metal composite parts and metal composite parts - Google Patents

The manufacture method of polybutylene terephthalate resin combination, metal composite parts and metal composite parts Download PDF

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Publication number
CN102933655B
CN102933655B CN201180027832.7A CN201180027832A CN102933655B CN 102933655 B CN102933655 B CN 102933655B CN 201180027832 A CN201180027832 A CN 201180027832A CN 102933655 B CN102933655 B CN 102933655B
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polybutylene terephthalate
terephthalate resin
metal composite
parts
mass parts
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CN102933655A (en
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若塚圣
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Poly Plastics Co., Ltd.
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WinTech Polymer Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14311—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/006—PBT, i.e. polybutylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2707/00—Use of elements other than metals for preformed parts, e.g. for inserts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals

Abstract

Even if the polybutylene terephthalate resin combination of the metal composite parts of the excellent adhesion of metal parts and polybutylene terephthalate resin combination and the manufacture method of metal composite parts also can be manufactured under providing the die temperature below 100 DEG C.In addition, the metal composite parts of the excellent adhesion of metal parts and polybutylene terephthalate resin combination are provided.In polybutylene terephthalate resin, compounding specified quantitative manufactures metal composite parts by the pet resin of the dicarbonyl unit modification except terephthaloyl unit.

Description

The manufacture method of polybutylene terephthalate resin combination, metal composite parts and metal composite parts
Technical field
The polybutylene terephthalate resin combination of the metal composite parts of the excellent adhesion of metal parts and polybutylene terephthalate resin combination can be obtained when to the present invention relates to metal parts and polybutylene terephthalate resin combination Composite to manufacture metal composite parts.In addition, the present invention relates to the manufacture method of the metal composite parts of that formed by metal parts and polybutylene terephthalate resin combination, metal parts and polybutylene terephthalate resin combination excellent adhesion.And then, the invention still further relates to the metal composite parts of that formed by metal parts and polybutylene terephthalate resin combination, metal parts and polybutylene terephthalate resin combination excellent adhesion.
Background technology
All the time, by manufacturing process such as insert molding (insertmolding), injection moulding (outsertmolding), hoops shaping (hoopmolding), metal composite parts thermoplastic resin and metal parts Composite manufactured are widely used in household appliances, information communication device, trolley part etc.
In addition, by in the metal composite parts of thermoplastic resin and metal parts Composite, such as,, the viewpoint such as light weight, designability functional from intensity etc., the metallic composite laminated parts that the part of metal sheet surface or whole be laminated with thermoplastic resin receive publicity as the housing of the small information such as mobile telephone, notebook personal computer signal equipment.
For the thermoplastic resin for described metal composite parts, require the weather resistance to the various stimulations from outside, therefore, expect the various excellents such as mechanical characteristics, thermotolerance, electrical characteristic, weathering resistance, water tolerance, chemical proofing, solvent resistant, from the viewpoint manufacturing efficiency, expecting can by method melt-shapings such as injection formings.Therefore, studying the use of these each physical property with the metal composite parts of the polybutylene terephthalate resin combination had excellent formability.
But, when using polybutylene terephthalate resin or polybutylene terephthalate resin combination to manufacture metal composite parts by methods such as injection formings, the linear expansivity of resin is larger than metal, shrinking percentage after the metal parts of low temperature and the ester moulding of high processing temperature exists very large difference, thus, even if exist at mould inner metal component and resin closely sealed well, the problem that the adaptation of be shaped metal parts and resin afterwards also can reduce.In addition, the processing temperature of polybutylene terephthalate resin is high, therefore, the thermoplastic resin snap cure of metal part surface is caused because the thermoplastic resin of molten state contacts in mould with the metal sheet of low temperature, in common manufacture method, there is the problem of the metal composite parts being difficult to the excellent adhesion manufacturing metal parts and polybutylene terephthalate resin combination.
Therefore, when using polybutylene terephthalate resin or polybutylene terephthalate resin combination to manufacture metallic composite laminated parts, the manufacturing process such as injection forming cannot be applied because of the problem of the adaptation of metal parts and resin, need numerous and diverse operation of the molding using self adhesive tape, the stacked metal parts of caking agent and polybutylene terephthalate resin.
In view of the foregoing, during by methods such as injection formings by metal parts and polybutylene terephthalate resin or polybutylene terephthalate resin combination form metal composite component, expect the method for the adaptation of development and improvement metal parts and resin.
The method of the adaptation of metal parts in the metal composite parts of polybutylene terephthalate resin or polybutylene terephthalate resin combination and resin is used as improvement, such as, known following method: successively anodic oxidation treatment is implemented to the metal parts formed by aluminium alloy, the machinery removing process of oxide skin epithelium, based on the etch processes of acidic aqueous solution, with the contact pairs based on hydrazine etc., carry out microetch, metal parts microetch crossed by injection forming and the polybutylene terephthalate resin combination Composite comprising pet resin, manufacture the method (patent documentation 1) of metal composite parts, the metal parts crossed by microetch impregnated in after in the aqueous solution of water-soluble alcohol, by injection forming, metal parts and the polybutylene terephthalate resin combination Composite comprising pet resin is manufactured the method (patent documentation 2) etc. of metal composite parts.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-001216 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2006-027018 publication
Summary of the invention
the problem that invention will solve
According to the method that patent documentation 1 and 2 is recorded, part polybutylene terephthalate resin combination infiltrates the recess be formed on metal part surface, therefore anchor effect is passed through, improve the adaptation of metal parts and polybutylene terephthalate resin combination to a certain extent, for the metal composite parts obtained, metal parts and polybutylene terephthalate resin combination are still easily peeled off at contact surface place.
In addition, in the method that patent documentation 1 and 2 is recorded, the recess be formed on metal part surface is infiltrated fully in order to make polybutylene terephthalate resin combination, in order to prevent causing the snap cure of resin because the molten resin of high temperature in mould contacts with the metal parts of low temperature, needing is the high temperature more than 100 DEG C by mold temperature set.
Therefore, in the method that patent documentation 1 and 2 is recorded, the normally used temperature control equipment making the mould of Warm water circulation cannot be used, need to use high boiling oil is used as the temperature control equipment of thermal medium, expend at the manpower of the management of thermal medium, cost of equipment in etc. existing problems.In addition, when mould is high temperature, also have problems in the operability when manufacturing metal composite parts.
for the scheme of dealing with problems
The present inventor finds; specified quantitative compounding in polybutylene terephthalate resin manufacture metal composite parts by the pet resin of the dicarbonyl unit modification except terephthaloyl unit time; even if the metal composite parts of the excellent adhesion of metal parts and polybutylene terephthalate resin combination also can be obtained under the low die temperature below 100 DEG C, and then complete the present invention.Specifically, the invention provides following technical scheme.
(1) a polybutylene terephthalate resin combination for metal composite shape components, it comprises (A) polybutylene terephthalate resin and (B) modification pet resin,
Aforementioned (B) modification pet resin comprises more than 5 % by mole and the dicarbonyl unit except terephthaloyl unit of less than 50 % by mole in total dicarbonyl unit,
Relative to the total mass of aforementioned (A) polybutylene terephthalate resin and aforementioned (B) modification pet resin, the content of aforementioned (B) modification pet resin is more than 10 quality % and below 50 quality %.
(2) the polybutylene terephthalate resin combination of the metal composite shape components Gen Ju (1), wherein, the fusing point of aforementioned (B) modification pet resin is less than 245 DEG C.
(3) the polybutylene terephthalate resin combination of basis (1) or the metal composite shape components described in (2), wherein, also comprises (C) fire retardant.
(4) the polybutylene terephthalate resin combination of the metal composite shape components Gen Ju (3), wherein, described (C) fire retardant is more than one the phosphorus flame retardant in the group that forms of the salt of the phospho acid condenses be selected from more than by phosphinates, diphosphinic acid salt (diphosphinate) and tripolymer
Relative to total amount 100 mass parts of aforementioned (A) polybutylene terephthalate resin and aforementioned (B) modification pet resin, the content of aforementioned (C) fire retardant is more than 10 mass parts and below 100 mass parts.
(5) the polybutylene terephthalate resin combination of the metal composite shape components Gen Ju (4), wherein, aforementioned phosphorus flame retardant is the phosphinates shown in following general formula (1) and/or the diphosphinic acid salt shown in following general formula (2).
[chemical formula 1]
(in general formula (1), (2), R 1, R 2be phenyl, hydrogen, can the C of straight or branched containing a hydroxyl 1-6-alkyl, R 3the C of straight or branched 1-10-alkylidene group, arylidene, alkyl arylene or aryl alkylene, M is alkaline-earth metal, basic metal, Zn, Al, Fe, boron, and m is the integer of 1 ~ 3, and n is the integer of 1 or 3, and x is 1 or 2.)
(6) the polybutylene terephthalate resin combination of the metal composite shape components Gen Ju (5), wherein, aforementioned phosphorus flame retardant is aluminum diethylphosphinate.
