CN1396207A - Flame-retarded resin composition and its forming product - Google Patents
Flame-retarded resin composition and its forming product Download PDFInfo
- Publication number
- CN1396207A CN1396207A CN 02140952 CN02140952A CN1396207A CN 1396207 A CN1396207 A CN 1396207A CN 02140952 CN02140952 CN 02140952 CN 02140952 A CN02140952 A CN 02140952A CN 1396207 A CN1396207 A CN 1396207A
- Authority
- CN
- China
- Prior art keywords
- series
- resin composition
- fire
- acid
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
To provide a flame-retardant resin composition which can improve fabricability, particularly non-mold-staining properties and mold release characteristics in injection molding even when a flame-retardant is incorporated thereinto. The flame-retardant resin composition comprises 100 pts.wt. sum of (A) a thermoplastic polyester based resin (a PBT resin or the like) and (B) a styrenic resin (an ABS resin or the like), (C) about 1-25 pts.wt. halogenated bisphenol A type epoxy resin having >=50% blocked terminal epoxy groups and a number average molecular weight of <=8,000, (D) about 1-15 pts.wt. antimony compound, (E) about 1-60 pts.wt. inorganic filler, and (F) about 0.1-5 pts.wt. >=24C aliphatic monocarboxylic acid (a montanic ester or the like) at a ratio [(A)/(B)] (weight ratio) of the above component (A) to the above component (B) of 30/70 to 95/5. The flame-retardant resin composition is useful as the chassis member.
Description
Technical field
The present invention relates to fire-proof resin composition, it has excellent size stability, thermotolerance and flame retardant resistance, and excellent molding processability (mould-processibility), especially, flowability in molding processing, with long-pending attached formation (amount of the long-pending addendum that forms on the finger print tool) of the mould that in molding, reduces and the release property (mould-detachment) in injection-molded, and with the moulded products of said composition preparation.
Background technology
Traditionally, metal chassis parts or element for example aluminium type are cast vehicle chassis component or the element that has been used as driving arrangement, and this device drives is as the disk of information medium.Yet in order to make the cost in integral device miniaturization and weight reduction and the reduction device fabrication, the resin combination alternative metals is used as the material that is used for vehicle chassis component or element.
The resin combination that is used for vehicle chassis component or element need be in the high workability of molding processing, and molding approaches parts, pinpoint accuracy in molding or precision etc.In addition, for example disk drive miniaturization day by day recently of equipment self, to the equipment of miniaturization like this, it is difficult making its heat that produces that leaves effectively.Therefore, the resin combination that exploitation has an excellent heat resistance wishes, and especially resistance to heat distorsion (for example, heat-drawn wire is not less than 100 ℃) and high flame retardant are so that assurance safety.
Usually, styrene butadiene-acrylonitrile copolymer (being called ABS resin later on sometimes) is used as the material that is used for vehicle chassis component or element.Yet ABS degenerates its mouldability that is used for the thin-walled chassis, intensity and thermotolerance.Therefore, the resin combination of replacement ABS resin is in the research.
On the other hand, poly terephthalic acid Aden ester (being called the PBT resin later on sometimes) is one of thermoplastic polyester series plastics, and its mouldability, intensity and thermotolerance that is used for the thin-walled chassis is better than ABS, but it is not so good as ABS aspect warpage deformation.Therefore, by the PBT resin is mixed or blend with ABS resin, its warpage deformation, thermotolerance, the mouldability that is used for the thin-walled chassis, intensity etc. are improved.
Yet, the resin combination of the simple blend of PBT resin and ABS resin, its molding processability degenerates, and especially the amount of the long-pending addendum on mould increases (mould-nonstaining property degenerates), and mould-detachment degenerates in injection-molded.Therefore, the use of blended resin composition causes the productive rate of moulded products to descend, because need frequent cleaning mold (metal die), or the production cycle is longer.
The open No.18453/1980 (JP-55-18453B) of Japanese Patent discloses as the poly terephthalic acid Aden ester resin composition with releasable resin composition of improvement, and wherein poly terephthalic acid Aden ester contains the aliphatic monocarboxylic acid that is no less than 27 carbon atoms, a kind of ester therefrom and a kind of salt therefrom and mixes with at least a being selected from.Yet realize that in poly terephthalic acid Aden ester resin composition enough dimensional stabilitys are difficult.
On the other hand, as the flame-retarded technology that is used for resin combination, the method for adding as the halogenated epoxy resin of fire retardant to resin combination is known.Yet the resin combination that adds this fire retardant has low thermostability, and because the fusion of forcing machine is kneaded, the thermal history of the retention time in injection molding machine etc., its viscosity significantly increases.Therefore, the flowability of resin combination degenerates, and the result causes its molding processability to worsen sometimes or the final sometimes gelation of resin combination and form the incipient scorch product.
The technology of the gelification of the resin combination that causes as the interpolation that is used to suppress by fire retardant, for example, Japanese Unexamined Patent Application No.118849/1983 (JP-58-118849A) discloses the method that increases the epoxy amount in fire retardant, it is by using halogenated bisphenol A-basic ring epoxy resins fire retardant, this Resins, epoxy has high molecular, wherein the average repeating unit " n " of dihydroxyphenyl propane skeleton is not less than 11, comprises the melt-stability with the resin combination that prevents the gelification fire retardant so that improve.In addition, Japanese Unexamined Patent Application No.349793/1999 (JP-11-349793A) discloses the thermoplastic flame-proof polyester and resin composition that prevents gelification in the melt kneading, and it has excellent flowability and have excellent flame in molding processing.Described resin combination comprises, as main ingredient, and thermoplastic polyester, halogenated bisphenol A-basic ring epoxy resins, terminal epoxy groups group and weight-average molecular weight that this Resins, epoxy has the 30-95% of end capped or sealing are 1600-12000, and antimony containing compounds.Yet according to the method, when suppressing the gelification that is caused by melt kneading, it is difficult that the inhibition dimensional stability degenerates.In addition, because the mould-nonstaining property of resin combination degenerates, the amount that therefore is reduced in the long-pending addendum on the mould is difficult.Therefore, often mould (metal die) cleaning that will use of requirement or the productive rate that prolongs the production cycle of moulded products and use this resin combination to prepare moulded products can not improve.
Summary of the invention
Therefore, the purpose of this invention is to provide fire-proof resin composition, it has the molding processability (processibility) of improvement, the especially long-pending attached formation of reduction mould in injection-molded, and mobile, although the moulded products that it comprises fire retardant and prepares with said composition.
Another object of the present invention provides fire-proof resin composition, its have excellent size stability, thermotolerance and flame retardant resistance and in molding processing mould-detachment, and with the moulded products of said composition preparation.
Inventor of the present invention has done intensive research, so that finish above-mentioned purpose, has finally found the mixture of polymer blending-system, and it comprises thermoplastic polyester-series plastics and phenylethylene resin series; Halogenated bisphenol A-basic ring epoxy resins, this Resins, epoxy is no less than 50% by terminal epoxy groups group end capped or sealing, and number-average molecular weight is no more than 8000; Antimony containing compounds; Mineral filler and special aliphatic monocarboxylic acid component, described composition for improved molding processability (processibility), especially be reduced in the amount (improving mould-nonstaining property) of the long-pending addendum that forms on the mould, and flowability, and can prepare have excellent flame retardancy, dimensional stability and stable on heating moulded products.Finished the present invention based on above discovery.
Just; fire-proof resin composition of the present invention comprises (A) thermoplastic polyester-series plastics; (B) phenylethylene resin series; (C) halogenated bisphenol A-basic ring epoxy resins; its have be no less than 50% terminal epoxy groups group by end capped (sealing; that protect or block) structure; number-average molecular weight was no more than for 8000 (being called for short halogenated bisphenol A-basic ring epoxy resins later on); (D) a kind of antimony containing compounds; (E) mineral filler and (F) at least a aliphatic monocarboxylic acid component, it is selected from has the aliphatic monocarboxylic acid that is no less than 24 carbon atoms; its ester and its salt (being called for short the aliphatic monocarboxylic acid component later on).
Thermoplasticity-polyester series resin (A) can comprise crystalline polyester-series plastics or polyalkylene arylide (polyalkylene arylate)-series plastics, and its at least a unit is selected from terephthalic acid alkylene ester unit and alkylene naphthalate (alkylenenaphthalate) unit.For example, thermoplastic polyester-series plastics (A) can comprise (1) poly terephthalic acid Aden ester, (2) comprise the copolyesters of the terephthalic acid Aden ester units that is no less than 60 weight %, (3) polyester-series plastics composition, it comprises as poly terephthalic acid Aden ester of main ingredient etc.
Phenylethylene resin series (B) can comprise modified rubber (comprise rubber or rubber enhanced) phenylethylene resin series, maybe can comprise graft copolymer, wherein at least a aromatic vinyl monomer and vinyl cyanide monomers are by grafting-be aggregated on the rubber components.
Halogenated bisphenol A-basic ring epoxy resins (C) can contain a kind of unit by general formula (1) expression:
Wherein X represents halogen atom, and n representative is no more than 10 integer and wherein is no less than 50% terminal epoxy groups group by halogenated aryl group end capping (sealing, protection or block).
