CN104272885A - Case for electronic devices - Google Patents
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- CN104272885A CN104272885A CN201380022684.9A CN201380022684A CN104272885A CN 104272885 A CN104272885 A CN 104272885A CN 201380022684 A CN201380022684 A CN 201380022684A CN 104272885 A CN104272885 A CN 104272885A
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- China
- Prior art keywords
- polybutylene terephthalate
- pbt
- resin
- electronic equipment
- housing
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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
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- 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
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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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
- C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
Abstract
To provide a case for electronic devices, which has a good balance between impact resistance and flame retardancy, while having excellent appearance. Produced is a case for electronic devices, which is configured of a polybutylene terephthalate resin composition that contains (A) a polybutylene terephthalate resin, (B) a modified polyethylene terephthalate resin, (C) a flame retardant that does not contain a halogen atom and (D) a thermoplastic polyester elastomer. The Charpy impact value of the polybutylene terephthalate resin composition as determined in accordance with ISO-179 is 7 kJ/m2 or more, and the polybutylene terephthalate resin composition meets 5VA standard by a test according to UL-94 standard.
Description
Technical field
The present invention relates to housing for electronic equipment.
Background technology
Each excellent such as engineering properties, electrical properties, chemical property of polybutylene terephthalate (PBT) resin, and processability is good, is therefore used to the purposes widely such as electronic equipment part, automobile component as engineering plastics.
Especially, among electronic equipment part, for the housing easily contacting human eye, require to have both resistance to impact and anti-flammability, also possess excellent aesthetic appearance.
As the polybutylene terephthalate (PBT) resin combination that may be used for electronic equipment part, disclose the composition (patent documentation 1) of compounding modified poly ester and phosphinates etc. in polybutylene terephthalate (PBT) resin.But the formed body that this technology is difficult to make to obtain takes into account anti-flammability and resistance to impact, be difficult to obtain the good aesthetic appearance etc. required by parts that housing etc. easily contacts human eye.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2007-91865 publication
Summary of the invention
the problem that invention will solve
The object of the present invention is to provide the housing for electronic equipment having both resistance to impact and anti-flammability, also possess excellent aesthetic appearance.
for the scheme of dealing with problems
The discoveries such as the present inventor, by fire retardant (C) and the thermoplastic polyester elastomer (D) of compounding in polybutylene terephthalate (PBT) resin (A) modification pet resin (B), not halogen atom, above-mentioned problem can be solved, thus complete the present invention.More specifically, the invention provides following technical scheme.
(1)
A kind of housing for electronic equipment, it is made up of polybutylene terephthalate (PBT) resin combination,
Described polybutylene terephthalate (PBT) resin combination comprises:
Polybutylene terephthalate (PBT) resin (A),
Modification pet resin (B),
Not halogen atom fire retardant (C) and
Thermoplastic polyester elastomer (D),
The charp impact value according to ISO-179 mensuration of above-mentioned polybutylene terephthalate (PBT) resin combination is 7kJ/m
2above,
Above-mentioned polybutylene terephthalate (PBT) resin combination meets 5VA standard in the test method(s) meeting foundation UL94 standard.
(2) housing for electronic equipment Gen Ju (1), it meets the following conditions: when above-mentioned polybutylene terephthalate (PBT) resin (A) is set to 100 quality % with the summation of above-mentioned modification pet resin (B), polybutylene terephthalate (PBT) resin (A) is more than 50 quality % and be below 70 quality %, and modification pet resin (B) is more than 30 quality % and less than 50 quality %.
(3) according to (1) or the housing for electronic equipment described in (2), wherein, the fire retardant (C) of above-mentioned not halogen atom and mass ratio (C)/(D) of above-mentioned thermoplastic polyester elastomer (D) are the scope of more than 4/6 and less than 6/4.
(4) according to the housing for electronic equipment according to any one of (1) ~ (3), wherein, above-mentioned thermoplastic polyester elastomer (D) is polyether-polyester type elastomer or polyester-polyester type elastomer.
(5) according to the housing for electronic equipment according to any one of (1) ~ (4), wherein, above-mentioned housing for electronic equipment is for holding office automation (Office Automation; The housing of the parts of the arbitrary electronic equipment OA) in the group that forms of equipment, home appliance or electric automobile.
(6) housing for electronic equipment Gen Ju (5), wherein, the parts of above-mentioned electronic equipment are supply unit parts.
the effect of invention
According to the present invention, provide the housing for electronic equipment having both resistance to impact and anti-flammability, also possess aesthetic appearance.
Accompanying drawing explanation
Fig. 1 be illustrate for measure flatness, the figure of test film that is made up of polybutylene terephthalate (PBT) resin combination of the present invention.
Embodiment
Below, an embodiment of the invention are described in detail, but the present invention is not by any restriction of following execution mode, in the scope of object of the present invention, can suitably be changed to implement.
< polybutylene terephthalate (PBT) resin combination >
Housing for electronic equipment of the present invention is formed by comprising polybutylene terephthalate (PBT) resin (A), the fire retardant (C) of modification pet resin (B), not halogen atom and the polybutylene terephthalate (PBT) resin combination of thermoplastic polyester elastomer (D), has the character of regulation.Below, each composition etc. is described.
[polybutylene terephthalate (PBT) resin (A)]
The polybutylene terephthalate (PBT) resin (A) used in the present invention is by least comprising terephthalic acid (TPA) or its ester-forming derivatives (C
1-6arrcostab, etheride etc.) dicarboxylic acid component, with at least to comprise carbon number be the polybutylene terephthalate (PBT) system resin that the aklylene glycol (BDO) of 4 or the diol component polycondensation of its ester-forming derivatives (acetylate etc.) obtain.Polybutylene terephthalate (PBT) resin is not limited to homopolymerization polybutylene terephthalate (PBT) resin, can also be the copolymer of the mutual-phenenyl two acid bromide two alcohol ester's unit containing more than 90 % by mole.