(7) according to the polybutylene terephthalate resin combination of the metal composite shape components described in any one in (4) ~ (6), wherein, also contain nitrogenous flame retardant as (D) flame retardant, aforementioned nitrogenous flame retardant is the salt of the triazine based compound shown in following general formula (3) and cyanuric acid or tricarbimide
Relative to total amount 100 mass parts of aforementioned (A) polybutylene terephthalate resin and aforementioned (B) modification pet resin, (D) content of flame retardant is more than 1 mass parts and below 50 mass parts
[chemical formula 2]
(in formula, R 4, R 5the oxyalkyl of hydrogen atom, amino, aryl or carbon number 1 ~ 3, R 4, R 5can be identical or different.)
(8) the polybutylene terephthalate resin combination of the metal composite shape components Gen Ju (7), wherein, aforementioned nitrogenous flame retardant is melamine cyanurate.
(9) according to the polybutylene terephthalate resin combination of the metal composite shape components described in any one in (1) ~ (3), wherein, aforementioned (C) fire retardant is bromide fire retardant, relative to total amount 100 mass parts of aforementioned (A) polybutylene terephthalate resin and aforementioned (B) modification pet resin, the content of (C) fire retardant is more than 10 mass parts and below 100 mass parts.
(10) the polybutylene terephthalate resin combination of the metal composite shape components Gen Ju (9), wherein, also contains antimony based compound as (D) flame retardant,
Relative to total amount 100 mass parts of aforementioned (A) polybutylene terephthalate resin and aforementioned (B) modification pet resin, the content of (D) flame retardant is more than 1 mass parts and below 50 mass parts.
(11) according to the polybutylene terephthalate resin combination of the metal composite shape components described in any one in (1) ~ (10), wherein, also containing (E) packing material,
Relative to total amount 100 mass parts of aforementioned (A) polybutylene terephthalate resin and aforementioned (B) modification pet resin, the content of (E) packing material is more than 5 mass parts and below 120 mass parts.
(12) according to the polybutylene terephthalate resin combination of the metal composite shape components described in any one in (1) ~ (11), wherein, also containing (F) fluorine resin,
Relative to total amount 100 mass parts of aforementioned (A) polybutylene terephthalate resin and aforementioned (B) modification pet resin, the content of (F) fluorine resin is more than 0.1 mass parts and below 5 mass parts.
(13) according to the polybutylene terephthalate resin combination of the metal composite shape components described in any one in (1) ~ (12), wherein, also containing (G) elastomerics,
Relative to total amount 100 mass parts of aforementioned (A) polybutylene terephthalate resin and aforementioned (B) modification pet resin, (G) elastomeric content is more than 1 mass parts and below 100 mass parts.
(14) metal composite parts, it is formed by the polybutylene terephthalate resin combination of the metal composite shape components described in any one in (1) ~ (13) and metal parts.
(15) the metal composite parts Gen Ju (14), wherein, aforementioned metal parts are the parts carrying out surface coarsening process.
(16) according to (14) or the metal composite parts described in (15), wherein, it is Personal Computer parts, portable terminal end pieces or office automation (OA) equipment unit.
(17) manufacture method for metal composite parts, wherein, is supplied to the mould being placed with metal parts by shaped material by forming mill,
Described shaped material comprises (A) polybutylene terephthalate resin and (B) modification pet resin,
Aforementioned (B) modification pet resin comprises more than 5 % by mole and the dicarbonyl unit except terephthaloyl unit of less than 50 % by mole in total dicarbonyl unit,
Relative to the total mass of aforementioned (A) polybutylene terephthalate resin and aforementioned (B) modification pet resin, the content of described (B) modification pet resin is more than 10 quality % and below 50 quality %.
(18) manufacture method of the metal composite parts Gen Ju (17), wherein, aforementioned shaped material is the polybutylene terephthalate resin combination of the metal composite shape components described in any one in (1) ~ (13).
(19) manufacture method of basis (17) or the metal composite parts described in (18), wherein, aforementioned metal parts are through the parts of surface coarsening process.
(20) according to the manufacture method of the metal composite parts described in any one in (17) ~ (19), wherein, the temperature of foregoing mould is less than 100 DEG C.
(21) metal composite parts, it is obtained by the manufacturing process described in any one in (17) ~ (20).
the effect of invention
According to the present invention, even if also can the polybutylene terephthalate resin combination of metal composite parts of excellent adhesion of turned metal parts and polybutylene terephthalate resin combination under providing the die temperature below 100 DEG C.In addition, according to the present invention, even if the manufacture method of the metal composite parts of the metal composite parts of the excellent adhesion of metal composite parts and polybutylene terephthalate resin combination also can be manufactured under providing the die temperature below 100 DEG C.And then, according to the present invention, provide the metal composite parts of the excellent adhesion of metal parts and polybutylene terephthalate resin combination.
Accompanying drawing explanation
Fig. 1 is the schematic diagram observed from upper surface of the test film for evaluating metal adaptation in embodiment.
Fig. 2 is the schematic diagram of the evaluation method of the metal adaptation illustrated in embodiment.
Embodiment
Below, embodiments of the present invention are described in detail, but the present invention is not by any restriction of following embodiment, in the scope of object of the present invention, can suitably be changed to implement.It should be noted that, for the place of repeating is described, sometimes suitably omits the description, but do not limit the purport of invention.
Below, successively the shaped material of metal composite parts, the manufacture method of metal composite parts and metal composite parts are described.
[shaped materials of metal composite parts]
First, the shaped material of metal composite parts is described.According to expecting (A) polybutylene terephthalate resin and compounding more than one the composition be selected from the group be made up of (C) fire retardant, (D) flame retardant, (E) packing material, (F) tetrafluoro ethylene polymer, (G) elastomerics and (H) other additive of (B) modification pet resin for the manufacture of the shaped material of metal composite parts in the present invention.
When the shaped material of the metal composite parts used in the present invention contains the composition of (A) ~ (H) of specified amount, its mixed style is not particularly limited.As the object lesson of the form of the shaped material of metal composite parts, (i) can be listed by mixing for whole components fuse contained in shaped material and the particle of the polybutylene terephthalate resin combination that obtains, thin slice or powder, (ii) by (A) polybutylene terephthalate resin, or the particle of polybutylene terephthalate resin combination that the composition of (A) polybutylene terephthalate resin and expectation is formed, thin slice or powder, with by (B) modification pet resin, or the particle of (B) modification pet resin composition that the composition of (B) modification pet resin and expectation is formed, thin slice, or the mixture of powder.
It should be noted that, in the specification sheets and claims of the application, by the whole compositions in shaped material, by the method such as melting mixing or melt-shaping, the material of integration is called " polybutylene terephthalate resin combination ", is called " polybutylene terephthalate resin compound " by material not integrated with other composition at least one composition in shaped material.
In these forms, in the metal composite parts of the easy Homogeneous phase mixing of composition each shaped material, easily shaping homogeneous, preferably (i) is by mixing for whole components fuse contained in shaped material and the particle of the polybutylene terephthalate resin combination that obtains, thin slice or powder.In addition, shaped material be by whole components fuse mixing and obtain polybutylene terephthalate resin combination time, from the viewpoint of operability excellence when being shaped, preferably its shape is particulate state.
For according to expectation to (A) polybutylene terephthalate resin and compounding more than one the composition be selected from the group be made up of (C) fire retardant, (D) flame retardant, (E) packing material, (F) tetrafluoro ethylene polymer, (G) elastomerics and (H) other additive of (B) modification pet resin, by mixing for these components fuse, obtain the method for polybutylene terephthalate resin combination, can according to the manufacture method of existing known resin combination.As the suitable method being manufactured polybutylene terephthalate resin combination by melting mixing, the method using the melting mixing such as singe screw or twin screw extruder device can be listed.
Below, successively (A) polybutylene terephthalate resin of the composition of the shaped material as metal composite parts, (B) modification pet resin, (C) fire retardant, (D) flame retardant, (E) packing material, (F) tetrafluoro ethylene polymer, (G) elastomerics and (H) other additive are described.
((A) polybutylene terephthalate resin)
(A) polybutylene terephthalate resin that the present invention uses will at least comprise terephthalic acid or its ester-forming derivatives (C 1-6alkyl ester, etheride etc.) dicarboxylic acid component, with at least to comprise carbonatoms be the polybutylene terephthalate system resin that the aklylene glycol (BDO) of 4 or the diol component polycondensation of its ester-forming derivatives (acetylate etc.) obtain.(A) polybutylene terephthalate resin is not limited to equal polybutylene terephthalate resin, also can be the multipolymer of the mutual-phenenyl two acid bromide two alcohol ester's unit containing more than 60 % by mole (particularly more than 75 % by mole and less than 95 % by mole).
For the terminal carboxyl(group) amount of (A) polybutylene terephthalate resin used in the present invention, as long as do not hinder object of the present invention to be just not particularly limited.The terminal carboxyl(group) amount of (A) polybutylene terephthalate resin used in the present invention is preferably below 30meq/kg, is more preferably below 25meq/kg.When using the polybutylene terephthalate resin of the terminal carboxyl(group) amount of described scope, the metal composite parts obtained become the intensity being less likely to occur to cause because of the hydrolysis under hygrothermal environment to be reduced.