Antimony containing compounds (D) can comprise weisspiessglanz etc.Mineral filler (E) can comprise glass fibre, glass flake, talcum, mica etc.Aliphatic monocarboxylic acid component (F) can comprise the aliphatic monocarboxylic acid that contains 26-34 carbon atom.Aliphatic monocarboxylic acid component (F) can comprise aliphatics C
26-34Monocarboxylic acid and the ester of polyhydroxy-alcohol.
Thermoplastic polyester-series plastics (A) with respect to the ratio of phenylethylene resin series (B) (for example, the phenylethylene resin series of modified rubber) can be the former/latter=30/70-95/5 (weight ratio).Resin combination comprises, with respect to the thermoplastic polyester-series plastics (A) of 100 weight parts and phenylethylene resin series (B) (for example, the phenylethylene resin series of modified rubber) total amount, the halogenated bisphenol A-basic ring epoxy resins (C) of about 1-25 weight part, the antimony containing compounds of about 1-15 weight part (D), the montanic acid component as aliphatic monocarboxylic acid component (F) of the mineral filler of about 1-60 weight part (E) and about 0.1-5 weight part (for example, montanate).
In addition, the present invention includes the moulded products for preparing with above-mentioned fire-proof resin composition.Described moulded products can be used as vehicle chassis component or element.
Fire-proof resin composition of the present invention comprises (A) thermoplastic polyester-series plastics as base resin, (B) phenylethylene resin series, (C) halogenated bisphenol A-basic ring epoxy resins, (D) a kind of antimony containing compounds, (E) mineral filler and (F) aliphatic monocarboxylic acid component.In these components, described thermoplastic polyester-series plastics (A) and phenylethylene resin series (B) constitute main resin Composition.
[(A) thermoplastic polyester-series plastics]
The preparation of thermoplastic polyester-series plastics (A) be by, for example, dicarboxylic acid component and dihydroxy component polycondensation, hydroxycarboxylic acid component and lactone component polycondensation or these component polycondensations are carried out.Thermoplastic polyester-series plastics (A) can be equal polyester or copolyesters.In addition, thermoplastic polyester-series plastics (A) can be used alone or in combination.
The dicarboxylic acid component comprises, for example, aromatic dicarboxylic acid [for example, the aromatic dicarboxylic acid that contains 8-16 carbon atom is terephthalic acid for example, m-phthalic acid, phthalic acid, naphthalene dicarboxylic acids (2,6-naphthalene dicarboxylic acids etc.), the xenyl dicarboxylic acid, the diphenyl ether dicarboxylic acid, the ditan dicarboxylic acid, the diphenylethane dicarboxylic acid, diphenylketone dicarboxylic acid etc.] or derivatives thereof, the alicyclic dicarboxylic acid (for example, the alicyclic dicarboxylic acid of containing 8-12 carbon atom, for example, cyclohexane dicarboxylic acid, hexahydro-phthalic acid, the hexahydro-m-phthalic acid, hexahydroterephthalic acid, himic acid) or derivatives thereof, aliphatic dicarboxylic acid (for example, the aliphatic dicarboxylic acid that contains 2-40 carbon atom, for example, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, dodecanedicarboxylic acid, hexadecane dicarboxylic acid and dimeracid preferably contain the aliphatic dicarboxylic acid of 4-14 carbon atom and more preferably contain the aliphatic dicarboxylic acid of 6-10 carbon atom) or derivatives thereof.
Along band ground, the example of said derivative is to form ester, for example lower alkyl ester such as those acid anhydrides and the carboxylic acid halides such as the acyl chlorides of dimethyl ester.
Above-mentioned dicarboxylic acid can be used alone or as a mixture.Be aromatic dicarboxylic acid such as terephthalic acid and naphthalene dicarboxylic acids preferably as the dicarboxylic acid component.
As dihydroxy component, exemplary aliphatics aklylene glycol is arranged (for example, the aklylene glycol that contains the line style or the branching of 2-12 the carbon atom of having an appointment, for example, ethylene glycol, 1, ammediol, trimethylene glycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, neopentyl glycol, hexylene glycol, ethohexadiol and dodecanediol, preferably contain have an appointment the aklylene glycol of 2-10 carbon atom and more preferably be the aklylene glycol that contains 2-8 the carbon atom of having an appointment), alicyclic diol (for example, cyclohexane diol, cyclohexanedimethanol, hydrogenant dihydroxyphenyl propanes etc.), aromatic diol [for example, Resorcinol, Resorcinol, dihydroxy phenyl, naphthalenediol, dihydroxydiphenyl ether, 2, two (4-hydroxy phenyl) propane (claiming dihydroxyphenyl propane later on) of 2-, addition compound, it is to add alkylene oxide (C to dihydroxyphenyl propane
2-4Alkylene oxide is oxyethane and propylene oxide for example) form (for example, the dihydroxyphenyl propane of diethoxyization)], (containing wherein, the alkylidene group carbonatoms is the unitary glycol of a plurality of oxyalkylenes of about 2-4 to the poly suboxygen alkyl glycol, for example, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, dibutylene glycol, polytetramethylene ether diol, dipropylene glycol, tripropylene glycol, poly suboxygen propyl group glycol, polytetramethylene ether diol etc.).
Along band ground, described dihydroxy component can be alkyl group-, alkoxy base-or halogen substituted compounds.Dihydroxy component can be used alone or in combination.Preferred dihydroxy component is aklylene glycol (C especially
2-4Aklylene glycol) and alicyclic diol.
Exemplary as the hydroxycarboxylic acid component be hydroxycarboxylic acid, for example, hydroxy-benzoic acid, hydroxynaphthoic acid and diphenylene hydroxycarboxylic acid and its derivative.In addition, the example of derivative comprises and can form the sort of of ester by carboxylic group, for example, and than lower alkyl esters (for example, methyl esters, acid anhydrides, acyl halide for example chloride of acid).Described derivative is passable, for example, be alkyl group-, alkoxy base-or the compound of halogen-replacement.Hydroxycarboxylic acid can be by separately or be used in combination.
Exemplary lactone component is C
3-12Lactone such as propiolactone, butyrolactone, valerolactone, caprolactone (for example, 6-caprolactone) and other lactone.
In addition, in copolyesters, copolymerizable monomer comprises C
2-6Aklylene glycol (the line style aklylene glycol is ethylene glycol, trimethylene glycol and 1 for example, 4-butyleneglycol etc.), poly suboxygen alkyl glycol, it contains to have an appointment 2-4 and repeats oxyalkylene unit (glycol comprises poly-(oxygen base-C
2-4Alkylidene unit, for example, Diethylene Glycol etc.), C
6-12Aliphatic dicarboxylic acid (hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid etc.), have the aromatic dicarboxylic acid (phthalic acid, m-phthalic acid) and other the diacid of unsymmetrical structure.
In addition, except above-mentioned every kind of component, a spot of polyfunctional monomer, for example, poly carboxylic acid is as 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid and 1,2,4,5-pyromellitic acid, polyhydroxy-alcohol (many alcohol) can randomly be mixed as glycerine, TriMethylolPropane(TMP) and tetramethylolmethane.According to the present invention, also can be used by the polyester-series plastics that uses this class polyfunctional monomer preparation with branching or crosslinking structure.Therefore, as long as its fusion-mouldability does not degenerate, thermoplastic polyester-series plastics (A) not only can have the linear chain structure, and can have the chain structure or the crosslinking structure of branching.In addition, thermoplastic polyester-series plastics (A) can be a liquid crystal polyester.
Preferred thermoplastic polyester-series plastics (A) comprises saturated polyester-series plastics, especially, and aromatic polyester-series plastics.For example, exemplary thermoplastic polyester-series plastics (A) is to comprise unitary equal polyester of alkylidene aryl thing or copolyesters, for example, as the terephthalic acid alkylene ester of major constituent and/or alkylene naphthalate (for example, about 50-100wt%, about 75-100wt% preferably) [for example, all (for example poly terephthalic acid 1,4-cyclohexanedimethyleterephthalate ester (PCT) for polyester such as polyalkylene terephthalates; Poly terephthalic acid C
2-4Alkylene ester such as polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PPT), polybutylene terephthalate (PBT)), poly-alkylene naphthalate (for example, poly-naphthalic acid C
2-4Alkylene ester is as poly-naphthalic acid ethylidene ester, poly-naphthalic acid butylidene ester); Comprise terephthalic acid alkylene ester and/or the unitary copolyesters of alkylene naphthalate as major constituent (for example, being not less than 50wt%)] and aromatic polyester completely, wherein dicarboxylic acid component and diol component all are aromatics.Especially, comprising the mutual-phenenyl two acid bromide two alcohol ester unit is preferred as the polybutylene terephthalate-series (for example, polybutylene terephthalate and polybutylene terephthalate copolyesters) of major constituent.