In the polybutylene terephthalate (PBT) resin (A) used in the present invention, as the dicarboxylic acid component's (comonomer components) except terephthalic acid (TPA) 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 butanedioic acid, adipic acid, azelaic acid, decanedioic acid
4-16alkane dicarboxylic acids; The C such as cyclohexane dicarboxylic acid
5-10cycloalkane dicarboxylic acid; Ester-forming derivatives (the C of these dicarboxylic acid component
1-6alkyl derivative, etheride etc.).These dicarboxylic acid component may be used alone, can also be used in combination 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 adipic acid, azelaic acid, decanedioic acid
6-12alkane dicarboxylic acids.
In the polybutylene terephthalate resin used in the present invention, as the diol component (comonomer components) beyond BDO, include, for example out ethylene glycol, propylene glycol, 1,3-PD, 1,3-BDO, 1, the C such as 6-hexylene glycol, neopentyl glycol, 1,3-ethohexadiol
2-10aklylene glycol; The polyether polyols such as diethylene glycol, triethylene glycol, DPG; The ester ring type such as cyclohexanedimethanol, hydrogenated bisphenol A glycol; Bisphenol-A, 4, the aromatic diols such as 4 '-dihydroxybiphenyl; The C of the bisphenol-As such as oxirane 2 moles of addition products of bisphenol-A, expoxy propane 3 moles of addition products of bisphenol-A
2-4alkylene oxide addition product; Or the ester-forming derivatives of these glycol (acetylate etc.).These diol components may be used alone, can also be used in combination two or more.
In these diol components, more preferably ethylene glycol, the C such as 1,3-PD
2-6polyether polyols or the cyclohexanedimethanol etc. such as aklylene glycol, diethylene glycol ester ring type dihydroxylic alcohols etc.
As comonomer components operable except dicarboxylic acid component and diol component, include, for example out 4-HBA, 3-hydroxybenzoic acid, 6-hydroxyl 2-naphthoic acid, 4-carboxyl-4 ' 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.).
The polybutylene terephthalate (PBT) copolymer of comonomer components copolymerization described above all suitably can use as polybutylene terephthalate (PBT) resin (A).In addition, as polybutylene terephthalate (PBT) resin (A), also can be that the mode of more than 90 % by mole combinationally uses homopolymerization polybutylene terephthalate (PBT) polymer and polybutylene terephthalate (PBT) copolymer with the mutual-phenenyl two acid bromide two alcohol ester's unit in the polybutylene terephthalate (PBT) resin (A) obtained.
For the terminal carboxyl group amount of the polybutylene terephthalate (PBT) resin (A) 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 the polybutylene terephthalate (PBT) resin used in the present invention is preferably below 30meq/kg, is more preferably below 25meq/kg.When using the polybutylene terephthalate (PBT) resin of the terminal carboxyl group amount of this scope, the polybutylene terephthalate (PBT) resin combination obtained becomes the intensity being less likely to occur to cause because of the hydrolysis under hygrothermal environment to be reduced.
The lower limit of the terminal carboxyl group amount of polybutylene terephthalate (PBT) resin (A) is had no particular limits, is preferably more than 10meq/kg, is more preferably more than 5meq/kg.Usually, terminal carboxyl group is difficult less than the manufacture of the polybutylene terephthalate (PBT) resin of 5meq/kg.
In addition, the inherent viscosity of the polybutylene terephthalate (PBT) resin (A) used in the present invention is not particularly limited in the scope not hindering object of the present invention.In order to make the mouldability of the polybutylene terephthalate (PBT) resin combination obtained excellent especially, the inherent viscosity (IV) of polybutylene terephthalate (PBT) resin (A) is preferably more than 0.60dL/g and below 1.2dL/g.More preferably more than 0.65dL/g and below 0.9dL/g.In addition, the polybutylene terephthalate (PBT) resin that also blendedly can have different inherent viscosities carrys out regulating characteristics viscosity.Such as, by the polybutylene terephthalate (PBT) resin of azeotropic nature viscosity to be the polybutylene terephthalate (PBT) resin of 1.0dL/g and inherent viscosity be 0.7dL/g, the polybutylene terephthalate (PBT) resin that inherent viscosity is 0.9dL/g can be prepared.The inherent viscosity (IV) of polybutylene terephthalate (PBT) resin (A) such as can measure in o-chlorphenol, under the condition of temperature 35 DEG C.
[modification pet resin (B)]
In the past, as the compounding ingredient of the alloying of the excellent compatibility with polybutylene terephthalate (PBT) resin (A), also use the pet resin not comprising altered contents, the modification polybutylene terephthalate (PBT) resin etc. comprising more than 10 % by mole altered contents.But, in the present invention, by using modification pet resin (B) the polybutylene terephthalate (PBT) resin combination comprised containing regulation altered contents, the casting of electronic device that mobility, warpage and anti-flammability are excellent especially can be obtained.
The modification pet resin (B) used in the present invention is the mylar obtained according to known method polycondensation by following material:
1) terephthalic acid (TPA) or its ester-forming derivatives (C
1-6arrcostab, etheride etc.),
2) ethylene glycol or its ester-forming derivatives (acetylate etc.) and
3) other dicarboxylic acids beyond terephthalic acid (TPA), its ester-forming derivatives (C
1-6arrcostab, etheride etc.), other glycol beyond ethylene glycol or its ester-forming derivatives (acetylate etc.) i.e. altered contents.
As other dicarboxylic acids beyond terephthalic acid (TPA), its ester-forming derivatives (C
1-6arrcostab, etheride etc.), the material same with the composition illustrated in (A) composition can be listed.In the present invention, preferably M-phthalic acid is used as altered contents.