For the limiting viscosity of (A) polybutylene terephthalate resin used in the present invention, be not particularly limited in the scope not hindering object of the present invention.(A) limiting viscosity (IV) of polybutylene terephthalate resin is preferably more than 0.60dL/g and below 1.2dL/g.More preferably more than 0.65dL/g and below 0.9dL/g.When using the polybutylene terephthalate resin of the limiting viscosity of described scope, the plasticity of the polybutylene terephthalate resin combination obtained becomes excellent especially.In addition, the polybutylene terephthalate resin with different qualities viscosity can be mixed and carry out Adjustment Performance viscosity.Such as, by the polybutylene terephthalate resin of mixed characteristic viscosity 1.0dL/g and the polybutylene terephthalate resin of limiting viscosity 0.7dL/g, the polybutylene terephthalate resin of limiting viscosity 0.9dL/g can be prepared.(A) limiting viscosity (IV) of polybutylene terephthalate resin such as can measure in ortho chloro phenol under the condition of temperature 35 DEG C.
In (A) polybutylene terephthalate resin used in the present invention, as the dicarboxylic acid component's (comonomer components) except terephthalic acid and ester-forming derivatives thereof, include, for example out m-phthalic acid, phthalic acid, 2,6-naphthalene diacid, 4, the C such as 4 '-dicarboxydiphenyl ether 8-14aromatic dicarboxylic acid; The C such as succsinic acid, hexanodioic acid, nonane diacid, sebacic acid 4-16alkane dicarboxylic acid; The C such as cyclohexane dicarboxylic acid 5-10naphthenic hydrocarbon dicarboxylic acid; Ester-forming derivatives (the C of these dicarboxylic acid component 1-6alkyl derivative, etheride etc.).These dicarboxylic acid component may be used singly or in combination of two or more.
In these dicarboxylic acid component, the more preferably C such as m-phthalic acid 8-12the C such as aromatic dicarboxylic acid and hexanodioic acid, nonane diacid, sebacic acid 6-12alkane dicarboxylic acid.
In (A) polybutylene terephthalate resin used in the present invention, as 1, diol component (comonomer components) beyond 4-butyleneglycol, include, for example out ethylene glycol, propylene glycol, 1, ammediol, 1, the C such as 3-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol, 1,3-ethohexadiol 2-10aklylene glycol; The polyether polyols such as Diethylene Glycol, triethylene glycol, dipropylene glycol; The ester ring type such as cyclohexanedimethanol, Hydrogenated Bisphenol A glycol; Dihydroxyphenyl propane, 4, the aromatic diols such as 4 '-dihydroxybiphenyl; The C of the dihydroxyphenyl propanes such as oxyethane 2 moles of affixtures of dihydroxyphenyl propane, propylene oxide 3 moles of affixtures of dihydroxyphenyl propane 2-4oxirane affixture; Or the ester-forming derivatives of these glycol (acetylate etc.).These diol components may be used singly or in combination of two or more.
In these diol components, the more preferably C such as ethylene glycol, 1,3-PD 2-6polyether polyols or the cyclohexanedimethanol etc. such as aklylene glycol, Diethylene Glycol ester ring type glycol etc.
As comonomer components operable except dicarboxylic acid component and diol component, such as, 4-HBA, 3-hydroxy-benzoic acid, 6-Hydroxy-2-naphthoic acid, 4-carboxyl-4 can be listed ' aromatic hydroxy-carboxylic such as-xenol; The aliphatic hydroxyl such as glycolic acid, hydroxycaproic acid carboxylic acid; The C such as propiolactone, butyrolactone, valerolactone, caprolactone (6-caprolactone etc.) 3-12lactone; Ester-forming derivatives (the C of these comonomer components 1-6alkyl derivative, etheride, acetylate etc.).
For the polybutylene terephthalate multipolymer making comonomer components copolymerization described above, all (A) polybutylene terephthalate resin preferably can be used as.In addition, as (A) polybutylene terephthalate resin, equal polybutylene terephthalate polymkeric substance and polybutylene terephthalate multipolymer can also be combinationally used.
((B) modification pet resin)
(B) modification pet resin used in the present invention is the vibrin obtained according to known method polycondensation by altered contents.
Described altered contents must contain:
1) terephthalic acid or its ester-forming derivatives (C 1-6alkyl ester, etheride etc.),
2) ethylene glycol or its ester-forming derivatives (acetylate etc.) and
3) dicarboxylic acid except terephthalic acid or its ester-forming derivatives (C 1-6alkyl ester, etheride etc.).
Can infer, in metal composite parts of the present invention, the improved effect of the adaptation of metal parts and polybutylene terephthalate resin combination owing to: by (B) modification pet resin being compounded in the mobility improveing polybutylene terephthalate resin combination when being shaped in (A) polybutylene terephthalate resin, further, because crystallization rate reduces, shrinking percentage reduces.
Namely, can infer, by the mobility of improvement polybutylene terephthalate resin combination, resin combination becomes the fine concave portions easily infiltrated to metal part surface, and, due to the reduction of shrinking percentage, the resin that have cured at recess after cooling becomes and not easily departs from from recess, thus the adaptation of metal parts and polybutylene terephthalate resin combination is improved.
Therefore, from the viewpoint of the mobility of polybutylene terephthalate resin combination, the fusing point of (B) modification pet resin is preferably less than 245 DEG C, is particularly preferably less than 240 DEG C.
(B) fusing point of modification pet resin can use differential scanning calorimeter (DSC) to measure according to JISK7121.
(B) modification pet resin must comprise the dicarboxylic acid except terephthalic acid contained by coming from altered contents or its ester-forming derivatives (C 1-6alkyl ester, etheride etc.) dicarbonyl unit.(B) amount of contained in the modification pet resin dicarbonyl unit except terephthaloyl unit except preferably in total dicarbonyl unit more than 5 % by mole and less than 50 % by mole; be more preferably more than 7 % by mole and less than 30 % by mole, be particularly preferably more than 10 % by mole and less than 25 % by mole.
Being used as dicarboxylic acid contained in altered contents or the compound of its ester-forming derivatives as being suitable for, m-phthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acids, 4, the C such as 4 '-dicarboxydiphenyl ether can be listed 8-14aromatic dicarboxylic acid; The C such as succsinic acid, hexanodioic acid, nonane diacid, sebacic acid 4-16alkane dicarboxylic acid; The C such as cyclohexane dicarboxylic acid 5-10naphthenic hydrocarbon dicarboxylic acid; Ester-forming derivatives (the C of these dicarboxylic acid component 1-6alkyl derivative, etheride etc.).These dicarboxylic acid can be used alone or combinationally use two or more.
In these dicarboxylic acid or its ester-forming derivatives, the more preferably C such as m-phthalic acid 8-12aromatic dicarboxylic acid or its ester-forming derivatives, and, the C such as hexanodioic acid, nonane diacid, sebacic acid 6-12alkane dicarboxylic acid or its become ester derivative.In addition, from the viewpoint of the metal adaptation of the polybutylene terephthalate resin combination obtained and mechanical characteristics excellence, ester derivative, the particularly preferably ester-forming derivatives (dimethyl isophthalate, dimethyl isophthalate, m-phthalic acid diacid chloride etc.) of m-phthalic acid or m-phthalic acid is become as the dicarboxylic acid in altered contents or its.
The altered contents used in manufacture for (B) modification pet resin, in the scope not hindering object of the present invention, except the dicarboxylic acid of specified amount or its ester-forming derivatives, the diol component, hydroxycarboxylic acid component, Ginkgolide Component etc. except ethylene glycol and its ester-forming derivatives can also be comprised.In (B) modification pet resin composition, less than 30 % by mole are preferably in total repeating unit of the amount coming from the repeating unit of the altered contents such as these diol components, hydroxycarboxylic acid component, Ginkgolide Component in (B) modification pet resin, be more preferably less than 25 % by mole, be particularly preferably less than 20 % by mole.
As diol component contained in altered contents, the C such as propylene glycol, 1,3-PD, BDO, 1,3 butylene glycol, 1,6-hexylene glycol, neopentyl glycol, 1,3-ethohexadiol can be listed 2-10aklylene glycol; The polyoxalkylene glycol such as Diethylene Glycol, triethylene glycol, dipropylene glycol; The ester ring type such as cyclohexanedimethanol, Hydrogenated Bisphenol A glycol; Dihydroxyphenyl propane, 4, the aromatic diols such as 4 '-dihydroxybiphenyl; The C of the dihydroxyphenyl propanes such as oxyethane 2 moles of affixtures of dihydroxyphenyl propane, propylene oxide 3 moles of affixtures of dihydroxyphenyl propane 2-4oxirane affixture; Or the ester-forming derivatives of these glycol (acetylate etc.).These diol components can be used alone or combinationally use two or more.