Thermoplastic polyester-series plastics (A) can be a crystalline or amorphous.Consider that from molding processability (workability), mechanical property and others described thermoplastic polyester-series plastics (A) is crystalline preferably.For example, as this crystalline thermoplastic polyester-series plastics, can should be mentioned that thermoplastic polyester-series plastics, it comprises the C that is not less than 60wt% at least
2-4Alkylidene aryl unit (for example, terephthalic acid C
2-4Alkylene ester unit or naphthalic acid C
2-4The alkylene ester unit).
For example, exemplary above-mentioned crystallization thermoplastic polyester-series plastics (A) of mentioning is (1) poly terephthalic acid C
2-4Alkylene ester (for example, polyethylene terephthalate) and poly-naphthalic acid C
2-4Alkylene ester (for example, PEN); (2) copolyesters, it comprises the terephthalic acid C that is not less than 60wt% (for example, about 60-98wt%)
2-4Alkylene ester unit or naphthalic acid C
2-4The alkylene ester unit; (3) polyester-series plastics composition, it contains the poly terephthalic acid C as major constituent
2-4Alkylene ester or poly-naphthalic acid C
2-4Alkylene ester (for example, 60-95wt%).
Especially, as this class crystalline polyester-series plastics, (1) polybutylene terephthalate (PBT), (2) (for example contain the unitary copolyesters of mutual-phenenyl two acid bromide two alcohol ester, contain the unitary polyalkylene terephthalates of mutual-phenenyl two acid bromide two alcohol ester of 60-98wt% or the copolyesters of poly-alkylene naphthalate), (3) containing polybutylene terephthalate is preferred as the polyester-series plastics composition of major constituent (for example, following polyester-series plastics composition: the polyalkylene terephthalates composition or the poly-alkylene naphthalate composition that contain the polybutylene terephthalate of 60-95wt%).
The number-average molecular weight of thermoplastic polyester-series plastics (A) does not limit especially and can be selected from following scope: for example, and about 0.5 * 10
4-100 * 10
4, preferably about 1 * 10
4-70 * 10
4, more preferably about 1.2 * 10
4-30 * 10
4
The concentration (amount) of the terminal carboxyl groups of thermoplastic polyester-series plastics (A) is no more than 50meq/kg (for example, about 1-40meq/kg), preferably about 2-40meq/kg, about 3-30meq/kg more preferably.In this case, when terminal carboxyl groups concentration (amount) was too big, described resin combination was easy to gelationization in melt kneading processing and other processing.
Thermoplastic polyester-series plastics (A) can prepare by common mode, for example, and transesterification, direct esterification.
[(B) phenylethylene resin series]
Phenylethylene resin series (B) comprises the homopolymerization of (1) aromatic vinyl monomer-or multipolymer, (2) aromatic vinyl monomer and at least a multipolymer that is selected from copolymerisable monomer are [for example, vinyl cyanide monomers (for example undersaturated nitrile, as vinyl cyanide etc.), the unsaturated carboxylic acid or derivatives thereof (for example, the α of olefinic, β-unsaturated monocarboxylic acid is as (methyl) vinylformic acid, the α of olefinic, the ester of β-unsaturated monocarboxylic acid is as (methyl) acrylic acid ester, the α of olefinic, the acid anhydrides of β-unsaturated monocarboxylic acid such as maleic anhydride etc.)] and rubber components and other.This quasi-styrene is that resin (B) can be by separately or be used in combination.
Exemplary copolymers (2) be aromatic vinyl monomer and copolymerisable monomer multipolymer, by aromatic vinyl monomer to the graft copolymer of the graft polymerization of rubber components preparation, by aromatic vinyl monomer and copolymerisable monomer to the graft copolymer of the graft polymerization preparation of rubber components, by aromatic vinyl monomer to the segmented copolymer of the block polymerization preparation of rubber components and other.
In addition, according to flame-retarded resin mixture of the present invention, use rubber-modified (or contain rubber or rubber enhanced) phenylethylene resin series, as being especially preferred to the graft copolymer of the graft polymerization preparation of rubber components by aromatic vinyl monomer (especially, aromatic vinyl monomer and vinyl cyanide monomers) at least.The normally amorphous class rubber polymer of the phenylethylene resin series of described modified rubber.
Rubber components comprises conjugated diene-serial rubber (polyhutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile butadiene copolymer, ethylene-propylene-5-ethylidene-2-norbornene multipolymer etc.), ethylene-propylene rubber (EPR rubber), ethylene-propylene-dience rubber (EPDM rubber), acrylic rubber, vinyl-vinyl acetate copolymer, halogenated polyolefin (as chlorinatedpolyethylene) etc., or its hydrogenated compound.Rubber components can be used alone or as a mixture.As preferred rubber components, conjugated diene-serial rubber often is used.In addition, the gel content of rubber components such as conjugated diene-serial rubber at all without limits.In addition, can prepare rubber components by the following method: letex polymerization, solution polymerization, suspension polymerization, mass polymerization, solution-mass polymerization, solution-suspension polymerization and additive method etc.
Exemplary aromatic ethenyl-series monomers is a vinylbenzene, ring-alkylated styrenes (for example, Vinyl toluene, o-, m-or p-vinyl toluene, vinyl-dimethyl benzene is as 2, the 4-dimethyl styrene, alkyl-substituted styrene such as ethyl styrene, p-isopropyl benzene ethene, butylstyrene and p-t-butylstyrene), the vinylbenzene of alpha-alkyl-replacement (for example, alpha-methyl styrene, α-ethyl styrene, Alpha-Methyl-p-vinyl toluene etc.), o-, m-or p-hydroxy styrenes, the vinylbenzene of halogen-replacement (for example, o-, m-or p-chlorostyrene, dichlorobenzene ethene, the p-bromostyrene, tribromo-benzene ethene, fluorostyrene etc.) etc.Described aromatic vinyl monomer can be by separately or be used in combination.Preferred aromatic vinyl monomer comprises vinylbenzene, Vinyl toluene, alpha-methyl styrene etc.Especially, vinylbenzene is preferred.
As vinyl cyanide monomers, can should be mentioned that vinyl cyanide, methacrylonitrile etc.Described vinyl cyanide monomers also can be by separately or be used in combination.Preferred vinyl cyanide monomers is a vinyl cyanide.
Aromatic vinyl monomer and vinyl cyanide monomers can be used in combination with other copolymerisable monomer (being called for short copolymerisable monomer later on).Described copolymerisable monomer comprises, for example, and (methyl) acrylate [for example, (methyl) acrylic acid C
1-18Alkyl ester, for example, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) vinylformic acid t-butyl ester, (methyl) Ethyl acrylate, (methyl) Octyl acrylate and (methyl) 2-EHA; (methyl) acrylate that comprises oh group is as (methyl) vinylformic acid 2-hydroxy methacrylate and (methyl) vinylformic acid 2-hydroxy propyl ester; (methyl) glycidyl acrylate etc.], [for example, unsaturated monocarboxylic acid is as (methyl) vinylformic acid and Ba Dousuan to comprise the monomer of carboxylic group; Aliphatics unsaturated dicarboxylic acid or its acid anhydrides such as maleic anhydride, toxilic acid, fumaric acid and methylene-succinic acid; The monoesters of unsaturated dicarboxylic acid is as monoesters (the toxilic acid list C of toxilic acid
1-10Alkyl ester such as toxilic acid monomethyl ester, toxilic acid list ethyl ester, toxilic acid monobutyl ester and toxilic acid single 2-ethyl polyhexamethylene), the corresponding monoesters of fumaric acid etc.] and maleimide-series monomers (for example, maleimide, N-alkyl maleimide such as N-methyl maleimide, N-phenylmaleimide etc.).Described copolymerisable monomer can be by separately or be used in combination.
In above-mentioned copolymerisable monomer, preferred copolymerisable monomer comprises (methyl) acrylate (especially methyl methacrylate), maleimide-series monomers (especially N-phenylmaleimide), (methyl) vinylformic acid, maleic anhydride etc.
With regard to aromatic vinyl monomer (especially aromatic vinyl monomer and vinyl cyanide monomers) was used at least, the ratio of aromatic vinyl monomer, vinyl cyanide monomers and copolymerisable monomer was not particularly limited.For example, aromatic vinyl monomer is about 10/90-90/10, preferably about 20/80-80/20 and more preferably about 30/70-70/30 to the ratio [(aromatic vinyl monomer)/(vinyl cyanide monomers)=] (weight ratio) of vinyl cyanide monomers.In addition, aromatic vinyl monomer is about 10/90-100/0 and about in particular 30/70-70/30 with respect to the ratio [(aromatic vinyl monomer)/(copolymerisable monomer)=] (weight ratio) of copolymerisable monomer.
Rubber components is about 10/90-75/25, preferably about 10/90-50/50 and about in particular 10/90-40/60 with respect to monomeric ratio [(the former)/(latter)=] (weight ratio) in graftomer.When described rubber components was no more than 10wt%, the shock-resistance of resin combination degenerated.In addition, when rubber components content surpasses 75wt%, probably be easy in moulded products, form flow cracks and destroy products appearance and degenerate for the affinity of thermoplastic polyester-series plastics (A).