As other glycol beyond ethylene glycol or its ester-forming derivatives (acetylate etc.), the C such as propylene glycol, 1,3-PD, BDO, 1,3-BDO, 1,6-hexylene glycol, neopentyl glycol, 1,3-ethohexadiol can be listed
2-10aklylene glycol; The polyether polyols such as diethylene glycol, triethylene glycol, DPG; The ester ring type such as cyclohexanedimethanol, hydrogenated bisphenol A glycol; Bisphenol-A, 4, the aromatic diols such as 4 '-dihydroxybiphenyl; The C of the bisphenol-As such as oxirane 2 moles of addition products of bisphenol-A, expoxy propane 3 moles of addition products of bisphenol-A
2-4alkylene oxide addition product; Or the ester-forming derivatives of these glycol (acetylate etc.).These diol components may be used alone, can also be used in combination two or more.
The altered contents used in the manufacture of the modification pet resin (B) used in the present invention also can comprise hydroxycarboxylic acid component, Ginkgolide Component etc. in the scope not hindering object of the present invention.In total repetitive in (B) pet resin, the amount derived from the repetitive of these compositions be preferably more than 5 % by mole and less than 30 % by mole, be more preferably more than 7 % by mole and less than 20 % by mole, be particularly preferably more than 10 % by mole less than 15 % by mole.
As the hydroxycarboxylic acid component comprised in altered contents, can list: 4-HBA, 3-hydroxybenzoic acid, 6-Hydroxy-2-naphthoic acid, 4-carboxyl-4 ' 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 may be used alone, can also be used in combination two or more.
As the Ginkgolide Component comprised in altered contents, can list: the C such as propiolactone, butyrolactone, valerolactone, caprolactone (6-caprolactone etc.)
3-12lactone.These Ginkgolide Components may be used alone, can also be used in combination two or more.
From the viewpoint of the mobility of polybutylene terephthalate (PBT) resin combination, the fusing point of modification pet resin (B) is preferably less than 245 DEG C, is particularly preferably less than 240 DEG C.The fusing point of modification pet resin (B) can, according to JIS K7121, use differential scanning calorimeter (DSC) to measure.
About the modification pet resin (B) in the polybutylene terephthalate (PBT) resin combination used in the present invention, when polybutylene terephthalate (PBT) resin (A) is set to 100 quality % with the summation of above-mentioned modification pet resin (B), polybutylene terephthalate (PBT) resin (A) is more than 50 quality % and be below 70 quality %, and modification pet resin (B) is more than 30 quality % and is preferred less than 50 quality %, polybutylene terephthalate (PBT) resin (A) is more than 55 quality % and below 65 quality %, and modification pet resin (B) is more than 35 quality % and below 45 quality % are preferred.When polybutylene terephthalate (PBT) resin (A) is set to 100 quality % with the summation of above-mentioned modification pet resin (B), if polybutylene terephthalate (PBT) resin (A) is below 50 quality %, then the possibility that the mouldability that there is polybutylene terephthalate (PBT) resin combination reduces.When polybutylene terephthalate (PBT) resin (A) is set to 100 quality % with the summation of above-mentioned modification pet resin (B), if polybutylene terephthalate (PBT) resin (A) is more than 70 quality %, then there is the not preferred possibility of the aesthetic appearance of products formed, warpage and anti-flammability.
The consumption of the modification pet resin (B) in the polybutylene terephthalate (PBT) resin combination used in the present invention be preferably more than 30 mass parts relative to 100 mass parts polybutylene terephthalate (PBT) resins (A) and less than 100 mass parts, be more preferably more than 40 mass parts and less than 100 mass parts.For during less than 30 mass parts, the not preferred possibility of the aesthetic appearance of the housing for electronic equipment obtained, warpage and anti-flammability is there is in the consumption of modification pet resin (B) relative to 100 mass parts polybutylene terephthalate (PBT) resins (A).When the consumption of modification pet resin (B) is more than 100 mass parts relative to 100 mass parts polybutylene terephthalate (PBT) resins (A), the possibility that the mouldability that there is polybutylene terephthalate (PBT) resin combination reduces.
[not the fire retardant (C) of halogen atom]
As the fire retardant (C) of the not halogen atom used in the present invention, there is no particular limitation, can list: phosphorus flame retardant, Sb system fire retardant and nitrogenated flame retardant etc.
As phosphorus flame retardant, as long as the compound with phosphorus atoms just has no particular limits, include, for example out organic phosphorus flame retardant, Phos flame retardant.As organic phosphorus flame retardant, can list: phosphate (aromatic phosphoric ester etc. such as triphenyl phosphate), phosphoric ester amides, phosphazene compound ((gathering) phenoxy phosphazene etc.), organic phosphonic compound (phosphonate ester etc. such as diphenyl methylphosphonate, phenyl-phosphonic acid diethylester), organophosphinic acids compound (phosphinic acid methyl ester etc.), phosphine oxide (triphenylphosphine oxide, trimethylphenyl phosphine oxide etc.).
As Phos flame retardant, can list: the non-condensations such as red phosphorus, orthophosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acids (metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, four phosphoric acid etc.), poly phosphorous acid (methylisothiouronium methylphosphite, pyrophosphorous acid etc.) or condensation (Asia) phosphate (slaine etc. such as calcium) etc.
Can enumerate as Sb system fire retardant: antimony trioxide, antimony pentaoxide, sodium antimonate etc.As nitrogenated flame retardant, the salt of triazine based compound and cyanuric acid or isocyanuric acid, the double salt etc. containing amino nitrogen compound and polyphosphoric acids.
Among above-mentioned fire retardant, not producing the viewpoint of toxic gas from obtaining high resistant burning effect, preferably using organic phosphorus flame retardant.In addition, above-mentioned fire retardant may be used singly or in combination of two or more use.