As hydroxycarboxylic acid component contained in altered contents, 4-HBA, 3-hydroxy-benzoic acid, 6-Hydroxy-2-naphthoic acid, 4-carboxyl-4 can be listed ' aromatic hydroxy-carboxylic such as-xenol; The aliphatic hydroxyl such as glycolic acid, hydroxycaproic acid carboxylic acid; Or the ester-forming derivatives (C of these hydroxycarboxylic acids 1-6alkyl derivative, etheride, acetylate etc.).These hydroxycarboxylic acid component can be used alone or combinationally use two or more.
As Ginkgolide Component contained in altered contents, the C such as propiolactone, butyrolactone, valerolactone, caprolactone (6-caprolactone etc.) can be listed 3-12lactone.These Ginkgolide Components can be used alone or combinationally use two or more.
In the shaped material of metal composite parts, relative to the total mass of (A) polybutylene terephthalate resin with (B) modification pet resin, (B) consumption of modification pet resin is more than 10 quality % and below 50 quality %, be more preferably more than 15 quality % and below 45 quality %, be particularly preferably more than 20 mass parts and below 40 quality %.(B) when the consumption of modification pet resin is too much, the mechanical characteristics, chemical proofing etc. of the metal composite parts sometimes obtained are impaired, when consumption is very few, sometimes can not get the improved effect of the adaptation expected.
((C) fire retardant)
In the present invention, the shaped material of metal composite parts is often used to need in the purposes of flame retardant resistance.Now, preferably on the basis of (A) polybutylene terephthalate resin with (B) modification pet resin, (C) fire retardant is also comprised.For the kind of (C) fire retardant, do not limit in the scope not hindering object of the present invention, the various fire retardants of the fire retardant being all the time used as thermoplastic resin can be used.
As the example that can be suitable for (C) fire retardant used in the present invention, (c-1) phosphorus flame retardant and (c-2) bromide fire retardant can be listed.Successively (c-1) phosphorus flame retardant and (c-2) bromide fire retardant are described.
< (c-1) phosphorus flame retardant >
As (c-1) phosphorus flame retardant, phosphinates, diphosphinic acid salt, phosphate compound and phosphazene compound (phosphonitrile compound) etc. can be listed.Wherein, from the viewpoint of the flame retardant resistance of the polybutylene terephthalate resin combination easily obtaining, obtain and mechanical characteristics excellence, more than one being selected from the salt of the phospho acid condenses more than by phosphinates, diphosphinic acid salt and tripolymer are preferred, more preferably phosphinates and/or diphosphinic acid salt.
As the metal of the salt of phospho acid condenses more than formation phosphinates, diphosphinic acid salt or tripolymer, basic metal (potassium, sodium etc.), alkaline-earth metal (magnesium, calcium etc.), transition metal (iron, cobalt, nickel, copper etc.), periodictable 12 race metal (zinc etc.), metal belonging to group 13 of periodic table (aluminium etc.) etc. can be listed.Aforementioned metal salt containing these metals a kind of, also can be able to combine containing two or more.In aforementioned metal, preferred bases earth metals (magnesium, calcium etc.) and metal belonging to group 13 of periodic table (aluminium etc.).
The valence number of metal forming salt is not particularly limited, preferably more than 1 and less than 4, more preferably more than 2 and less than 4, particularly preferably 2 or 3.
As the phosphinates being used as (c-1) phosphorus flame retardant in the present invention, the compound shown in preferred following general formula (1), as diphosphinic acid salt, the compound shown in preferred formula (2).
[chemical formula 3]
In above-mentioned general formula (1), (2), R 1, R 2be phenyl, hydrogen, can the C of straight or branched containing a hydroxyl 1-6-alkyl.Preferred R 1, R 2all ethyls.
In addition, R 3the C of straight or branched 1-10alkylidene group, arylidene, alkyl arylene or aryl alkylene.
In addition, M is alkaline-earth metal, basic metal, Zn, Al, Fe, boron.Wherein, preferred Al.
M is the integer of 1 ~ 3, and n is the integer of 1 or 3, and x is 1 or 2.
As the object lesson that can be suitable for the phosphinates used in the present invention, dimethylphosphinic acid calcium, dimethylphosphinic acid magnesium, dimethylphosphinic acid aluminium, dimethylphosphinic acid zinc, ethylimethyphosphinic acid calcium, ethylimethyphosphinic acid magnesium, ethylimethyphosphinic acid aluminium, ethylimethyphosphinic acid zinc, diethyl phospho acid calcium, diethyl phospho acid magnesium, aluminum diethylphosphinate, diethyl phospho acid zinc, methyl-n-propylphosphinic acid calcium, methyl-n-propylphosphinic acid magnesium, methyl-n-propylphosphinic acid aluminium, methyl-n-propylphosphinic acid zinc etc. can be listed.
As the object lesson of the diphosphinic acid salt that can be suitable in the present invention using, methane two (methyl-phosphorous acid) calcium, methane two (methyl-phosphorous acid) magnesium, methane two (methyl-phosphorous acid) aluminium, methane two (methyl-phosphorous acid) zinc, benzene-1 can be listed, 4-(dimethyl phosphonic acids) calcium, benzene-Isosorbide-5-Nitrae-(dimethyl phosphonic acids) magnesium etc.
In above-mentioned phosphinates and/or diphosphinic acid salt, particularly preferably use aluminum diethylphosphinate.
For the shape of (c-1) phosphorus flame retardant, be not particularly limited in the scope not hindering object of the present invention.As the shape of (c-1) phosphorus flame retardant, from can dispersed polybutylene terephthalate resin combination, the viewpoint that obtains good flame retardant effect, be preferably powder shaped.
Relative to total amount 100 mass parts of (A) polybutylene terephthalate resin with (B) modification pet resin, the consumption of (c-1) phosphorus flame retardant in the present invention is preferably more than 10 mass parts and below 100 mass parts, be more preferably more than 10 mass parts and below 80 mass parts, be particularly preferably more than 15 mass parts and below 60 mass parts.(c-1), when the consumption of phosphorus flame retardant is too much, mechanical characteristics, plasticity are impaired sometimes, when consumption is very few, sometimes can not get good flame retardant resistance.
< (c-2) bromide fire retardant >
(c-2) bromide fire retardant used in the present invention is the organic compound containing bromine, as long as the flame-retarded material of macromolecular material can be made just to be not particularly limited, can use the various fire retardants of commercially available macromolecular material.
(c-2) amount of contained in bromide fire retardant bromine is preferably more than 20 quality %.When the amount of bromine is very few, then need to use a large amount of fire retardants to obtain the flame retardant resistance expected, the mechanical characteristics of metal composite parts is impaired sometimes.
For the molecular weight of (c-2) bromide fire retardant, in the scope not hindering object of the present invention, be not particularly limited, (c-2) bromide fire retardant can be low molecular compound, also can be macromolecular compound.As the object lesson of (c-2) bromide fire retardant used suitable in the present invention, hexabromobenzene, decabrominated dipheny base ether, tetrabromo-bisphenol, bromination imide compound can be listed, comprise the polycarbonate of the unit coming from brominated bisphenol A, the di-epoxy compounds, brominated Polystyrene, bromination acrylic acid polymer etc. as the reaction product of brominated bisphenol A and epoxy chloropropane.These (c-2) bromide fire retardants can combinationally use two or more.
Relative to total amount 100 mass parts of (A) polybutylene terephthalate resin with (B) modification pet resin, in the present invention, the consumption of (c-2) bromide fire retardant is preferably more than 10 mass parts and below 100 mass parts, is more preferably more than 15 mass parts and below 50 mass parts.By the content of (c-2) bromide fire retardant is set to above-mentioned scope, the polybutylene terephthalate resin combination with good flame-retardance can be prepared.
((D) flame retardant)
In the present invention, when the shaped material of metal composite parts needs flame retardant resistance, preferably on the basis of (A) polybutylene terephthalate resin, (B) modification pet resin and (C) fire retardant, also comprise (D) flame retardant.For the kind of (D) flame retardant, in the scope not hindering object of the present invention, do not limit, can from being used as (D) flame retardant suitable according to the kind choice for use of (C) fire retardant the various fire retardants of the fire retardant of thermoplastic resin all the time.
For (c-1) phosphorus flame retardant as the suitable fire retardant used in the present invention, preferred use (d-1) nitrogenous flame retardant is as (D) flame retardant, for (c-2) bromide fire retardant, preferably use (d-2) antimony compounds as (D) flame retardant.Below, successively (d-1) nitrogenous flame retardant and (d-2) antimony compounds are described.
The nitrogenous flame retardant > of < (d-1)
(d-1) the nitrogenous flame retardant used in the present invention can obtain good flame retardant effect, in the scope not hindering object of the present invention, is not particularly limited, and can be used as the known various nitrogenous compound that flame retardant uses.As the example of (d-1) nitrogenous flame retardant used suitable in the present invention, the salt of triazine based compound and cyanuric acid or tricarbimide can be listed, contain amino nitrogen compound and the double salt etc. of Tripyrophosphoric acid.These (d-1) nitrogenous flame retardants can combinationally use two or more.