The phenylethylene resin series of modified rubber can comprise the phenylethylene resin series of the modified rubber with above-mentioned rubber content.In addition, the rubber content of the phenylethylene resin series of modified rubber also can have the phenylethylene resin series of higher concentration rubber components by use and mixes with the phenylethylene resin series of modified rubber not and be adjusted to aforementioned proportion.In addition, the phenylethylene resin series of described modified rubber can be used alone or in combination.
The phenylethylene resin series of exemplary modified rubber is a vinylbenzene, the graft copolymer of vinyl cyanide and rubber components [for example, Acrylonitrile-Butadiene-Styrene Copolymer (ABS resin), styrene-acrylonitrile-acrylic rubber multipolymer (AAS resin), styrene-acrylonitrile-ethylene copolymer, ACS (ACS resin), styrene-acrylonitrile-EPDM (ethylene-propylene rubber) multipolymer, styrene-acrylonitrile-ethylene-propylene-ethylidene norbornene multipolymer (AES resin), styrene-acrylonitrile-vinyl-vinyl acetate copolymer etc.], styrene block copolymer [for example, styrene-butadiene-styrene (SBS) multipolymer, styrene-isoprene-phenylethene (SIS) multipolymer, styrene-ethylene-butylene-styrene multipolymer etc.], vinylbenzene-methyl methacrylate butadi ene copolymer (MBS resin) and its hydrogenation product.
The phenylethylene resin series of preferred modified rubber comprises ABS resin, styrene-acrylonitrile-ethylene copolymer, AES resin, SBS multipolymer, SIS multipolymer, styrene-ethylene-butylene-styrene multipolymer and its hydrogenation product etc.As the phenylethylene resin series of especially preferred modified rubber, can should be mentioned that ABS resin, AES resin and its hydrogenation product.
The number-average molecular weight of phenylethylene resin series (B) (under the rubber modified styrene series resin situation, matrix resin) is not specifically limited, and can be selected from following scope, for example, and about 0.5 * 10
4-200 * 10
4, preferably about 1 * 10
4-150 * 10
4, more preferably about 1 * 10
4-100 * 10
4
Can adopt usual manner to prepare phenylethylene resin series (B), for example, various polymerization processs such as solution polymerization, suspension polymerization, mass polymerization and additive method etc.
Thermoplastic polyester-series (A) can be selected from following wide scope with respect to the ratio of phenylethylene resin series (B), for example, the former/the about 30/70-95/5 of latter's (weight ratio) (for example, about 30/70-90/10).Especially, consider from the thermotolerance viewpoint, the former/latter's (weight ratio) is about 40/60-90/10, more preferably about 40/60-80/20 and 50/50-80/20 in fact.
[(C) halogenated bisphenol A-basic ring epoxy resins]
The number-average molecular weight of halogenated bisphenol A-basic ring epoxy resins (C) is no more than 8000 (for example, about 1000-8000, preferably about 2000-7000 and 3000-6000 more preferably).When the number-average molecular weight of halogenated bisphenol A-basic ring epoxy resins (C) was too big, the flowability of resin combination degenerated sometimes in molding processing, or dimensional stability degenerates sometimes.
In addition, halogenated bisphenol A-basic ring epoxy resins (C) has following structure, wherein be not less than 50% (50-100%), preferably be not less than 60% (60-100%), more preferably be not less than 70% (70-100%), in fact about 60-95% and more preferably from about the terminal epoxy groups group of 70-95% by end-blocking.When with respect to the ratio of the total terminal epoxy groups group of Resins, epoxy (end-blocking than) too hour by end capped epoxide group, the gelationization of decline of the thermostability of resin combination and generation resin combination in melt-processed (state), therefore, its viscosity increases in molding processing.In addition, can determine the end-blocking ratio by following formula (a):
End-blocking than (%)=(E0-E1)/E0 * 100 (a) wherein E0 represent epoxy group content (eq/kg) after epoxy group content (eq/kg) before the end-blocking and E1 represent end-blocking.In addition, epoxy content means the inverse of the epoxy equivalent (weight) that obtains by perchloric acid-tetraethyl ammonium bromide method.
The compound (end-capping reagent or encapsulant) that is used for end-blocking or Closed loop epoxy resins end group is not specifically limited.For example, as this compounds, can use the active hydrogen-contg compound of simple function such as monofunctional alcohol (t-butanols etc.), acid [for example, aliphatic carboxylic acid (acetate etc.) and aromatic carboxylic acid (phenylformic acid etc.)] and other.Especially, consider, preferably use phenols such as phenol, naphthols, alkylphenol (C from reactive and stability viewpoint
1-10Alkylphenol such as cresols, tert-butyl phenol), halogenated phenol (tribromophenol, Trichlorophenol etc.) etc.From the viewpoint of increase content of halogen halogenated bisphenol A-basic ring epoxy resins, exemplary especially preferred end-capping reagent or list-to five-halogenated phenols such as dibromophenol, tribromophenol, tetrabromo phenol and Trichlorophenol (especially bromophenol).
Especially, halogenated bisphenol A-basic ring epoxy resins (C) can contain the unit by general formula (1) representative:
On behalf of halogen atom and n, X refer to that mean polymerisation degree and representative are no more than 10 integer and have following structure, and wherein being not less than 50% terminal epoxy groups group can be by halogenated aryl group end capping (or sealing, protection or end-blocking), and it is represented by general formula (2):
Wherein X has the meaning same with above-mentioned definition.
Mean polymerisation degree " n " is, for example, and 1.5-12, preferably 2-10 and 2.5-8 more preferably.When mean polymerisation degree " n " was too big, the flowability of resin combination degenerated sometimes in molding processing, or dimensional stability degenerates sometimes.In addition, as halogen atom, chlorine atom and/or bromine atoms (especially bromine atoms) are used usually.
The production method of halogenated bisphenol A-basic ring epoxy resins (C) is not particularly limited and is concrete grammar, it comprises, for example, (1) comprises that the reaction of halogenated bisphenol A and Epicholorohydrin forms halogenated bisphenol A-basic ring epoxy resins, Zhi Bei Resins, epoxy and method thus as the reaction of the simple function active hydrogen-contg compound of end-blocking or encapsulant, (2) comprise that the reaction of halogenated bisphenol and Epicholorohydrin forms halogenated bisphenol A diglycidyl ether (Resins, epoxy), the method of the reaction of Zhi Bei Resins, epoxy that contains halogenated bisphenol and simple function active hydrogen-contg compound and (3) comprise that halogenated bisphenol A and Epicholorohydrin reaction form halogenated bisphenol A diglycidyl ether (Resins, epoxy) thus, Zhi Bei Resins, epoxy and halogenated bisphenol A reaction thus, so that form halogenated bisphenol A-basic ring epoxy resins, and the method for the reaction of Resins, epoxy for preparing thus further and simple function active hydrogen-contg compound.
In addition, in every kind of method of above-mentioned (1)-(3), the speed of the starting material component that the end-blocking ratio in halogenated bisphenol A-basic ring epoxy resins, its number-average molecular weight and mean polymerisation degree " n " can be by controlling every kind of use is conditioned.
The amount of the halogenated bisphenol A-basic ring epoxy resins (C) of adding is not specifically limited special amount, for example, total amount with respect to the thermoplastic polyester-series plastics (A) and the phenylethylene resin series (B) of 100 weight parts, be about 1-25 weight part (for example, about 5-25 weight part), preferably about 5-23 weight part, about 7-20 weight part more preferably.With respect to the phenylethylene resin series (B) of 100 weight parts, the amount of the halogenated bisphenol A-basic ring epoxy resins (C) of interpolation is about 5-95 weight part, preferably about 10-80 weight part and more preferably about 20-70 weight part.
In addition, the amount of the halogenated bisphenol A-basic ring epoxy resins (C) of interpolation with respect to the fire-proof resin composition of 100 weight parts is, for example, and about 1-30 weight part, preferably about 3-20 weight part and more preferably about 5-15 weight part.When the amount of the halogenated bisphenol A-basic ring epoxy resins (C) of adding during in above-mentioned scope, flame retardant resistance, the intensity mobile and resistant to gelling in the resin combination melt kneading and moulded products in molding processing become excellent.
[(D) antimony containing compounds]
Antimony containing compounds (D) is not specifically limited special compound.For example, as antimony containing compounds (D), weisspiessglanz compound (ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide etc.), stibnate (metal-salt of metaantimmonic acid such as sodium antimonate, metaantimmonic acid magnesium, ammonium antimonate etc.) can be used.Especially, using ANTIMONY TRIOXIDE SB 203 99.8 PCT is preferred as fire-retardant secondary additive.
The amount of the antimony containing compounds (D) that adds with respect to the thermoplastic polyester-series plastics (A) of 100 weight parts and the total amount of phenylethylene resin series (B) is, for example, about 1-15 weight part, preferably about 3-15 weight part is (for example, about 3-10 weight part) and more preferably about 5-15 weight part (for example, about 7-15 weight part).The amount of the antimony containing compounds (D) that adds with respect to the phenylethylene resin series (B) of 100 weight parts is, for example, and about 5-50 weight part, preferably about 10-45 weight part and more preferably about 15-45 weight part.