The fire retardant (C) of the not halogen atom in the polybutylene terephthalate (PBT) resin combination used in the present invention is preferably more than 4/6 with the not fire retardant (C) of halogen atom and the mass ratio ((C)/(D)) of aftermentioned thermoplastic polyester elastomer (D) and the mode of the scope of less than 6/4 uses.By making the fire retardant of not halogen atom (C) be in above-mentioned scope with the mass ratio of thermoplastic polyester elastomer (D), thus anti-flammability and the resistance to impact of the housing for electronic equipment obtained can be taken into account aptly.When the fire retardant (C) of halogen atom and the mass ratio of thermoplastic polyester elastomer (D) are not less than 4/6, there is the possibility of not giving the sufficient anti-flammability of the housing for electronic equipment obtained.The fire retardant (C) of halogen atom and the mass ratio of thermoplastic polyester elastomer (D) be not for during more than 6/4, there is the possibility of the resistance to impact deficiency of the housing for electronic equipment obtained.
In addition, in the polybutylene terephthalate (PBT) resin combination used in the present invention, not the consumption of the fire retardant (C) of halogen atom to be preferably more than 40 mass parts relative to 100 mass parts polybutylene terephthalate (PBT) resins (A) and below 100 mass parts, be more preferably more than 40 mass parts and below 65 mass parts.By comprising the fire retardant (C) of not halogen atom in housing for electronic equipment of the present invention with above-mentioned compounding amount, thus can be flame-retarded by housing for electronic equipment aptly.
It is flame-retarded that housing for electronic equipment of the present invention utilizes the fire retardant of not halogen atom, and the worry therefore generating harmful substance is few, environmentally preferred.
[thermoplastic polyester elastomer (D)]
Usually, the thermoplastic polyester elastomer (D) used in the present invention is for having the block copolymer of the structure of hard block (being formed by hard segments such as aromatic polyesters) and soft block (soft chain segment) bonding.Thermoplastic polyester elastomer (D) is categorized as polyester-polyester type elastomer and polyether-polyester type elastomer according to the kind of soft block, and any one all can be suitable for the present invention, can appropriately combined use two or more.Even if increase the viewpoint of the anti-flammability that fire retardant (C) that elastomeric compounding amount do not sacrifice not halogen atom yet plays from water-disintegrable low viewpoint and be also adapted at the viewpoint of outdoor application, be more preferably polyether-polyester type elastomer.
Below, to thermoplastic polyester elastomer (D), be described according to the order of hard segment, soft chain segment, polyester elastomer.
(hard segment)
Hard segment is made up of hard polyesters such as aromatic polyesters.Hard polyester can be obtained by dicarboxylic acids and the polycondensation of glycol, the polycondensation etc. of hydroxycarboxylic acid.As hard polyester, preferably will at least comprise a kind of monomer polycondensation of aromatic monomer and the aromatic polyester obtained.
As the suitable aromatic monomer used in the manufacture of aromatic polyester, terephthalic acid (TPA), M-phthalic acid, phthalic acid, NDA, 4, the aromatic dicarboxylic acids such as 4 '-dicarboxydiphenyl ether; Quinhydrones, resorcinol, 4, the aromatic diol such as 4 '-dihydroxybiphenyl, bisphenol-A; 4-HBA, 3-hydroxybenzoic acid, 6-Hydroxy-2-naphthoic acid, 4-carboxyl-4 ' aromatic hydroxy-carboxylic such as-xenol; The alkyl of these aromatic monomers, alkoxyl or halogen substiuted body; The C of these aromatic monomers
1-6the ester-forming derivatives such as Arrcostab, etheride, acetylate.These aromatic monomers can appropriately combined two or more use.
Aromatic polyester also can be by above-mentioned aromatic monomer beyond the material of comonomer components copolymerization.As the object lesson of comonomer components, can list: the aklylene glycol such as ethylene glycol, propylene glycol, 1,3-PD, 1,3-BDO, 1,6-hexylene glycol, neopentyl glycol, 1,3-ethohexadiol; The polyether polyols such as diethylene glycol, triethylene glycol, DPG; The ester ring type such as cyclohexanedimethanol, hydrogenated bisphenol A glycol; The alkane dicarboxylic acids such as butanedioic acid, adipic acid, azelaic acid, decanedioic acid; The Cycloalkane dicarboxylic acids such as cyclohexane dicarboxylic acid; The aliphatic hydroxyl such as Glycolic acid, hydroxycaproic acid carboxylic acid; The C of these comonomer components
1-6the ester-forming derivatives such as Arrcostab, etheride, acetylate.These comonomer components can appropriately combined two or more use.
As long as just there is no particular limitation for the material that the aromatic polyester forming hard segment uses aromatic monomer to obtain.As the suitable aromatic polyester forming hard segment, include, for example out: the Wholly aromatic polyester obtained by more than one the monomer polycondensation be selected from the group that is made up of aromatic dicarboxylic acid, aromatic diol and aromatic hydroxy-carboxylic; The aromatic polyester obtained by aromatic dicarboxylic acid and (aliphatic diol, the alicyclic diol etc.) polycondensation of non-aromatic dihydroxylic alcohols; The aromatic polyester obtained by non-aromatic dicarboxylic acids (alkane dicarboxylic acids, Cycloalkane dicarboxylic acid etc.) and aromatic diol polycondensation; The aromatic polyester obtained by aromatic hydroxy-carboxylic and aliphatic hydroxyl carboxyl acid copolymer.