As (d-1) the nitrogenous flame retardant used in the present invention, from the viewpoint of flame retardant effect excellence when combining with (c-1) phosphorus flame retardant, the more preferably salt of triazine based compound and cyanuric acid or tricarbimide and/or the double salt containing amino nitrogen compound and Tripyrophosphoric acid.
As the salt of above-mentioned triazine based compound and cyanuric acid or tricarbimide, preference illustrates the salt of the triazine based compound shown in following general formula (3) and cyanuric acid or tricarbimide.
[chemical formula 4]
In formula, R 4, R 5for hydrogen atom, amino, aryl or C 1-3oxyalkyl, R 4, R 5can be identical or different.
As (d-1) the nitrogenous flame retardant used in the present invention, in the salt of the triazine based compound shown in above-mentioned general formula (3) and cyanuric acid or tricarbimide, particularly preferably use melamine cyanurate.
In addition, for the nitrogen compound containing amino contained in the double salt containing amino nitrogen compound and Tripyrophosphoric acid, comprise and there is at least one amino and there is the heteroatomic assorted ring compound of at least one nitrogen-atoms as ring, except nitrogen, heterocycle also can have other heteroatoms such as sulphur, oxygen.For this nitrogen heterocyclic ring, comprise imidazoles, thiadiazoles, Thiadiazoline, furazan, triazole, thiadiazine, pyrazine, pyrimidine, pyridazine, triazine, purine etc. and there are five yuan or hexa-atomic unsaturated nitrogen heterocyclic ring etc. of multiple nitrogen-atoms as the constituting atom of ring.This containing in azo-cycle, preferably there is multiple nitrogen-atoms unsaturated containing azo-cycle, particularly preferably triazole and triazine as five yuan or hexa-atomic of constituting atom of ring.Further, in the double salt containing amino nitrogen compound and Tripyrophosphoric acid, preferred Tripyrophosphoric acid melam.
(A) total amount 100 mass parts of polybutylene terephthalate resin and (B) modification pet resin, in the shaped material of metal composite parts, the consumption of (d-1) nitrogenous flame retardant is preferably more than 1 mass parts and below 50 mass parts, more preferably more than 1 mass parts and below 40 mass parts, particularly preferably more than 1 mass parts and below 30 mass parts.By using (d-1) nitrogenous flame retardant as (C) fire retardant using the amount of above-mentioned scope, the metal composite parts of excellent in flame retardance can be obtained.
< (d-2) antimony compounds >
(d-2) that use in the present invention, as long as antimony compounds contains antimony and can obtain the material of good flame retardant effect, in the scope not hindering object of the present invention, is just not particularly limited.As the object lesson of suitable (d-2) antimony compounds, ANTIMONY TRIOXIDE SB 203 99.8 PCT, four weisspiessglanzs, antimony pentaoxide, sodium antimonate, antimony halides etc. can be listed.These antimony compoundss can combinationally use two or more, also can combinationally use with other flame retardants such as aluminium hydroxide, magnesium hydroxide, zinc sulphide.
For the form of (d-2) antimony compounds, as long as the resin portion of metal composite parts has good flame retardant resistance, be just not particularly limited, but be preferably particulate state, be more preferably the particulate state of median size 0.1 ~ 10 μm.
Relative to total amount 100 mass parts of (A) polybutylene terephthalate resin with (B) modification pet resin, in the present invention, the consumption of (d-2) antimony compounds is preferably more than 1 mass parts and below 50 mass parts, is more preferably more than 5 mass parts and below 20 mass parts.By using (d-2) antimony compounds as (C) fire retardant using the amount of above-mentioned scope, the metal composite parts of excellent in flame retardance can be obtained.
((E) packing material)
In the present invention, in order to improve the mechanical characteristics of metal composite parts, the shaped material of metal composite parts preferably also contains (E) packing material on the basis of (A) polybutylene terephthalate resin with (B) modification pet resin.For the kind of (E) packing material used in the present invention, in the scope not hindering object of the present invention, be not particularly limited, can use all the time as the packing material of macromolecular material and the various packing materials used, any one of inorganic filling material and organic filler material can be used.In addition, for the shape of (E) packing material used in the present invention, in the scope not hindering object of the present invention, do not limit, any one in fibrous filler material, granular packing material and sheet packing material can be used aptly.
As the suitable fibrous filler material used in the present invention, the inorganic fibre shape materials such as the fibrous material of the metals such as glass fibre, fibrous magnesium silicate, silica fiber, silica alumina fiber, sapphire whisker, Zirconium oxide fibre, boron nitride fibre, silicon nitride fiber, boron fibre, potassium titanate fiber and stainless steel, aluminium, titanium, copper, brass can be listed.
As the suitable granular packing material used in the present invention, the silicate such as carbon black, graphite, silicon-dioxide, quartz powder, granulated glass sphere, milled glass fibre, glass sacculus, glass powder, Calucium Silicate powder, pure aluminium silicate, kaolin, talcum, clay, diatomite, wollastonite can be listed; The oxide compound of the metals such as ferric oxide, titanium oxide, zinc oxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, aluminum oxide; The carbonate of the metal such as calcium carbonate, magnesiumcarbonate; The vitriol of the metal such as calcium sulfate, barium sulfate and, ferrite, silicon carbide, silicon nitride, boron nitride, various metal-powders etc.In addition, as suitable sheet packing material, mica, glass flake, various tinsels etc. can be listed.
In these (E) packing materials, from the viewpoint of the balancing good of cost and the physical property of metal composite parts obtained, particularly preferably use glass fibre.
As glass fibre, preferably use any one known glass fibre, length when not relying on cross-sectional shape or the manufacture for chopped strand, rove etc. of glass fiber diameter, cylinder, cocoon shape cross section, oval cross-section etc., the method for glass cutting.In the present invention, the kind of the glass of the raw material as glass fibre is not also limited, from the viewpoint of quality, preferably use the corrosion-resistant glass comprising zr element in E glass, composition.
In addition, in order to improve (E) packing material and the interfacial characteristics of the resinous substrates formed by (A) polybutylene terephthalate resin and (B) modification pet resin, preferably using and carrying out surface-treated packing material by the organic agent such as silane compound, epoxy compounds.As the silane compound used in described packing material, epoxy compounds, preferably can use any one known packing material, not rely in the present invention for the surface-treated silane compound of packing material, the kind of epoxy compounds.
Relative to total amount 100 mass parts of (A) polybutylene terephthalate resin with (B) modification polyethylene terephthalate, in the present invention, the consumption of (E) packing material is preferably more than 5 mass parts and below 120 mass parts, more preferably, more than 10 mass parts and below 100 mass parts, more than 15 mass parts are particularly preferably and below 80 mass parts.(E), when the consumption of packing material is too much, the mobility of resin combination when being sometimes shaped is impaired.
((F) fluorine resin)
In the present invention, the shaped material of metal composite parts preferably also contains (F) fluorine resin on the basis of (A) polybutylene terephthalate resin with (B) modification pet resin.By using (F) fluorine resin, the drippage of molten resin when polybutylene terephthalate resin combination can be suppressed to contact flame, obtains the metal composite parts that flame retardant resistance is more excellent.
As suitable (F) fluorine resin, the homopolymer of the fluorochemical monomers such as tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, R 1216, perfluoroalkyl vinyl ether or the multipolymer of the copolymerization monomer such as multipolymer, aforementioned fluorochemical monomer and ethene, propylene, (methyl) acrylate can be listed.These (F) fluorine resins can use one or combinationally use two or more.
As such (F) fluorine resin, such as, the multipolymers such as the homopolymer such as tetrafluoroethylene, polychlorotrifluoroethylene, poly(vinylidene fluoride), tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoro-ethylene copolymer are exemplified.In addition, (F) fluorine resin can use with the form of the mixture with other resins such as the polyamide series resin such as polyester based resin or polyamide 6 such as (methyl) acrylic ester resin, polyethylene terephthalate such as methyl methacrylate butyl acrylate copolymer.
Relative to total amount 100 mass parts of (A) polybutylene terephthalate resin with (B) modification pet resin, in the present invention, the consumption of (F) fluorine resin is preferably more than 0.1 mass parts and below 5 mass parts, is more preferably more than 0.2 mass parts and below 2 mass parts.
((G) elastomerics)
In the present invention, the shaped material of metal composite parts preferably also comprises (G) elastomerics on the basis of (A) polybutylene terephthalate resin with (B) modification pet resin.By using (G) elastomerics, the adaptation of metal parts and polybutylene terephthalate resin combination can be made excellent especially.
As suitable (G) elastomerics operable in the present invention, polyester-based elastomer, ethylene series elastomerics, polyvinyl acetate (PVA), fluoro-resin, ammonia ester based elastomers, acid amides based elastomers, acrylate based elastomers, styrene series elastomer, Fuoroelastomer, butadiene-based elastomerics etc. can be listed.And then can use the polymkeric substance of the core-shell-type formed by the shell portion of the glassy polymers such as core and methacrylic ester, wherein, described core is formed by rubber-like crosslinkeds such as butyl acrylates.These elastomericss can carry out modification by introducing the known methods such as epoxy group(ing), isocyanate group, amino isoreactivity group, crosslinked, grafting.