In addition, the amount of the antimony containing compounds of interpolation (D) with respect to the total amount of the fire-proof resin composition of 100 weight parts is, for example, and about 1-15 weight part and preferably about 3-10 weight part (for example, about 5-8 weight part).
[(E) mineral filler]
According to fire-proof resin composition of the present invention, the interpolation of mineral filler (E) realizes high heat resistance (heat-resistant deforming).For example, the heat-drawn wire of measuring according to ASTM D-648 is not less than 100 ℃ (for example, about 100-250 ℃, preferably about 150-220 ℃ and more preferably about 160-210 ℃).
Mineral filler (E) can be used for any purpose [for example, bat wool, granular (powder) filler or sheet (or flat) filler] with various forms or shape.
Bat wool comprises, for example, inorganic fibre such as glass fibre, silica/alumina fiber, Zirconium oxide fibre, fibrous magnesium silicate, carbon fiber, silica fiber, potassium titanate fiber, boron nitride fiber and other steel fiber (fibrous matters of metal such as stainless steel, aluminium, titanium, copper, brass etc.) and other.Common fibrous packing is glass fibre or carbon fiber.In addition, also can use and have dystectic organic fibre (for example, aliphatics or aromatic polyamide, aromatic polyester, fluorine resin and acrylic resin such as polyacrylonitrile).
In addition, the fiber diameter of fibrous packing is, for example, and about 0.1-10 μ m, the more preferably about 0.1-3 μ of about 0.1-5 μ m m preferably.The length-to-diameter ratio of fibrous packing is about 2-1000, preferably about 3-500 and more preferably about 5-300.
Exemplary particulate filler is various powder, for example, and metal oxide such as silicon-dioxide, powder quartz, ferric oxide, titanium oxide, zinc oxide and aluminum oxide; Silicate such as granulated glass sphere, powder glass, milled glass fibre, Calucium Silicate powder, pure aluminium silicate, kaolin, talcum, clay, diatomite, wollastonite; The metal-salt of carbonic acid (metal carbonate) is as lime carbonate and magnesiumcarbonate; The vitriol of metal (metal sulfate) is as calcium sulfate and barium sulfate; Silicon carbide and other.
In addition, the average particle diameter of particulate filler (size) is, for example, and about 0.1-10 μ m, the more preferably about 0.1-3 μ of about 0.1-5 μ m m preferably.
Described sheet (flat) filler comprises, for example, and mica, sheet glass, various sheet metal and other.
Above-mentioned mineral filler can be used alone or as a mixture.In addition, for the mechanical property (for example, physical strength) and the rigidity that improve fire-proof resin composition of the present invention, it is preferred using the fibrous packing at least in the above-mentioned mineral filler.In addition, using sheet glass, powder mica, talcum, granulated glass sphere, milled glass fibre etc. is preferred as non--fiber mineral filler.In addition, mix use with granular and/or sheet (or flat) filler, can prepare and have size accuracy (or precision) and stable on heating goods by fibrous packing (especially glass fibre).
In addition, when using mineral filler, can randomly be used in combination tackiness agent or surface treatment agent.This class tackiness agent or surface treatment agent comprise functional compound, for example, and epoxy-series compound, vinylformic acid-series compound, isocyanic ester-series compound, silane-series compound, titanic acid ester-series compound.
Under mineral filler and situation that tackiness agent or surface treatment agent are used in combination, mineral filler can be with functional compound surface-treated or gluing processing in advance, or mineral filler is added in the preparation of resin combination with functional compound.
The amount of the mineral filler of adding (E) is not specifically limited special amount.Under the situation that the mineral filler of huge amount is added, own product surface inorganic filler is separated out with products appearance and is degenerated.In addition, under the too little situation of the amount of the mineral filler of adding, thermotolerance and size accuracy (or precision) are subjected to harmful effect and can not obtain enough (fully) physical strength and rigidity.Therefore, the amount of the mineral filler of adding (E) is, for example, with respect to the about 1-100 weight part of total amount of the thermoplastic polyester-series plastics (A) of 100 weight parts and phenylethylene resin series (B) (for example, about 1-60 weight part), preferably about 5-50 weight part (for example, 10-50 weight part) and more preferably about 10-30 weight part.The amount of the mineral filler of adding (E) is, for example, and with respect to the about 10-100 weight part of phenylethylene resin series (B) of 100 weight parts, preferably about 20-90 weight part and more preferably about 30-80 weight part.
In addition, total amount with respect to thermoplastic polyester-series plastics (A), phenylethylene resin series (B), halogenated bisphenol A-basic ring epoxy resins (C) and the antimony containing compounds (D) of 100 weight parts, the amount of the mineral filler of adding (E) is, for example, about 1-60 weight part, preferably about 5-50 weight part (for example, about 10-50 weight part) and more preferably about 10-30 weight part.
In addition, under tackiness agent or surface treatment agent and situation that mineral filler (E) is used in combination, with respect to the mineral filler (E) of 100 weight parts, the tackiness agent of interpolation or the amount of surface treatment agent are no more than 10 weight parts (for example, about 0.01-10 weight part) and preferably about 0.05-5 weight part.
[(F) aliphatics monocarboxylic acid component]
As the aliphatics monocarboxylic acid, can should be mentioned that the aliphatics monocarboxylic acid such as carnaubic acid, cerinic acid, carboceric acid, montanic acid, nonacosanoic acid, myricyl acid, lacceroic acid and the geddic acid that contain 24 or more (for example, 24-40 carbon atom) carbon atom.
In addition, the monocarboxylic ester of aliphatics comprises ester [for example, the C that contains polyhydroxy-alcohol
2-10Aklylene glycol such as ethylene glycol, trimethylene glycol, propylene glycol, 1,3 butylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol and neopentyl glycol; C
2-10Alkane polyol such as glycerine, trimethylolethane (TME), TriMethylolPropane(TMP) (TMP) and tetramethylolmethane; (many) oxygen base C
2-4Aklylene glycol such as Diethylene Glycol and dipropylene glycol] or MHA is (for example, contain 1-18 the carbon atom of having an appointment, the alkyl alcohol of about 2-10 carbon atom preferably, for example, methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, octanol, decyl alcohol, lauryl alcohol and stearyl alcohol).
In addition, as the monocarboxylic metal-salt of aliphatics, can should be mentioned that the salt of basic metal such as sodium and potassium; The salt of alkaline-earth metal such as calcium and magnesium, the metal that belongs to periodic table of elements 2B family such as the salt of zinc; The metallic element of periodic table of elements 3B family such as the salt of aluminium and other salt.
Above-mentioned aliphatics monocarboxylic acid, its ester and its metal-salt can be used alone or as a mixture.
Exemplary preferred aliphatics monocarboxylic acid component (F) is for example, to contain aliphatics monocarboxylic acid, aliphatics monocarboxylic acid and the C of the individual carbon atom of 26-34 (for example 26-30) (especially 28-34)
2-6Alkane polyol, (gathering) oxygen base C
2-4Aklylene glycol or C
2-6The salt of the ester of alkyl alcohol and aliphatics monocarboxylic acid and above-mentioned metal.Industrial, it is preferred using following material: the ester of montanic acid, montanic acid and polyhydroxy-alcohol (for example, glycol ester, macrogol ester, propylene glycol ester, butanediol ester, glyceryl ester, pentaerythritol ester etc.), the ester (for example, methyl alcohol ester, propyl alcohol ester, bay alcohol ester, stearic alcohol ester etc.) of montanic acid and monohydroxy-alcohol and its partly-hydrolysed ester etc.Especially, it is preferred using the montanic acid and the ester of polyhydroxy-alcohol such as the glycol ester of montanic acid and the glyceryl ester of montanic acid.
In addition, the aliphatics monocarboxylic acid of formation aliphatics monocarboxylic acid component can be that independent compound maybe can comprise the aliphatics monocarboxylic acid that multiple carbon number differs from one another.For example, in aliphatics monocarboxylic acid component, the aliphatics monocarboxylic acid can only comprise that montanic acid maybe can comprise the montanic acid and the C that is different from montanic acid as main ingredient
24-36The aliphatics monocarboxylic acid.
For example, the fusing point of aliphatics monocarboxylic acid component is about 75-100 ℃, preferably about 80-98 ℃ and more preferably about 80-95 ℃.
The amount (ratio) of described aliphatic carboxylic acid component (F) is, for example, total amount with respect to the thermoplastic polyester-series plastics (A) and the phenylethylene resin series (B) of 100 weight parts, about 0.05-15 weight part, preferably about 0.1-10 weight part is (for example, 0.5-5 weight part) and more preferably about 0.5-5 weight part (for example, about 1-3 weight part).With respect to the phenylethylene resin series (B) of 100 weight parts, the amount (ratio) of aliphatics monocarboxylic acid component (F) is about 0.1-20 weight part, preferably about 0.5-10 weight part and more preferably about 2-8 weight part.