As the aromatic polyester forming hard segment, crystalline aromatic polyester or liquid crystal polyester can be used, preferably use crystalline aromatic polyester.As the suitable crystalline aromatic polyester forming hard segment, include, for example out: the C such as PETG, polybutylene terephthalate (PBT), PEN, PBN
2-4alkylene arylate; Utilize and be more than 1 % by mole and the modification C of the comonomer components modification of less than 30 % by mole (are more preferably more than 3 % by mole and less than 25 % by mole, are particularly preferably more than 5 % by mole and less than 20 % by mole) relative to monomer total amount
2-4alkylene arylate.As thermoplastic polyester elastomer (D), from the processing and forming of the polybutylene terephthalate (PBT) resin combination obtained easily, viewpoint that the engineering properties of formed body that obtains is high, preferably use and there is the polyester elastomer of polybutylene terephthalate (PBT) segment as hard segment.
(soft chain segment)
Among thermoplastic polyester elastomer (D), polyester-polyester type elastomer is made up of aforementioned hard segment and soft chain segment, and described soft chain segment is made up of flexible polyester.The flexible polyester forming soft chain segment can by the polycondensation of dicarboxylic acids and glycol, and the polycondensation etc. of hydroxycarboxylic acid, lactone obtains.Flexible polyester uses the polyester of the structure than the hard polyester softness forming hard segment, usually the monomer polycondensation comprising at least one aliphatic monomer composition is obtained.
As the aliphatic monomer composition of the monomer as flexible polyester, can list: the aklylene glycol such as ethylene glycol, propylene glycol, 1,3-PD, 1,3-BDO, 1,6-hexylene glycol, neopentyl glycol, 1,3-ethohexadiol; The polyether polyols such as polyoxyethylene glycol, polyoxypropylene glycol and polyoxytetramethylene glycol; The alkane dicarboxylic acids such as butanedioic acid, adipic acid, azelaic acid, decanedioic acid; The aliphatic hydroxyl such as Glycolic acid, hydroxycaproic acid carboxylic acid; The lactones such as propiolactone, butyrolactone, valerolactone, caprolactone (6-caprolactone etc.); The C of these aliphatic monomer compositions
1-6the ester-forming derivatives such as Arrcostab, etheride, acetylate.These aliphatic monomer compositions can appropriately combined two or more use.As required, these aliphatic monomer compositions can use with the non-aromatic such as alicyclic diol, Cycloalkane dicarboxylic acid combination of monomers.
As the flexible polyester forming the elastomeric soft chain segment of polyester-polyester type, the aliphatic polyester preferably obtained by alkane dicarboxylic acids and aliphatic diol, the polylactone obtained by the ring-opening polymerisation of lactone.
Among thermoplastic polyester elastomer (D), polyether-polyester type elastomer is made up of aforementioned hard segment and the soft chain segment with polyether units.
As the polyether units comprised in the elastomeric soft chain segment of polyether-polyester type, can list: comprise the polyoxy C such as polyoxyethylene glycol, polyoxypropylene glycol and polyoxytetramethylene glycol
2-6the aliphatic poly ether unit of aklylene glycol unit; Have and comprise polyoxy C
2-6the polyester unit etc. of the aliphatic poly ether unit of aklylene glycol unit.
As aliphatic poly ether unit, preferably derived from polyoxy C such as polyethylene glycol, polyoxypropylene glycol and polyoxytetramethylene glycol
2-4the unit of aklylene glycol.
As the polyester unit with aliphatic poly ether unit, preferably by polyether polyols, the polyester unit that obtains with the ester-forming derivatives of the non-aromatic dicarboxylic acids such as alkane dicarboxylic acids, Cycloalkane dicarboxylic acid, non-aromatic dicarboxylic acids.
(polyester elastomer)
The thermoplastic polyester elastomer (D) used in the present invention can by carrying out copolymerization to prepare with the composition giving soft chain segment by the composition giving above-mentioned hard segment according to known method.
As the suitable elastomeric example of polyester-polyester type used in the present invention, can list: the block copolymer be made up of following hard segment and soft chain segment, described hard segment is made up of the aromatic series crystalline polyester such as copolymer of polybutylene terephthalate (PBT) resin, polybutylene terephthalate (PBT) resin and copolymer composition (ethylene glycol, M-phthalic acid etc.) or liquid crystal polyester, and described soft chain segment is by passing through C
2-6aklylene glycol and C
6-12the copolymerization of alkane dicarboxylic acids and the aliphatic polyester that obtains is formed.
As the suitable elastomeric example of polyether-polyester type used in the present invention, can list: the block copolymer be made up of hard segment and soft chain segment, described hard segment is made up of the aromatic series crystalline polyester such as copolymer of polybutylene terephthalate (PBT) resin, polybutylene terephthalate (PBT) resin and copolymer composition (ethylene glycol, M-phthalic acid etc.) or liquid crystal polyester, and described soft chain segment is by by polyoxy C such as polyoxytetramethylene glycol
2-4the polycondensation of aklylene glycol and dicarboxylic acids and the polyester obtained are formed.
In thermoplastic polyester elastomer (D), about the mass ratio of hard segment and soft chain segment, in the mass ratio of soft chain segment/hard segment, be preferably more than 10/90 and less than 90/10, be more preferably more than 20/80 and less than 80/20, be particularly preferably more than 30/70 and less than 70/30, most preferably be more than 40/60 and less than 60/40.
In order to the resistance to impact of the formed body obtained can be improved well, obtain having the formed body of excellent engineering properties, the content of the thermoplastic polyester elastomer (D) in the polybutylene terephthalate (PBT) resin combination used in the present invention be preferably more than 30 mass parts relative to 100 mass parts polybutylene terephthalate (PBT) resins (A) and below 120 mass parts, be more preferably more than 40 mass parts and below 120 mass parts.
The thermoplastic polyester elastomer (D) used in the present invention is preferably more than 20 according to the hardness that the Shore hardness (D scale) in JIS K7215 specifies and less than 80.Being in above-mentioned scope by making the hardness of thermoplastic polyester elastomer (D) can give housing for electronic equipment preferred resistance to impact.