In the present invention, for (G) elastomeric consumption, in the scope not hindering object of the present invention, be not particularly limited.Relative to total amount 100 mass parts of (A) polybutylene terephthalate resin with (B) modification pet resin, (G) elastomeric consumption is preferably more than 1 mass parts and below 100 mass parts, be more preferably more than 3 mass parts and below 50 mass parts, be particularly preferably more than 5 mass parts and below 30 mass parts.By elastomeric to (G) consumption is set to above-mentioned scope, the adaptation of metal parts and polybutylene terephthalate resin combination can be made excellent especially.
(G) elastomerics preferably used in the present invention is ethylene series elastomerics, styrene series elastomer, core shell based elastomers and polyester-based elastomer.Below, successively ethylene series elastomerics, styrene series elastomer, core shell based elastomers and polyester-based elastomer are described.
< ethylene series elastomerics >
As ethylene series elastomerics, preferably comprise ethene and/or the propylene multipolymer as composition, specifically, can list ethylene propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, ethene-the third rare-butylene copolymer, ethylene-propylene-diene multipolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate glycidyl ester copolymer etc., but be not limited to this.And then, in ethylene series elastomerics, also following graft copolymer can be utilized: at (I) ethene-unsaturated carboxylic acid alkyl ester multipolymer or (II) by alpha-olefin and α, in the olefin copolymer of the glycidyl ester formation of beta-unsaturated acid, with side chain or crosslinking structure, chemical bonding has one or more graft copolymer of polymkeric substance or the multipolymer be made up of the repeating unit shown in following general formula (4).(wherein, R 6represent hydrogen or low alkyl group, X represents and is selected from-COOCH 3,-COOC 2h 5,-COOC 4h 9,-COOCH 2cH (C 2h 5) C 4h 9,-C 6h 5, one or more group in-CN)
[chemical formula 5]
< styrene series elastomer >
As being used as (G) elastomeric styrene series elastomer in the present invention, preferably use the segmented copolymer be made up of the elastomeric blocks of polystyrene block and polyolefin structure.As the concrete example of styrene series elastomer, styrene isoprene styrene block copolymer (SIS) (SIS), styrene-ethylene propylene-styrene block copolymer (SEPS), styrene-ethylene butylene-styrene block copolymer (SEBS), styrene-ethylene ethylene/propene-styrene block copolymer (SEEPS) etc. can be enumerated.
< core shell based elastomers >
Be used as (G) elastomeric core shell based elastomers in the present invention and there is the multilayered structure be made up of the shell on the surface at least partially of sandwich layer (core) and this sandwich layer coating.The sandwich layer of core shell based elastomers is preferably made up of rubber constituent (soft composition), and rubber constituent preferably can use acrylic rubber.The second-order transition temperature (Tg) of the rubber constituent that sandwich layer uses preferably lower than 0 DEG C (such as less than-10 DEG C), be more preferably less than-20 DEG C (such as more than-180 DEG C less than-25 DEG C), be particularly preferably less than-30 DEG C (such as more than-150 DEG C less than-40 DEG C).
For being used as the acrylic rubber of rubber constituent, preferably, with acrylic monomers such as alkyl acrylates for the polymkeric substance that principal constituent carries out being polymerized and obtain.Alkyl acrylate as the monomer of acrylic rubber is preferably acrylic acid C such as butyl acrylate 1~ C 12alkyl ester, is more preferably acrylic acid C 2~ C 6alkyl ester.
Acrylic rubber can be the homopolymer of acrylic monomer, also can be multipolymer.When acrylic rubber is the multipolymer of acrylic monomer, can be acrylic monomer multipolymer each other, also can be acrylic monomer and other multipolymers containing unsaturated link(age) monomer.When acrylic rubber is multipolymer, acrylic rubber also can be the rubber making cross-linkable monomer copolymerization.
< polyester-based elastomer >
For being used as (G) elastomeric polyester-based elastomer in the present invention, be just not particularly limited as long as modulus in flexure is below 1000MPa, preferably below 700MPa, can use various elastomerics, polyether-type or polyester type elastomer body all can use.
The polyester-based elastomer of polyether-type refer to aromatic polyester unit be hard segment, the polyester elastomer that is soft chain segment with the polyester formed by polymkeric substance and the dicarboxylic acid of oxyalkylene glycol.
Aromatic polyester unit in hard segment is the unit of polycondensate coming from the polycondensate of dicarboxylic acid compound and dihydroxy compound, the polycondensate of hydroxy carboxylic acid compound or dicarboxylic acid compound and dihydroxy compound and hydroxy carboxylic acid compound.As the object lesson of hard segment, the unit coming from polybutylene terephthalate can be enumerated.
Soft chain segment is introduced in polyester-based elastomer by the compound generated by the polycondensation of polyalkylene ether and dicarboxylic acid compound.As the object lesson of soft chain segment, the unit in the ester cpds source of the polyoxytetramethylene glycol such as derived by tetrahydrofuran (THF) can be enumerated.
Polyether-type elastomerics can use synthetics, also can use commercially available product.As the elastomeric commercially available product of polyether-type, can enumerate such as: PELPRENEP-30B, P-70B, P-90B, P-208B of Toyo Boseki K. K; The HYTREL4057,4767,6347,7247 of Dong Li Dupont Kabushiki Kaisha; The RITEFLEX655 of Ticona Inc..
Polyester type elastomer body refer to aromatic polyester unit be hard segment, the polyester elastomer that is soft chain segment with amorphism polyester unit.Aromatic polyester unit in hard segment is same with polyether-type elastomerics.As the amorphism polyester unit in soft chain segment, the unit of the polycondensate of ring-opening polymerization polymer or aliphatic dicarboxylic acid and the aliphatic diol coming from lactone can be enumerated.
Polyester type elastomer body can use synthetics, also can use commercially available product.As the commercially available product of polyester type elastomer body, PELPRENES-1002, S-2002 etc. that such as Toyo Boseki K. K manufactures can be enumerated.
((H) other additive)
In the present invention, in the shaped material of metal composite parts, (C) fire retardant, (D) flame retardant, (E) packing material, (F) fluorine resin and (G) elastomerics and other additive can be comprised according to target on the basis of (A) polybutylene terephthalate resin with (B) modification pet resin.
For (H) other additive, in the scope not hindering object of the present invention, be not particularly limited, the various additives that various resin is used can be used.As the object lesson of (H) other additive, antioxidant, heat-resisting stabilizing agent, UV light absorber, static inhibitor, dyestuff, pigment, lubricant, releasing agent, crystallization promoter, crystallization nucleating agent etc. can be listed.
As (H) other additive in the present invention, from improving thermostability and suppressing the object of transesterify of polybutylene terephthalate resin and modification pet resin, particularly preferably interpolation phosphorus system stablizer.For phosphorus system stablizer, in the scope not hindering object of the present invention, be not particularly limited, the stablizer of macromolecular material can be used as and the known various P contained compound used.As the example of the phosphorus system stablizer used suitable in the present invention, phosphate compound, bi-ester of phosphite and phosphonate compound, phosphate metal salt compound etc. can be listed.These phosphorus system stablizers can combinationally use two or more.
In the present invention, the total amount of the content of (A) in the shaped material of metal parts ~ (G) composition is preferably more than the 70 quality % in shaped material, be more preferably more than 80 quality %, be particularly preferably more than 90 quality %, most preferably be more than 99 quality %.Be set to above-mentioned scope by the total amount of the content by (A) ~ (G) composition, be easy to obtain the metal composite parts that the adaptation of metal parts and polybutylene terephthalate resin combination is excellent especially.
[manufacture method of metal composite parts]
Then, for the manufacture method of metal composite parts, metal parts, manufacturing process are described successively.
(metal parts)
The material of the metal parts used in the present invention is not particularly limited, such as, the metals such as aluminium, copper, iron, magnesium, nickel, titanium can be listed; The alloys such as aluminium alloy, phosphor bronze, stainless steel; The fitting body etc. of metal not of the same race.In addition, the material forming metal parts is not limited to metal, as long as have the parts of metal level on the surface.As the example of parts on the surface with metal level, the parts etc. being carried out plating by metals such as nickel, chromium, gold can be listed.
For the shape of metal parts, as long as the shaped material Composite of metal parts and metal composite parts can be made, be just not particularly limited, the parts of sheet, tubular, the different shape such as bar-shaped can be used.The metal parts used in the present invention can have for screw threads for fastening hub (boss), for strengthen rib (rib), for installing the various composed components needed for the finished product such as the jack of the parts such as gear etc., assembling electrical and electronic product.Specific restriction is not had to the shape of the part that metal parts contacts with the shaped material of metal composite parts, the arbitrary shapes such as rectangle, circle, ellipse can be selected.In addition, being not particularly limited the shape in the face that metal parts contacts with the shaped material of metal composite parts, can be plane, also can be curved surface.For the face that metal parts contacts with the shaped material of metal composite parts, be not limited to single plane or curved surface, also can have protuberance, recess in the inside of the plane of metal sheet or curved surface.The area of the part that metal parts contacts with the shaped material of metal composite parts is not particularly limited.