In addition, for example, with respect to the total amount of thermoplastic polyester-series plastics (A), phenylethylene resin series (B), halogenated bisphenol A-basic ring epoxy resins (C) and the mineral filler (D) of 100 weight parts, the amount (ratio) of aliphatics monocarboxylic acid component (F) is about 0.1-5 weight part, preferably about 0.3-3 weight part and more preferably about 0.5-2 weight part.Under the too little situation of the ratio of aliphatics monocarboxylic acid component (F), mould-pollution-free performance and mould-detachment can not obtain enough improvement.On the other hand, described ratio is too big, because it is contaminated to ooze out the mould that with other reason the outward appearance of goods is degenerated or use.
Fire-proof resin composition of the present invention can randomly add various conventional additives [for example, stablizer such as oxidation inhibitor, UV light absorber and weather-proof (light) stablizer; Static inhibitor; Lubricant; Tinting material such as dyestuff and pigment; Softening agent].Especially, by lubricant is joined in the fire-proof resin composition of the present invention, the parent material feeding smoothness in molding step such as extrusion molding is improved.In addition, the interpolation of oxidation inhibitor provides and shows high thermal stability (especially long-term thermal stability) and than the moulded products of high-mechanical property.As this kind antioxidant, hindered phenol-series compound, amine-series compound, thioether-series compound etc. can be used.
Hindered phenol-series compound comprises, for example, and C
2-4Alkane diol-two [3-(3, the C of 5-two-side chain
3-6Alkyl-4-hydroxy phenyl) propionic ester] as 1, two [3-(3, the 5-two-t-butyl-4-hydroxy phenyl) propionic esters of 6-hexylene glycol; Two-or three-oxygen base C
2-4Alkane diol-two [3-(3, the C of 5-two-side chain
3-6Alkyl-4-hydroxy phenyl) propionic ester] as triethylene glycol-two [3-(3-t-butyl-5-methyl-4-hydroxy phenyl) propionic esters; C
3-8Alkane triol-two [3-(3, the C of 5-two-side chain
3-6Alkyl-4-hydroxy phenyl) propionic ester] as glycerine three [3-(3,5-two-t-butyl-4-hydroxy phenyl) propionic ester]; C
4-8Alkane tetrol-four [3-(3, the C of 5-two-side chain
3-6Alkyl-4-hydroxy phenyl) propionic ester] as tetramethylolmethane four [3-(3,5-two-t-butyl-4-hydroxy phenyl) propionic ester].
In addition, exemplary amine-series compound is N-phenyl-N '-sec.-propyl-p-phenylenediamine, N, N '-phenylbenzene-p-phenylenediamine, 4,4-pair-(4-α, α-Er Jiajibianji) condensation reaction prod of diphenylamine, pentanoic and acetone, N-phenyl naphthyl amines, N, N '-two-betanaphthyl phenylenediamine etc.
In addition, as thioether-series compound, can should be mentioned that dilauryl thiodipropionate, myristyl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, four [methylene radical-3-(dodecyl sulfo-) propionic ester] methane, two C
12-18Alkyl-3,3-thiodipropionate etc.
In addition, preferred oxidation inhibitor comprises hindered phenol-series compound, for example, and tetramethylolmethane four [3-(3,5-two-t-butyl-4-hydroxy phenyl) propionic ester], triethylene glycol-two [3-(3-t-butyl-5-methyl-4-hydroxy phenyl) propionic ester etc.
In addition, give comprise fire-proof resin composition of the present invention moulded products than high flame retardant (for example, be categorized as by being used for those of " V-0 " that flammable UL standard No.94 measures) time, asbestos or fluorine resin [for example, granular or (powdery) fluorine resin] as the drippage inhibitor can mix use with described resin combination.Described fluorine resin comprises the homopolymerization of fluorochemical monomer-or multipolymer, and described fluorochemical monomer for example is tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, R 1216, perfluoroalkyl vinyl ether etc.; The multipolymer of fluorochemical monomer and copolymerisable monomer such as ethene, propylene, (methyl) acrylate etc.
As this class fluorine resin, for example, can should be mentioned that homopolymer such as tetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene difluoride (PVDF) etc.; Multipolymer such as tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoro-ethylene copolymer etc.Described fluorine resin can be used alone or as a mixture.
The amount of described drippage inhibitor (ratio) is, for example, is the thermoplastic polyester-series plastics (A) and the phenylethylene resin series (B) of 100 weight parts with respect to total amount, about 0.5-5 weight part, preferably about 0.7-4 weight part and more preferably about 1-3 weight part.
Fire-proof resin composition of the present invention can be granular (or powdery) mixture or molten mixture.Described fire-proof resin composition can easily or simply prepare by the formation component of blended resin composition and optional additive etc., and it is that (blending means for example, is done and mixed by conventional methods; Melting mixing as melt extrude, melt kneading etc.) carry out.The preparation of this class fire-proof resin composition can use conventional equipment easily or simply to carry out.In addition, join in other component by constituting component as the part of the resin combination of fine powder, described formation component can be mixed equably or in heterogeneity.
For example, as the method that is used for production fire-proof resin composition of the present invention, can should be mentioned that: (1) comprises following method: the component that will constitute resin combination according to predetermined proportion mixes respectively, mixture with single shaft or biaxial extruder melt kneading obtain has the pellet that target is formed to provide; Or (2) comprise following method: first venting port of resin, stablizer, pigment etc. being put into single shaft or biaxial extruder, described forcing machine contains a plurality of raw-material venting ports that are used to throw in, with the mixture melt kneading that obtains, then the mineral filler input is used to throw in raw-material second venting port of following, the mixture that obtains with melt kneading is to provide the pellet with predetermined composition.In addition, fire-proof resin composition of the present invention can be powdered, granulous, flaky etc. except that pellet.
Moulded products of the present invention can use described resin combination preparation [be fire-proof resin composition, it comprises described thermoplastic polyester-series plastics (A), described phenylethylene resin series (B), described halogenated bisphenol A-basic ring epoxy resins (C), described antimony containing compounds (D) and described aliphatics monocarboxylic acid component (F)].This class moulded products can easily or simply be produced, and it is by the described fire-proof resin composition of melt kneading, carries out molding with the method for routine such as extrusion molding, injection-molded, blow moulded, compression moulding etc. then.In addition, the molding methods that is used to produce moulded products of the present invention is not specifically limited special methods.Preferred molding methods is injection-molded.
For example, the method as being used for moulding (or molding) moulded products of the present invention can should be mentioned that: (1) comprises the pellet that uses method for preparing to have predetermined composition, uses the method for pellet moulding (or molding) moulded products then; (2) comprise that different pellets is formed in preparation each other respectively, these pellet predetermined amounts are mixed, so that moulding (or molding) comprises the method for moulded products of the resin combination of predetermined composition, (3) comprise every kind of direct feed of component or be fed in moulding (or molding) machine, with the method for moulding (or molding) moulded products.
Because moulded products of the present invention is with described fire-proof resin composition manufacturing (or moulding), therefore, its flame retardant resistance and thermotolerance (especially heat-resistant deforming) are excellent, wherein heat-drawn wire is measured in 1.82MPa load according to ASTM D-648, is not less than 100 ℃ (for example 100-250 ℃).In addition, the dimensional stability of moulded products of the present invention is excellent.In addition, moulded products of the present invention has excellent mouldability, the especially long-pending attached formation (mould-pollution-free performance) of reduction mould in injection-molded, and mould-detachment.Therefore, can and produce this based article continuously or constantly in high speed, as a result of, its production cycle can shorten, thereby improves productive rate.
Moulded products of the present invention can be used for the packing, shell, parts of various uses such as electronics etc., and it for example needs performances such as flame retardant resistance.Moulded products can be used as vehicle chassis component or element, especially the vehicle chassis component of disc driver or element, as floppy disk (flexible disk driving mechanism) (FDD), hard disk drive (HDD), CD (CD) driving mechanism, miniature hdd (MD) driving mechanism, a CD-reading memory (CD-ROM) driving mechanism, magneto optical driver (MODD), digital versatile disc (DVD) driving mechanism etc., and other application.
According to fire-proof resin composition of the present invention, the combination of said components (A)-(F) can improve molding processability (workability), especially in injection-molded, reduce the long-pending attached formation (improving mould-pollution-free performance) of mould and improve mould-detachment, even when resin combination comprises fire retardant.In addition, this resin combination has excellent size stability, thermotolerance and flame retardant resistance and excellent flowability in Mould Machining.
Embodiment
Embodiment
Following embodiment is in order to describing the present invention in more detail, but should not be construed as the definition to the scope of the invention.
In addition, in embodiment and Comparative Examples assessment item and evaluation method according to the following stated.
(1) dimensional stability (buckling deformation degree)
According to the shape of the mould that uses, prepare plate tensile sample (80mm length * 80mm wide * 2mm is thick) by injection molding machine in following condition.Use
Three-dimensional test equipment microcode A121(Mitsutoyo Corp. manufacturing) measures the buckling deformation degree for preparing sample thus.
(condition of moulding)
Injection molding machine: J75SA (Japan Steel Works, Ltd. makes)
Square and the thick tabular mould of 2mm of mould (metal die): 80mm
Die temperature: 65 ℃
Barrel temperature: 250 ℃
Injection speed: 2m/min
Injection pressure: 69MPa
(2) flammability test (UL-94)
According to the Subject 94 of Underwriters Laboratories (UL-94), described resin combination incendiary is flammable to use 5 test specimens (thickness 0.8mm) to test with the drippage feature, so that determine its flammable rank.