Shore hardness (D scale) can be regulated by the copolymerization ratios of soft chain segment/hard segment.Specifically, by improving the copolymerization ratios of the soft chain segment comprised in (D) composition, above-mentioned hardness can be reduced.On the other hand, by improving the copolymerization ratios of the hard segment comprised in (D) composition, above-mentioned hardness can be improved.In the present invention, above-mentioned hardness is more than 20 and situation less than 40 is set as soft, more than 40 and situation less than 60 is set as middle hardness, more than 60 and the situation of less than 80 is set as high rigidity.
Especially, suppress the resistance to impact of housing for electronic equipment, the reduction of hot strength well from the view point of balance, hardness (Shore hardness (D scale) preferably; 40 ~ less than 60) and high rigidity (Shore hardness (D scale); More than 60 and less than 80) thermoplastic polyester elastomer (D).
[inorganic filler]
The polybutylene terephthalate (PBT) resin combination used in the present invention, on the basis of above-mentioned required composition, preferably comprises inorganic filler.As inorganic filler, what can use in fibrous filler, granular filler, sheet filler etc. is any number of, also can be used in combination of two or more.
Preferably fibrous filler is used in the present invention.This is because, by using fibrous filler, the enhancing effect to formed body can be obtained, improving the mechanical property of formed body.Particularly preferably glass fibre among fibrous filler.As glass fibre, known glass fibre all can preferably use, length when not relying on the shapes such as glass fiber diameter, cylinder, cocoon shape section, elliptical profile or use in the manufacture of chopped strand, rove etc., the method for glass-cutting.In the present invention, the kind of glass does not also limit, and from the viewpoint of quality, preferably uses the corrosion-resistant glass containing zr element in E glass, composition.The fibre length of glass fibre, fibre diameter are also in general scope.Such as, fibre length can be used for more than 2.0mm and below 6.0mm, fibre diameter are more than 9.0 μm and the glass fibre of less than 14.0 μm.
In addition, to the content of the fibrous filler in polybutylene terephthalate (PBT) resin combination, there is no particular limitation, relative to more than 100 mass parts polybutylene terephthalate (PBT) resins preferably 100 mass parts and below 200 mass parts, be more preferably more than 100 mass parts and below 150 mass parts.
In addition, in the present invention, preferred compositions uses fibrous filler and sheet filler.Combinationally used by this, formed body resistance to impact can be given and significantly reduce warpage.Particularly preferredly be combined as glass fibre and sheet glass.
In addition, when combinationally using fibrous filler and sheet filler, the summation of the consumption of fibrous filling material and tabular filling material is preferably more than 100 mass parts relative to 100 mass parts polybutylene terephthalate (PBT) resins and below 200 mass parts.The ratio of threadiness filling material and tabular filling material can suitably be selected in the scope of effect not damaging the application.
[flame retardant]
The polybutylene terephthalate (PBT) resin combination used in the present invention preferably the basis of composition must comprise flame retardant above-mentioned.By combinationally using fire retardant and flame retardant, good flame retardant effect can be obtained.The kind of flame retardant is not particularly limited in the scope not hindering object of the present invention, flame retardant that can be suitable according to the kind choice for use of the not fire retardant (C) of halogen atom.
As the fire retardant (C) of the not halogen atom used in the present invention, when using organic phosphorus flame retardant, preferably use nitrogenous flame retardant as flame retardant.Wherein especially preferably use melamine cyanurate.
In addition, to the content of the flame retardant in polybutylene terephthalate (PBT) resin combination, there is no particular limitation, is preferably more than 20 mass parts and below 30 mass parts relative to 100 mass parts polybutylene terephthalate (PBT) resins.
[other composition]
In the polybutylene terephthalate (PBT) resin combination used in the present invention, other composition other than the above can also be comprised in the scope not damaging effect of the present invention.As other composition, include, for example out: the additives such as nucleator, pigment, antioxidant, stabilizer, plasticizer, lubricant, release agent and Antidrip agent, other resin etc.
To the content of other composition in polybutylene terephthalate (PBT) resin combination, there is no particular limitation, the content of other composition, relative to 100 mass parts polybutylene terephthalate (PBT) resins (A), is usually preferably below 30 mass parts with total amount, is more preferably below 20 mass parts.
[manufacture method of polybutylene terephthalate (PBT) resin combination]
To the concrete mode of the preparation method of polybutylene terephthalate (PBT) resin combination, there is no particular limitation.Such as, usually, as the preparation method of resin combination or its formed body, resin combination can be prepared by known equipment and method.Specifically, necessary composition can be mixed, use the extruder of singe screw or twin-screw or other melting mixing device to carry out mixing, prepare with the form of shaping particle.In addition, multiple extruder or other melting mixing device can also be used.In addition, whole composition can be dropped into from hopper simultaneously, also a part of composition can be dropped into from side material inlet.
< housing for electronic equipment >
Housing for electronic equipment of the present invention is made up of above-mentioned polybutylene terephthalate (PBT) resin combination." housing for electronic equipment of the present invention is made up of above-mentioned polybutylene terephthalate (PBT) resin combination " refers to, housing for electronic equipment of the present invention is by by shaping for this resin combination and obtain, and part or all of the constituent of housing for electronic equipment comes from above-mentioned polybutylene terephthalate (PBT) resin combination.
Such as, housing for electronic equipment of the present invention can use conventional forming machine to carry out shaping manufacture to above-mentioned polybutylene terephthalate (PBT) resin combination.As such forming machine, as long as usually at the forming machine of the shaping middle use of housing for electronic equipment with regard to there is no particular limitation, injection moulding machine, compacting shape machine etc. can be used.From metal parts to the aspect of the simplicity of the easy degree of the setting mould, device, productivity ratio excellence, preferably use injection moulding machine.