Roughening treatment is carried out at least partially preferably in advance to the part that metal parts contacts with the shaped material of metal composite parts.
Method surface to the metal parts used in the present invention being formed fine concavo-convex roughening treatment is not particularly limited, and can select aptly according to the material of metal, shape, desired characteristic etc. from the metal coarsing processing method all the time implemented.As the process forming micro concavo-convex on the metal surface, such as, can list based on chemical milling, processing to physical treatment and electroless platings etc. such as anodizing of aluminium process, liquid honing, sandblastings.Chemical milling is the method by process metal surfaces such as pharmaceutical chemicalss, and according to kind, the processing intent of metal, known various method, is used in various industrial circle.When carrying out the coarsing processing method of chemical milling as metal parts, method for chemially etching is not particularly limited, can selects arbitrarily from existing method.As the object lesson of method for chemially etching, include, for example out the method etc. recorded in Japanese Unexamined Patent Publication 10-96088 publication, Japanese Unexamined Patent Publication 10-56263 publication.
Such as, when the material of metal parts is aluminum or aluminum alloy, be preferably as follows method: after (1) forms oxide scale film based on the Micro etching of acidic aqueous solution and/or alkaline aqueous solution or (2) on metal part surface, removing oxide scale film, then by the method for the process metal part surfaces such as ammonia, hydrazine, water-soluble amine compound.Specifically, the metal parts that the method recorded by Japanese Unexamined Patent Publication 2006-001216 publication can be used to process.
In addition, according to the anodic oxidation treatment as the common surface preparation implemented aluminium, by use acid on anode by electrolysis of aluminum, the Porous of tens of nm ~ tens of μm of levels can be formed.In addition, as not only forming recess from the teeth outwards but also forming the method for protuberance on the contrary, known TRI process etc.
Thus, by using chemistry or physics, electric gimmick etc., or they are combined, the surface of metal parts forms the concavo-convex of tens of nm ~ tens of μm of sizes, thus the adaptation of metal parts and polybutylene terephthalate resin combination can be made more excellent.
(manufacturing process)
Metal parts described above is positioned in after on mould, by the shaped material of forming mill supply metal composite parts, thus manufactures metal composite parts of the present invention.The forming mill used in manufacture for metal composite parts, as long as the composite molded product that can form metal parts and polybutylene terephthalate resin combination is just not particularly limited, the existing various forming mills for metal composite shape components such as injection machine, extrusion shaper, compressing forming machine can be used.From the viewpoint of the easy degree of the setting of the mould to metal parts, the simplicity of device, the productivity excellence of metal composite parts, preferably use injection machine.
The temperature of mould during form metal composite component is not particularly limited.In order to improve the adaptation of metal parts and polybutylene terephthalate resin combination, high temperature, temperature such as more than 100 DEG C are preferred.During volume production metal composite parts, short from the viewpoint of cooling time, can shorten forming period, die temperature is preferably less than 100 DEG C, be more preferably more than 50 DEG C and less than 100 DEG C.When die temperature being set to below 100 DEG C, can by be typically used as mould thermostatic, be that the temperature control equipment of heating medium regulates die temperature with warm water, tool has the following advantages: do not need to prepare special temperature control equipment, and the manufacturing operation of metal composite parts becomes safety.
As long as (A) ~ (H) material that the shaped material of metal composite parts comprises specified amount is just not particularly limited, polybutylene terephthalate resin compound and polybutylene terephthalate resin combination all can use.As the suitable example of polybutylene terephthalate resin compound, can list: (1) will (C) ~ (H) of (A) polybutylene terephthalate resin and specified amount components fuse is mixing and the particle of the polybutylene terephthalate resin combination that obtains, and the mixture of particle of (B) modification pet resin; (2) particle of (A) polybutylene terephthalate resin, the mixture with the particle of the pet resin composition that components fuse is mixing by (C) ~ (H) of (B) modification pet resin and specified amount and obtain.
As the shaped material of the metal composite parts used in the present invention, from the viewpoint of being easy to the metal composite parts manufacturing homogeneous, more preferably use polybutylene terephthalate resin combination.
[metal composite parts]
For the metal composite parts of the present invention obtained by materials and methods described above, the excellent adhesion of metal parts and polybutylene terephthalate resin combination.Therefore, metal composite parts of the present invention can be used as the parts of such as various electrical and electronic product aptly.As the example of suitable electrical and electronic product using the metal composite parts obtained by method of the present invention, the OA equipment such as the computers such as portable terminal, notebook personal computer, desktop PC, duplicating machine, printer, facsimile recorder such as mobile telephone, digital camera, portable data assistance (PDA), portable game terminal, E-book reader can be listed.Metal composite parts of the present invention are due to metal and polybutylene terephthalate resin combination Composite, and the excellences such as intensity, light weight and designability, are particularly preferably used as the housing of portable terminal, computer, OA equipment etc.
Embodiment
Below, enumerate embodiment and in further detail the present invention is described, but the present invention does not limit by these embodiments.
< embodiment 1 ~ 5 and comparative example 1 ~ 6 >
In embodiment 1 ~ 5 and comparative example 1 ~ 6, use following material as the composition of polybutylene terephthalate resin combination.
It should be noted that, for following (B), (B '), use the DSCQ1000 of TAInstruments company to measure fusing point according to JISK7121 under heat-up rate 10 DEG C/min.
((A) polybutylene terephthalate resin)
The polybutylene terephthalate resin (WinTechpolymerLtd. manufacture) of A1: limiting viscosity 0.69dL/g
((B) modification pet resin)
B1: modification pet resin (BellPolyesterProducts, Inc. manufacture, by the isophthaloyl base unit modification of 12 % by mole in total dicarbonyl unit, and fusing point 232 DEG C, limiting viscosity 0.80dL/g)
((B ') non-modified pet resin)
B ' 1: pet resin (company of SK Chemical manufactures, fusing point 258 DEG C, limiting viscosity 0.76dL/g)
((C) fire retardant)
C1: aluminum diethylphosphinate (phosphorus flame retardant, Clariant company manufactures, ExolitOP1230)
C2: brominated polycarbonate (bromide fire retardant, Teijin Chemicals, Ltd. manufactures, FG-7500)
((D) flame retardant)
D1: melamine cyanurate (nitrogen system flame retardant, DSM N. V. manufactures, Melapure50)
D2: ANTIMONY TRIOXIDE SB 203 99.8 PCT (antimony compounds, Japanese concentrate Co., Ltd. manufactures, PATOX-M)
((E) packing material)
E1: glass fibre (Nitto Boseiki Co., Ltd. manufactures, CS3J648S)
((F) fluorine resin)
F1: tetrafluoro ethylene polymer (DuPont-MitsuiFluorochemicalsCo., Ltd. manufacture, PTFE850A)
((G) elastomerics)
G1: core shell based elastomers (RohmandHaasJapanCompany manufactures, ParaloidELX2311)
Composition shown in table 1 is dry mixed with the ratio of the content (mass parts) shown in table 1, and use twin screw extruder (the TEX-30 α that Corporation Japan Steel Works manufactures) to carry out melting mixing under the condition of barrel temperature 260 DEG C, spray volume 15kg/hr, screw speed 130rpm, make the particle of polybutylene terephthalate resin combination.Use the particle obtained in embodiment and comparative example to make test film, according to following method, adaptation is tested.The test-results of the adaptation of the polybutylene terephthalate resin combination about embodiment and comparative example is recorded in table 1.
< adaptation >
(test film making)
Below, see figures.1.and.2 and the evaluation method of adaptation is described.(Sodick company manufactures to use injection machine, TR-40VR), by using warm water to be 80 DEG C, load metal parts in mould after as the temperature control equipment of heating medium by mold temperature set, under the following conditions, the test film of injection forming adaptation evaluation.Wherein, metal parts uses aluminium (A1050) plate implementing to make surface coarsening as known " the NMT process of Taiseiplas company " of chemical milling class.The shape of the test film of adaptation evaluation as shown in Figure 1, uses the aluminium sheet 2 of 20mm × 50mm × thickness 1.6mm and the test film of polybutylene terephthalate resin combination 1 by the rectangular contact surface Composite of 10mm × 5mm.
[table 1]
[injection forming condition]
Barrel (resin) temperature 260℃
Injection speed 100mm/ second
Dwell pressure 98MPa
Forming period (pressurize-cooling time) 5 seconds-10 seconds
(adaptation evaluation)
First, by test film, after aluminium sheet 2 remove with the burr of the surrounding of the contact surface of polybutylene terephthalate resin combination 1, as shown in Figure 2, aluminium sheet 2 partial fixing of test film is fixed the recess of use fixture 4 in test film.Then, pressing fixture 3 is declined with the speed of 1mm/ minute, the polybutylene terephthalate resin combination 1 of pressure test, measures the ultimate load (N) when polybutylene terephthalate resin combination 1 is peeled off with aluminium sheet 2, observes the form destroyed.In addition, in the evaluation of adaptation, use OrientecCo., the TensilonUTA-50KN that Ltd. manufactures.