(3) be bonded at the amount of the gel eliminate indigestion addendum on the screw rod
Use Toyo Seiki Seisaku-sho, Ltd. makes
The ME-25 type The laboplastmill forcing machine(wherein D20-28 type single shaft forcing machine is used as measuring head), the resin combination pellet that will have following composition passes through extrusion molding under 275 ℃ of barrel temperatures, extrude 30 minutes with the extrusion capacity of 1kg/h.Then, screw rod slowed down 1 hour, and extrusion molding is extruded 30 minutes again with the extrusion capacity of 1kg/h.After this, product is cleaned with polyethylene, detecting by an unaided eye is bonded at the long-pending attached amount of screw surface, and wherein resin combination is by gelationization.Be bonded at the long-pending attached amount of gel of screw surface according to following judgement criteria evaluation.
(judgement criteria)
" A ": long-pending not attached
" B ": find a small amount of long-pending attached
" C ": find long-pending attached
" D ": find a large amount of long-pending attached
(4) melt viscosity (MV)
Use Toyo Seiki Seisaku-sho, Ltd. makes
Chapirograph 1B Capillary rheometerMeasure barrel temperature being 250 ℃ is 1216s with shearing rate
-1The melt viscosity of the resin combination under the condition (Pa.s).
(5) heat
DistortionTemperature (HDT)
According to ASTM D-648 and use sample (6.4mm is thick), use HDT ﹠amp; V.S.P.T tester (Toyo Seiki Seisaku-sho, Ltd. makes) is measured heat-drawn wire under the 1.82MPa load-up condition.
(6) mould-pollution-free performance
(amount of the long-pending addendum that on mould, forms)
Use injection molding machine according to following condition moulding or molding (2000 injections) sample continuously or constantly, measure (pollution level on mould) in long-pending attached (pollution) on the mould after estimating continuous or lasting molding then with mold shape.The pollution on mould behind the continuous or lasting molding that detects by an unaided eye, and according to following standard evaluation mould-pollution-free performance.
(condition of moulding)
Injection molding machine: IS30FPA (by Toshiba Machine Co., Ltd. makes)
Mould: the dish that 20mm diameter and 1mm are thick
Barrel temperature: 260 ℃
Injection speed: 2m/min
Dwell pressure: 69Mpa
Die temperature: 40 ℃
(judgement criteria)
" A ": find negligible long-pending attached amount
" B ": discovery is long-pending attached, based on area, and about 25% die surface
" C ": discovery is long-pending attached, based on area, and about 50% die surface
" D ": discovery is long-pending attached, based on area, and about 75% die surface
" E ": find a large amount of long-pending attached on the entire die surface
(7) molding cycle
Use injection moulding machine preparation under the following condition of moulding 15mm length * 20mm wide * have outstanding T-type (T-type) sample on the part of the sheet material that 2mm is thick, measure then and can remove sample and do not rupture or destructive the shortest molding cycle from mould.
(condition of moulding)
Injection molding machine: IS30FP (by Toshiba Machine Co., Ltd. makes)
Barrel temperature: 250 ℃
Injection speed: 2m/min
Dwell pressure: 73MPa
Die temperature: 60 ℃
In embodiment and Comparative Examples, use following component.
(A) thermoplastic polyester-series plastics
Polybutylene terephthalate (PBT) resin: by Polyplastics Co., Ltd. makes, IV (limiting viscosity)=0.75
(B) phenylethylene resin series
Styrene butadiene-acrylonitrile copolymer (ABS resin): by Daicel ChemicalIndustries, Ltd. makes, DP-611
(C1) halogenated bisphenol A-basic ring epoxy resins
(C1-1) by Dainippon Ink and Chemicals, Inc. makes, and ECX-30 (number-average molecular weight: about 3000, end-blocking ratio: about 80%)
(C1-2) Sakamoto Yakuhin Kogyo Co., Ltd. make, and SR-T3040 (number-average molecular weight: about 6000, end-blocking ratio: about 90%)
(C2) other halogenated bisphenol A-basic ring epoxy resins
(C2-1) by Dainippon Ink and Chemicals, Inc. makes, and EC-200 (number-average molecular weight: about 16000, end-blocking ratio: about 75%)
(C2-2) Sakamoto Yakuhin Kogyo Co., Ltd. make, and SR-T5000 (number-average molecular weight: about 10000, end-blocking ratio: about 0%)
(D) antimony containing compounds
ANTIMONY TRIOXIDE SB 203 99.8 PCT: by Nihon Seiko Co., Ltd. makes, PATOX M
(E) mineral filler
(E-1) glass fibre: by Nippon Electric Glass Co., Ltd. makes, ECS03T187
(E-2) sheet glass: by Nippon Glass Fiber Co., Ltd. makes, REFG-101
(F1) aliphatics monocarboxylic acid component
Montanate (ethylene glycol bisthioglycolate montanate): by Toyo-Petrolite Co., Ltd. makes, LUZAWAX EP
(F2) other carboxyl acid component
(F2-1) sorbitan three mountain acid esters: by Riken Vitamin Co., Ltd. makes, RIKEMAL B-150
(F2-2) pentaerythritol tetrastearate: make by NOF Corp.,
UNISTARH476
(G) fluorine resin
Tetrafluoroethylene: by
Hoechst AG HOSTAFLONMake TF1620
Embodiment 1-5 and Comparative Examples 1-8
Every kind of component of foregoing description is in the same place according to table 1 and 2 mixed, with biaxial extruder with the product mixtures melt kneading so that the preparation pellet form resin combination.Then, use the pellet that makes by injection-molded preparation sample, and according to above-mentioned every assess performance.Result such as table 1 and 2.
Table 1
Embodiment forms (C1-1) Mn=3000 12 12 12 8 of % (weight) 1234 5PBT resins (A) 32 45 32 32 35ABS resin (B) 32 19 32 32 35 Resins, epoxy (C1)
(C1-2) (C2-1) Mn=1600 of Mn=6000 12 Resins, epoxy (C2)
(C2-2) Mn=10000 ANTIMONY TRIOXIDE SB 203 99.8 PCT (D) 7.5 7.5 7.5 7.5 6 mineral fillers (E) (E-1) 15 15 10 15 15
(E-2) 5 aliphatics monocarboxylic acid components (F1), 11111 other carboxyl acid component (F2) (F2-1)
(F2-2) fluorine resin (G) 0.5 0.5 0.5 0.5 performance buckling deformation degree (mm) 23131 combustibility (UL94 grade) V-0 V-0 V-0 V-0 V-2 gel eliminate indigestion attached amount A A A A AMV (Pas) 150 145 145 170 110HDT (℃) 109 110 108 109 120 moulds-pollution-free performance A A A A A moulding cyclc (second) 77777
Table 2
Comparative Examples forms (C1-1) Mn=3000 12 12 12 12 20 of % (weight) 1234567 8PBT resins (A) 32 32 64 32 32 32.5 42 34ABS resins (B) 32 32 32 32 32.5 42 34 ring hydrogen resins (C1)
(C1-2) (C2-1) Mn=1600 12 of Mn=6000 Resins, epoxy (C2)
(C2-2) Mn=10000 12 ANTIMONY TRIOXIDE SB 203 99.8 PCT (D) 7.5 7.5 7.5 7.5 7.5 7.5 10.5 mineral fillers (E) (E-1) 15 15 15 15 15 15 15
(E-2) aliphatics monocarboxylic acid component (F1) 11111 other carboxyl acid component (F2) (F2-1) 1
(F2-2) 1 fluorine resin, (G) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 performance buckling deformation degree, (mm) 77 15 2223 0.5 combustibility, the attached amount C D of (UL94 grade) V-0 V-0 V-0 V-0 V-0 V-0 HB V-0 gel eliminate indigestion A A A A A AMV, (Pas) 225 220 140 149 148 143 130 90HDT, (℃) 111 110 200 109 109 110 112 85 moulds-pollution-free performance A A A D D E A A
60 or molding cycle (second) 775 20 30 77
More than
Claims (14)
1. fire-proof resin composition, it comprises:
(A) thermoplastic polyester-series plastics,
(B) phenylethylene resin series,
(C) halogenated bisphenol A-basic ring epoxy resins wherein is not less than 50% terminal epoxy groups group and is no more than 8000 by end-blocking and number-average molecular weight,
(D) antimony containing compounds,
(E) mineral filler and
(F) at least a aliphatics monocarboxylic acid component, it is selected from has aliphatics monocarboxylic acid, its ester and its metal-salt that is no less than 24 carbon atoms.
2. the fire-proof resin composition of claim 1, wherein (A) described thermoplastic polyester-series plastics comprises crystalline polyester-series plastics.
3. the fire-proof resin composition of claim 1, wherein (A) described thermoplastic polyester-series plastics comprises polyalkylene arylide-series plastics, and this resin contains at least a terephthalic acid alkylene ester unit and the unitary unit of alkylene naphthalate of being selected from.