As the electronic equipment of application housing for electronic equipment of the present invention, there is no particular limitation, is preferably any person in the group that forms of OA equipment, home appliance or electric automobile.Housing for electronic equipment of the present invention possesses anti-flammability and resistance to impact, thus can be preferably used as the housing holding these electronic equipment parts.Housing for electronic equipment of the present invention has both resistance to impact and anti-flammability, also possesses excellent aesthetic appearance, therefore preferably can be applied to and easily contact human eye, easily contact extraneous air, require fail safe, the electronic equipment of good appearance.
[characteristic of polybutylene terephthalate (PBT) resin combination and housing for electronic equipment]
The polybutylene terephthalate (PBT) resin combination that uses in the present invention gives the resistance to impact of products formed excellence, anti-flammability and aesthetic appearance etc.
Specifically, the charp impact value according to ISO-179 mensuration of the polybutylene terephthalate (PBT) resin combination used in the present invention is 7kJ/m
2above, the excellent impact resistance of the housing for electronic equipment of the present invention be therefore made up of this polybutylene terephthalate (PBT) resin combination.In addition, the polybutylene terephthalate (PBT) resin combination used in the present invention meets 5VA standard, the excellent in flame retardance of the housing for electronic equipment of the present invention be therefore made up of this polybutylene terephthalate (PBT) resin combination in the test method(s) according to UL94 standard.In addition, housing for electronic equipment of the present invention due to inhibit warpage, surface coarse, uneven, therefore aesthetic appearance is excellent.
In addition, housing for electronic equipment of the present invention, owing to having good phase ratio creepage tracking index, therefore also possesses the fail safe required by electronic equipment (especially supply unit parts).
Embodiment
Below, enumerate embodiment and in further detail the present invention is described, but the present invention does not limit by these embodiments.
< material >
The details of each composition used in embodiment and comparative example is as described below.
Polybutylene terephthalate (PBT) (PBT); WinTech Polymer.Co., Ltd. manufacture, ProductName DURANEX (IV=0.8)
Modification PETG (modified PET); 12.5 % by mole of isophthalate modified PETGs, TEIJIN FIBERS LIMITED is used to manufacture
PETG (unmodified PET); TEIJIN FIBERS LIMITED manufactures, ProductName TRF
Modification polybutylene terephthalate (PBT) (modified PBT); Use 25 % by mole of isophthalate modified polybutylene terephthalate (PBT)s, WinTech Polymer.Co., Ltd. manufacture
Fire retardant; Use organic phosphate, Clariant (Japan) K.K. manufacture, ProductName Exolit OP1240
Flame retardant; Use melamine cyanurate, BASF Japan Ltd. manufacture, ProductName MELAPUR MC50
Stabilizer; Use sodium dihydrogen phosphate, Yoneyama Kagaku Kogyo KK manufactures, ProductName sodium dihydrogen phosphate
Dripping inhibitor; Use the manufacture of PTFE, Mitsubishi Rayon Co., Ltd., ProductName METABLENLA3800
Glass fibre; Use E glass chopped strand, Nippon Electric Glass Co., Ltd. manufactures, ProductName ECS 03T-187
Sheet glass; Use E sheet glass, Nippon Sheet Glass Co., Ltd. manufactures, ProductName Micro Glass Flake REFG-101
Elastomer 1; Use polyester-type polyester elastomer, Toyo Boseki K. K's manufacture, ProductName Pelprene S2001, hardness 55
Elastomer 2; Use polyether type polyester elastomer, the manufacture of Toray Dupont Co., Ltd., ProductName Hytrel3046, hardness 27
Elastomer 3; Use polyether type polyester elastomer, the manufacture of Toray Dupont Co., Ltd., ProductName Hytrel2571, hardness 72
Elastomer 4; Use polyether type polyester elastomer, the manufacture of Toray Dupont Co., Ltd., ProductName Hytrel5557, hardness 55
Elastomer 5; Use nucleocapsid, RohmHaasJapan Company manufacture, ProductName Paraloid EXL2314
Elastomer 6; Use MBS resin, RohmHaasJapan Company manufacture, ProductName Paraloid EXL2602
Elastomer 7; Use alkene, Mitsui Chemicals, Inc manufactures, ProductName N TAFMER MP0620
" Pelprene S " for have polybutylene terephthalate (PBT) as hard segment, there is the block copolymer of flexible polyester as soft chain segment.
" Hytrel " for have polybutylene terephthalate (PBT) as hard segment, there is the block copolymer of polyethers as soft chain segment, from the ratio of the copolymerization of soft chain segment, there is different hardness according to hard segment.
The copolymer that " Paraloid EXL2314 " is alkyl acrylate and alkyl methacrylate.
The copolymer that " Paraloid EXL2602 " is butadiene, alkyl acrylate and alkyl methacrylate.
" N TAFMER MP0620 " is maleic anhydride modified polyolefin.
In addition, " hardness " represents the Shore hardness (D scale) in JIS K7215.
< embodiment and comparative example >
By the raw material supplying shown in table 1,2 to double screw extruder (the TEX-30 α that Corporation Japan Steel Works manufactures), carry out melting mixing, manufacture granular polybutylene terephthalate (PBT) resin combination.Melting mixing condition is as following.It should be noted that, the unit of the numeral of the consumption of each composition of the expression in table 1 and 2 is mass parts.
(melting mixing condition)
Barrel temperature: 260 DEG C
Screw speed: 170rpm
Spray volume: 20kg/hr
(condition of molding of evaluation test film)
By the granular resin combination that obtains at 140 DEG C after dry 3 hours, under the following conditions by test film injection mo(u)lding.
Forming machine: FANUC Corporation manufactures ROBOSHOT S2000i100B
Barrel temperature: 260 DEG C
Mold temperature: 80 DEG C (water use regulation temperature)
Injection speed: 17mm/s
Dwell pressure: 60MPa × 20s
The each evaluation test film obtained is evaluated various characteristic according to following condition.The results are shown in table 1 and 2.
