CN1497014A - Polyester type resin composition - Google Patents
Polyester type resin composition Download PDFInfo
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- CN1497014A CN1497014A CNA2003101010229A CN200310101022A CN1497014A CN 1497014 A CN1497014 A CN 1497014A CN A2003101010229 A CNA2003101010229 A CN A2003101010229A CN 200310101022 A CN200310101022 A CN 200310101022A CN 1497014 A CN1497014 A CN 1497014A
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Abstract
Provided is a polyester-based resin composition not only having high flame retardancy and antistatic properties but also inhibiting the formation of a black foreign matter in a molded product even in a severe molding condition using a hot runner system or the like. The polyester-based resin composition is composed of (A) 100pts.wt. polyester-based resin, (B) 5-60pts.wt. halogenated bisphenol-type epoxy resin having sealed terminal epoxy groups and <=8,000 number average molecular weight, (C) 1-20pts.wt. antimony-based flame retardant and (D) 0.1-10pts.wt. antistatic agent. The resin composition may contain (E) a phosphoric acid salt and/or (F) an antioxidant. The resin composition preferably has >=10% tensile elongation based on ISO 527. The resin composition is useful for molding a lighting part (especially holders for a light source such as a cap for a circular pipe of a fluorescent lamp).
Description
Technical field
The present invention relates to be applicable to the outward appearance purposes of illuminace component etc., particularly be applicable to the polyester resin composition of light source such as luminescent lamp pipe lamp socket with lamp socket.
Background technology
All the time, the normal excellent vibrin such as thermotolerance, mechanical characteristics, resistance to chemical reagents, plasticity that uses is as illuminace component, but recently, along with the miniaturization of lamp, utensil or the high brightnessization of light source develop, from guaranteeing the security of products viewpoint, require illuminace component to have flame retardant resistance.
In addition, if having dust to adhere in the manufacturing of illuminace component and assembling procedure, then reliability of products and life-span descend.In addition, the finished product such as luminescent lamp pipe lamp socket, if having dust to adhere to during the paving is showed, then commodity value is with impaired.Therefore, require illuminace component also will have static electricity resistance.But, if the polyester and resin composition of giving flame retardant resistance then will promote the decomposition of resin with static resistance, produce silver when processing, the outward appearance of damage molding and be shaped.
On the other hand, as the fire-retardantization technology of resin combination, be known that and add halogenated epoxy resin in the resin combination method as fire retardant.But, this resin combination that is added with fire retardant, melting mixing in extrusion machine or the thermal process medium viscosities such as delay in the injection molding machine will significantly rise.Therefore, the flowability of resin combination descends and makes the shaping processability variation, finally produces black impurity at pipe lamp sockets such as fluorescence.
In order to prevent owing to the gelation of adding the resin combination that fire-retardant machine causes, for example open in the clear 58-118849 communique and proposed the spy, by the average repeating unit n with the dihydroxyphenyl propane skeleton is that the halogenation bisphenol A type epoxy resin of the high molecular type more than 11 is as fire retardant, improve the epoxy equivalent (weight) in the fire retardant, thereby prevent the gelation of resin combination, improve the method for melt stability.In addition, open in the flat 11-349793 communique the spy, having proposed to add as shaping mobile excellent, the resin combination that can prevent that gelation takes place simultaneously and possess excellent flame in melting mixing in man-hour, is 1600～12000 halogenation bisphenol A type epoxy resin and antimony compounds as the thermoplastic flame-proof polyester and resin composition that must composition contains with 30～95% end-blockings of thermoplastic polyester, terminal epoxy groups and weight-average molecular weight.
In addition, for mechanical characteristics and the melting heat stability of improving flame-retardant polyester resin, for example open clear 54-83053 communique the spy, the spy opens clear 62-172052 communique etc. and has proposed, as fire retardant, with the brominated epoxy compound of the brominated polycarbonate oligopolymer of specified molecular weight and specified molecular weight method with specific ratios and usefulness.
But these methods also do not fit into as the shaping under the hot runner system of using in the shaping of illuminace components such as the lamp socket class severe condition such as (the heating and melting time are long, is exposed on 290～300 ℃ of left and right sides pyritous systems for the moment).For example, suppress effect or the high fire retardant of melt stability, can not give essential toughness such as lamp socket, in batch process, will produce a large amount of black impurities even select only to have the gelation of resin fused.