(flame retardant resistance)
About the polybutylene terephthalate resin combination obtained in embodiment 3 ~ 5 and comparative example 4 ~ 6, for test film (0.8mm thickness), implemented by the UL94 standard vertical combustion test of Underwriters Laboratories.
[table 2]
* in comparative example 4,5, resin and metal are not closely sealed, cannot evaluate adaptation.
From embodiment 1 ~ 5, relative to the total mass of polybutylene terephthalate resin and modification pet resin, in shaped material the content of modification pet resin be more than 10 quality % and below 50 quality % time, the metal composite parts of the excellent adhesion of metal parts and polybutylene terephthalate resin combination can be obtained.
In addition, from embodiment 3 ~ 5 and comparative example 4 ~ 6, by using the flame retardants such as the fire retardant such as phosphorus flame retardant, bromide fire retardant, nitrogenous flame retardant, antimony compounds to polybutylene terephthalate resin, the polybutylene terephthalate resin combination of excellent in flame retardance can be obtained.Especially, from embodiment 3 ~ 5, when the modification pet resin of sufficient quantity uses to polybutylene terephthalate resin, even if use fire retardant, flame retardant further, the adaptation of metal parts and polybutylene terephthalate resin combination also can not be impaired, can obtain the metal composite parts of excellent in flame retardance.
And then, according to embodiment 2 and 4, when shaped material comprises elastomerics, be easy to obtain the metal composite parts that the adaptation of metal parts and polybutylene terephthalate resin is excellent especially.
According to comparative example 1,4 and 5, when modification pet resin is added to polybutylene terephthalate resin, the metal composite parts that the adaptation of metal parts and polybutylene terephthalate resin combination is excellent especially cannot be obtained.In addition, according to comparative example 2,3 and 6, even if add unmodified pet resin in polybutylene terephthalate resin, the metal composite parts that the adaptation of metal parts and polybutylene terephthalate resin combination is excellent especially also cannot be obtained.
description of reference numerals
1 polybutylene terephthalate resin combination
2 aluminium sheets
3 pressing fixtures
4 test films fixedly use fixture

Claims (20)

1. a polybutylene terephthalate resin combination for metal composite shape components, it comprises (A) polybutylene terephthalate resin and (B) modification pet resin,
Described (B) modification pet resin comprises more than 10 % by mole and the dicarbonyl unit except terephthaloyl unit of less than 25 % by mole in total dicarbonyl unit,
Relative to the total mass of described (A) polybutylene terephthalate resin and described (B) modification pet resin, the content of described (B) modification pet resin is more than 10 quality % and below 50 quality %
The fusing point of described (B) modification pet resin is less than 240 DEG C,
Described dicarbonyl unit except terephthaloyl unit is derived from and is selected from by C 8-14aromatic dicarboxylic acid, C 4-16alkane dicarboxylic acid, C 5-10naphthenic hydrocarbon dicarboxylic acid and these dicarboxylic acid component ester-forming derivatives composition group at least any one.
2. the polybutylene terephthalate resin combination of metal composite shape components according to claim 1, wherein, also comprises (C) fire retardant.
3. the polybutylene terephthalate resin combination of metal composite shape components according to claim 2, wherein, described (C) fire retardant is more than one the phosphorus flame retardant in the group that forms of the salt of the phospho acid condenses be selected from more than by phosphinates, diphosphinic acid salt and tripolymer
Relative to total amount 100 mass parts of described (A) polybutylene terephthalate resin and described (B) modification pet resin, the content of described (C) fire retardant is more than 10 mass parts and below 100 mass parts.
4. the polybutylene terephthalate resin combination of metal composite shape components according to claim 3, wherein, described phosphorus flame retardant is the phosphinates shown in following general formula (1) and/or the diphosphinic acid salt shown in following general formula (2)
In general formula (1), (2), R 1, R 2be phenyl, hydrogen, can the C of straight or branched containing a hydroxyl 1-6-alkyl, R 3the C of straight or branched 1-10-alkylidene group, arylidene, alkyl arylene or aryl alkylene, M is alkaline-earth metal, basic metal, Zn, Al, Fe, boron, and m is the integer of 1 ~ 3, and n is the integer of 1 or 3, and x is 1 or 2.
5. the polybutylene terephthalate resin combination of metal composite shape components according to claim 4, wherein, described phosphorus flame retardant is aluminum diethylphosphinate.
6. the polybutylene terephthalate resin combination of the metal composite shape components according to any one in claim 3 ~ 5, wherein, also contain nitrogenous flame retardant as (D) flame retardant, described nitrogenous flame retardant is the salt of the triazine based compound shown in following general formula (3) and cyanuric acid or tricarbimide
Relative to total amount 100 mass parts of described (A) polybutylene terephthalate resin and described (B) modification pet resin, (D) content of flame retardant is more than 1 mass parts and below 50 mass parts
In formula, R 4, R 5the oxyalkyl of hydrogen atom, amino, aryl or carbon number 1 ~ 3, R 4, R 5can be identical or different.
7. the polybutylene terephthalate resin combination of metal composite shape components according to claim 6, wherein, described nitrogenous flame retardant is melamine cyanurate.
8. the polybutylene terephthalate resin combination of metal composite shape components according to claim 2, wherein, described (C) fire retardant is bromide fire retardant, relative to total amount 100 mass parts of described (A) polybutylene terephthalate resin and described (B) modification pet resin, the content of (C) fire retardant is more than 10 mass parts and below 100 mass parts.
9. the polybutylene terephthalate resin combination of metal composite shape components according to claim 8, wherein, also contains antimony based compound as (D) flame retardant,
Relative to total amount 100 mass parts of described (A) polybutylene terephthalate resin and described (B) modification pet resin, the content of (D) flame retardant is more than 1 mass parts and below 50 mass parts.
10. the polybutylene terephthalate resin combination of metal composite shape components according to claim 1 and 2, wherein, also containing (E) packing material,
Relative to total amount 100 mass parts of described (A) polybutylene terephthalate resin and described (B) modification pet resin, the content of (E) packing material is more than 5 mass parts and below 120 mass parts.
The polybutylene terephthalate resin combination of 11. metal composite shape components according to claim 1 and 2, wherein, also containing (F) fluorine resin,
Relative to total amount 100 mass parts of described (A) polybutylene terephthalate resin and described (B) modification pet resin, the content of (F) fluorine resin is more than 0.1 mass parts and below 5 mass parts.
The polybutylene terephthalate resin combination of 12. metal composite shape components according to claim 1 and 2, wherein, also containing (G) elastomerics,
Relative to total amount 100 mass parts of described (A) polybutylene terephthalate resin and described (B) modification pet resin, (G) elastomeric content is more than 1 mass parts and below 100 mass parts.
13. 1 kinds of metal composite parts, it is formed by the polybutylene terephthalate resin combination of the metal composite shape components described in any one in claim 1 ~ 12 and metal parts.
14. metal composite parts according to claim 13, wherein, described metal parts is the parts carrying out surface coarsening process.
15. metal composite parts according to claim 13 or 14, wherein, it is Personal Computer parts, portable terminal end pieces or business automation equipment parts.
The manufacture method of 16. 1 kinds of metal composite parts, wherein, is supplied to the mould being placed with metal parts by shaped material by forming mill,
Described shaped material comprises (A) polybutylene terephthalate resin and (B) modification pet resin,
Described (B) modification pet resin comprises more than 10 % by mole and the dicarbonyl unit except terephthaloyl unit of less than 25 % by mole in total dicarbonyl unit,
The fusing point of described (B) modification pet resin is less than 240 DEG C,
Described dicarbonyl unit except terephthaloyl unit is derived from and is selected from by C 8-14aromatic dicarboxylic acid, C 4-16alkane dicarboxylic acid, C 5-10naphthenic hydrocarbon dicarboxylic acid and these dicarboxylic acid component ester-forming derivatives composition group at least any one,
Relative to the total mass of described (A) polybutylene terephthalate resin and described (B) modification pet resin, the content of described (B) modification pet resin is more than 10 quality % and below 50 quality %.
The manufacture method of 17. metal composite parts according to claim 16, wherein, described shaped material is the polybutylene terephthalate resin combination of the metal composite shape components described in any one in claim 1 ~ 12.
The manufacture method of 18. metal composite parts according to claim 16 or 17, wherein, described metal parts is through the parts of surface coarsening process.
The manufacture method of 19. metal composite parts according to claim 16 or 17, wherein, the temperature of described mould is less than 100 DEG C.
20. 1 kinds of metal composite parts, it is obtained by the manufacture method described in any one in claim 16 ~ 19.
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