(tension test)
According to the metewands of ISO527-1,2 regulations, the hot strength of evaluation test film, tensile elongation are evaluated.
(bend test)
According to ISO178, the bending strength of evaluation test film, bending modulus are evaluated.
(charp impact value)
According to the metewand that ISO-179 (test film thickness 4mm) specifies, the charp impact value of evaluation test film is evaluated.
(melt viscosity)
According to ISO11443, the melt viscosity of the resin used in evaluation test film is measured.
(anti-flammability)
Evaluation test film (2mm thickness) is implemented to the UL94 standard vertical burning test of Underwriters Laboratories.The result of determination of UL94V-0, V-1, V-2 standard of each test film is shown in " UL94 " in table 1 and 2.In addition, the result of determination whether meeting 5VA among UL945VA, 5VB standard of each test film is shown in " 5VA " in table 1 and 2.
(outward appearance)
According to ISO178, visualization is carried out to the outward appearance of the test film after bend test.Metewand is as following.
Without coarse, without uneven, present the test film of good outward appearance; Zero
Surface finds test film that is coarse and/or inhomogeneity; △
(warpage)
The flatness of the test film of the writing board shape of measured length 120mm, width 120mm, thickness 2mm.The flatness of test film uses CNC determining image machine (ProductName; QVBHU404-PRO1F, Mitutoyo Corporation. manufactures) measure 9 points on the test film shown in Fig. 1.Metewand is as following.
Below 2mm; ◎
2～5mm；○
5～8mm；△
More than 8mm; ×
(phase ratio creepage tracking index (CTI))
Based on IEC112 the 3rd edition, use the phase ratio creepage tracking index (CTI) of 0.1% aqueous ammonium chloride solution and platinum electrode evaluation of measuring test film.In addition, based on following metewand, ranking is carried out to phase ratio creepage tracking index.
250～400V；2
400～600V；1
More than 600V; 0
[table 1]
[table 2]
Confirm in embodiment, by fire retardant (C) and the thermoplastic polyester elastomer (D) of compounding (B) modification PETG, not halogen atom in polybutylene terephthalate (PBT) resin (A), thus obtain possessing resistance to impact, resistance to electric trace and anti-flammability, suppress warpage, the formed body that outward appearance is good.
Claims (6)
1. a housing for electronic equipment, it is made up of polybutylene terephthalate (PBT) resin combination,
Described polybutylene terephthalate (PBT) resin combination comprises:
Polybutylene terephthalate (PBT) resin (A),
Modification pet resin (B),
Not halogen atom fire retardant (C) and
Thermoplastic polyester elastomer (D),
The charp impact value according to ISO-179 mensuration of described polybutylene terephthalate (PBT) resin combination is 7kJ/m
2above,
Described polybutylene terephthalate (PBT) resin combination meets 5VA standard in the test method(s) according to UL94 standard.
2. housing for electronic equipment according to claim 1, it meets the following conditions: when described polybutylene terephthalate (PBT) resin (A) is set to 100 quality % with the summation of described modification pet resin (B), polybutylene terephthalate (PBT) resin (A) is more than 50 quality % and be below 70 quality %, and modification pet resin (B) is more than 30 quality % and less than 50 quality %.
3. housing for electronic equipment according to claim 1 and 2, wherein, the fire retardant (C) of described not halogen atom and mass ratio (C)/(D) of described thermoplastic polyester elastomer (D) are the scope of more than 4/6 and less than 6/4.
4. the housing for electronic equipment according to any one of claims 1 to 3, wherein, described thermoplastic polyester elastomer (D) is polyether-polyester type elastomer or polyester-polyester type elastomer.
5. the housing for electronic equipment according to any one of Claims 1 to 4, wherein, described housing for electronic equipment is for holding the housing of the parts of the arbitrary electronic equipment in the group that forms of business automation equipment, home appliance or electric automobile.
6. housing for electronic equipment according to claim 5, wherein, the parts of described electronic equipment are supply unit parts.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012104679 | 2012-05-01 | ||
| JP2012-104679 | 2012-05-01 | ||
| PCT/JP2013/062673 WO2013165007A1 (en) | 2012-05-01 | 2013-04-30 | Case for electronic devices |
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| CN104272885A true CN104272885A (en) | 2015-01-07 |
| CN104272885B CN104272885B (en) | 2017-05-17 |
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Cited By (2)
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|---|---|---|---|---|
| CN109721970A (en) * | 2019-01-15 | 2019-05-07 | 胡敏悫 | A kind of shell and preparation method thereof |
| CN115135719A (en) * | 2020-02-19 | 2022-09-30 | 东洋纺株式会社 | Flame-retardant polyester resin composition and molded article containing same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2964033A1 (en) * | 2014-10-10 | 2016-04-14 | Basf Se | Deoxybenzoin containing flame retardant polymer compositions |
| DE102015223432A1 (en) | 2015-11-26 | 2017-06-01 | Clariant International Ltd | Polymeric flame retardant mixtures |
| CN111430185B (en) * | 2019-01-09 | 2022-06-17 | 厦门台松精密电子有限公司 | Relay structure with heat dissipation function |
| JP7259455B2 (en) * | 2019-03-22 | 2023-04-18 | 株式会社オートネットワーク技術研究所 | Case with connector, wire harness with connector, and engine control unit |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2013165007A1 (en) | 2015-12-24 |
| JP6117190B2 (en) | 2017-04-19 |
| CN104272885B (en) | 2017-05-17 |
| WO2013165007A1 (en) | 2013-11-07 |
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Effective date of registration: 20191111 Address after: Tokyo, Japan Patentee after: Poly Plastics Co., Ltd. Address before: Tokyo, Japan Patentee before: Win Tech Polymer Ltd. |