4. the fire-proof resin composition of claim 1, wherein (A) described thermoplastic polyester-series plastics comprises (1) polybutylene terephthalate, (2) copolyesters, it contains the mutual-phenenyl two acid bromide two alcohol ester unit that is no less than 60wt%, or (3) polyester-series plastics composition, it comprises that polybutylene terephthalate is as main ingredient.
5. the fire-proof resin composition of claim 1, wherein (B) described phenylethylene resin series comprises the phenylethylene resin series of modified rubber.
6. the fire-proof resin composition of claim 1, wherein (B) described phenylethylene resin series comprises graft copolymer, wherein at least a aromatic vinyl monomer and vinyl cyanide monomers are grafted on the rubber components.
7. the fire-proof resin composition of claim 1, wherein (C) described halogenated bisphenol A-basic ring epoxy resins contains the unit of following general formula (1) expression:
Wherein x represents halogen atom, and n representative is no more than 10 integer, wherein is not less than 50% terminal epoxy groups group by the halogenated aryl group end capping.
8. the fire-proof resin composition of claim 1, wherein (D) described antimony containing compounds comprises weisspiessglanz.
9. the fire-proof resin composition of claim 1, wherein (E) described mineral filler comprises at least a glass fibre, sheet glass, talcum and the micaceous material of being selected from.
10. the fire-proof resin composition of claim 1, wherein in described component (F), the aliphatics monocarboxylic acid comprises the aliphatics monocarboxylic acid that contains 26-34 carbon atom.
11. the fire-proof resin composition of claim 10, wherein said component (F) comprises aliphatics C
26-34The ester of monocarboxylic acid and polyhydroxy-alcohol.
12. the fire-proof resin composition of claim 1, comprising, with respect to total amount is (A) described thermoplastic polyester-series plastics of 100 weight parts and (B) phenylethylene resin series of described modified rubber, (C) described halogenated bisphenol A-basic ring epoxy resins of 1-25 weight part, (D) described antimony containing compounds of 1-15 weight part, (E) described mineral filler of 1-60 weight part and (F) montanate of 0.1-5 weight part, wherein (A) described thermoplastic polyester-series plastics is the former (A)/latter (B) (weight ratio)=30/70-95/5 with respect to the ratio of (B) described rubber modified styrene series resin.
13. moulded products with the fire-proof resin composition moulding of claim 1.
14. the moulded products of claim 12, it is a vehicle chassis component.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP210521/01 | 2001-07-11 | ||
| JP210521/2001 | 2001-07-11 | ||
| JP2001210521A JP4173653B2 (en) | 2001-07-11 | 2001-07-11 | Flame retardant resin composition and molded product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1396207A true CN1396207A (en) | 2003-02-12 |
| CN1264919C CN1264919C (en) | 2006-07-19 |
Family
ID=19045979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02140952 Expired - Fee Related CN1264919C (en) | 2001-07-11 | 2002-07-11 | Flame-retarded resin composition and its forming product |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4173653B2 (en) |
| CN (1) | CN1264919C (en) |
| MY (1) | MY136537A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101223237A (en) * | 2005-07-13 | 2008-07-16 | 巴斯福股份公司 | Flowable thermoplastic material containing halogen flameproffing agents |
| CN100410321C (en) * | 2004-03-12 | 2008-08-13 | 胜技高分子株式会社 | Polyester resin composition |
| WO2010043085A1 (en) * | 2008-10-17 | 2010-04-22 | 金发科技股份有限公司 | Flame retarding thermoplastic alloy and its preparation method |
| CN101007894B (en) * | 2006-01-23 | 2011-07-27 | 上海锦湖日丽塑料有限公司 | PBT and ABS flame-proof material |
| CN101724219B (en) * | 2008-10-17 | 2011-11-16 | 金发科技股份有限公司 | Thermoplastic flame-retardant alloy and preparation method thereof |
| TWI701290B (en) * | 2015-10-30 | 2020-08-11 | 日商東麗股份有限公司 | Thermoplastic polyester resin composition and molded products |
| CN114174426A (en) * | 2019-07-31 | 2022-03-11 | 宝理塑料株式会社 | Flame-retardant polybutylene terephthalate resin composition |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1940930A1 (en) * | 2005-09-12 | 2008-07-09 | Looi Wan Bew @ Loo on Bew | A process to convert thermoset plastic into recyclable and reusable plastic |
| CN102617971A (en) * | 2011-12-09 | 2012-08-01 | 上海锦湖日丽塑料有限公司 | Flame-retardant ABS (acrylonitrile-butadiene-styrene) resin with high weatherability |
| EP3766937B1 (en) | 2016-05-19 | 2022-07-13 | Mitsubishi Engineering-Plastics Corporation | Polybutylene terephthalate resin composition and molded article |
| JP6828745B2 (en) * | 2017-05-24 | 2021-02-10 | 三菱ケミカル株式会社 | Manufacturing method of sheet molding compound, fiber reinforced composite material and fiber reinforced composite material |
-
2001
- 2001-07-11 JP JP2001210521A patent/JP4173653B2/en not_active Expired - Fee Related
-
2002
- 2002-06-28 MY MYPI20022471 patent/MY136537A/en unknown
- 2002-07-11 CN CN 02140952 patent/CN1264919C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100410321C (en) * | 2004-03-12 | 2008-08-13 | 胜技高分子株式会社 | Polyester resin composition |
| CN101223237A (en) * | 2005-07-13 | 2008-07-16 | 巴斯福股份公司 | Flowable thermoplastic material containing halogen flameproffing agents |
| CN101223237B (en) * | 2005-07-13 | 2011-10-12 | 巴斯福股份公司 | Flowable thermoplastic material containing halogen flameproffing agents |
| CN101007894B (en) * | 2006-01-23 | 2011-07-27 | 上海锦湖日丽塑料有限公司 | PBT and ABS flame-proof material |
| WO2010043085A1 (en) * | 2008-10-17 | 2010-04-22 | 金发科技股份有限公司 | Flame retarding thermoplastic alloy and its preparation method |
| CN101724219B (en) * | 2008-10-17 | 2011-11-16 | 金发科技股份有限公司 | Thermoplastic flame-retardant alloy and preparation method thereof |
| US8486313B2 (en) | 2008-10-17 | 2013-07-16 | Kingfa Science & Technology Co., Ltd | Flame retarding thermoplastic alloy and its preparation method |
| TWI701290B (en) * | 2015-10-30 | 2020-08-11 | 日商東麗股份有限公司 | Thermoplastic polyester resin composition and molded products |
| CN114174426A (en) * | 2019-07-31 | 2022-03-11 | 宝理塑料株式会社 | Flame-retardant polybutylene terephthalate resin composition |
| CN114174426B (en) * | 2019-07-31 | 2023-08-11 | 宝理塑料株式会社 | Flame retardant polybutylene terephthalate resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| MY136537A (en) | 2008-10-31 |
| JP4173653B2 (en) | 2008-10-29 |
| JP2003026904A (en) | 2003-01-29 |
| CN1264919C (en) | 2006-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1077586C (en) | Flame-retardant resin composition | |
| CN1225504C (en) | Flame retardant resin composition | |
| CN1590458A (en) | Thermoplastic resin composition and shaped article | |
| EP2088168B1 (en) | High flow polyester composition | |
| CN100343324C (en) | Conductive thermoplastics with carbon black and carbon nanofibrils | |
| CN1142217C (en) | Flame-retardant polycarbonate resin composition with excellent melt flowability | |
| CN1146630C (en) | Flame resistant polycarbonate/ABS plastic molding materials | |
| CN1146641C (en) | Flame-resistant polycarbonate-ABS moulding material | |
| CN1097616C (en) | Thermoplastic resin composition and method of producing the same | |
| CN1168764C (en) | Flame resistant reinforced polycarbonate ABS moulding materials | |
| CN1408008A (en) | Flame-resistant polycarbonate moulding compounds | |
| CN1264919C (en) | Flame-retarded resin composition and its forming product | |
| CN1221441A (en) | Flame retardant thermo plastic resin composition | |
| CN1685011A (en) | Flame-resistant polycarbonate moulding materials | |
| CN1914279A (en) | Flame resistant thermoplastic resin composition | |
| CN1489618A (en) | Flame-retardant polycarbonate compositions, which are reinforced with minerals and having high seam resistance | |
| CN101040004A (en) | Resin composition | |
| CN1930243A (en) | Polycarbonate resin composition and molded article thereof | |
| CN1234758C (en) | Flame retardant resin compositon and molded products thereof | |
| CN1653133A (en) | Impact-modified polycarbonate compositions with calcined talc | |
| CN1347431A (en) | Flame-resistant, impact-resistant modified polycarbonate molding and extrusion masses | |
| CN1803908A (en) | Polypropylene plastic and preparation process thereof | |
| CN1198877C (en) | Polycarbonate molding compounds containing a special talc | |
| JP5108230B2 (en) | Electrical and electronic parts made of aromatic polycarbonate resin composition | |
| CN1636035A (en) | Impact resistant modified blends made of polyethylenterephthalate and at least one polycarbonate based on dihydroxydiarylcyclohexane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060719 Termination date: 20130711 |