Summary of the invention
The objective of the invention is to, a kind of have high flame retardant and static electricity resistance are provided, simultaneously, even under harsh molding conditions such as use hot runner system, also can be suppressed at polyester resin composition that produces black impurity in the molding and the illuminace component that utilizes it.
Another object of the present invention is to provide a kind of illuminace component that has the polyester resin composition of high tenacity and fast light discolouration and utilize it.
The inventor etc. are in order to finish above-mentioned problem, carried out the result of further investigation, found if will specific brominated flame retardant, antimony class flame retardant, antistatic agent, also as required with phosphoric acid salt and/or antioxidant combination use, then can not only improve the flame retardant resistance and the static electricity resistance of polyester resin, even under harsh molding condition, also can suppress the generation of black impurity, thereby finish the present invention.
That is, polyester resin composition of the present invention is to be that halogenation bisphenol-type epoxy resin (B), antimony class flame retardant (C) and antistatic agent (D) below 8000 constitutes by polyester resin (A), terminal epoxy groups by end capped number-average molecular weight.Described polyester resin (A) can constitute by containing the unitary polyester resin of the above alkylidene aryl thing of 50mol% at least.Described halogenation bisphenol-type epoxy resin (B) can be that 1000～7000 chlorination or brominated bisphenol type Resins, epoxy constitute by the number-average molecular weight of end capped structure by having terminal epoxy groups 60～100%.Described antimony class flame retardant (C) can be made of weisspiessglanz, stibnate etc.Described antistatic agent (D) can be anionic property antistatic agent, cationic antistatic agent, nonionic antistatic agent etc., for example can enumerate sulfonate such as alkylsulfonate, alkylaryl sulphonate, arylsulphonate etc.When antistatic agent (D) is made of anionic property antistatic agent and nonionic antistatic agent, the ratio of anionic property antistatic agent and nonionic antistatic agent approximately with the former/latter=90/10～10/90 (weight ratio) for well.In described resin combination, each components in proportions for example is, with respect to polyester resin (A) 100 weight parts, halogenation bisphenol-type epoxy resin (B) is about 5～60 weight parts, antimony class flame retardant (C) is about 1～20 weight part, and antistatic agent (D) is about 0.1～10 weight part.The ratio of antimony class flame retardant (C) with respect to halogenation bisphenol-type epoxy resin (B) 100 weight parts, also can be about 5～70 weight parts.The surface resistivity of this resin combination can be 5 * 10
13～1 * 10
10(Ω/cm
2) about.This resin combination can also contain phosphoric acid salt (E) or antioxidant (F) etc.Described phosphoric acid salt (E) can be phosphate metal salt.Described antioxidant (F) can be made of hindered phenol compound or thio-ether type compounds etc.Described resin combination for example with respect to polyester resin (A) 100 weight parts, contains about phosphoric acid salt (E) 0.01～5 weight part and about antioxidant (F) 0.01～5 weight part.Described resin combination preferably has the extensibility more than 10% in the tension test according to ISO527.Described composition can be used for being exposed on the shaping system of temperature more than 290 ℃.
Also comprise the illuminace component that forms by described resin combination (light source with lamp socket etc.) among the present invention.
In addition, in this manual, " illuminace component " be meant, near light source or be provided in the various members of light source periphery, for example can enumerate the socket class, lamp socket class, reverberator, stabilizer etc. with contact or non-contacting state.
Embodiment
Polyester resin (A) can be obtained by the polycondensation of polycondensation, hydroxycarboxylic acid composition or the lactone composition of dicarboxylic acid composition and dihydroxyl composition or polycondensation of these compositions etc.Polyester resin (A) can be in polyester homopolymer and the polyester copolymer any one.
As described dicarboxylic acid composition, for example [for example can enumerate aromatic dicarboxylic acid, carbon number is about 8～16 aromatic dicarboxylic acid (terephthalic acid, m-phthalic acid, phthalic acid, the phthalic acid that alkyl such as methyl terephthalic acid, methyl m-phthalic acid replace, naphthalene dicarboxylic acids (2,6-naphthalene dicarboxylic acids, 2,7-naphthalene dicarboxylic acids, 1,5-naphthalene dicarboxylic acids etc.), xenyl dicarboxylic acid (4,4 '-two phenyl dicarboxylic acid, 3,4 '-two phenyl dicarboxylic acid etc.); Two phenoxy group alkane dicarboxylic acid such as biphenoxyl ethane dicarboxylic acid; The diphenyl ether dicarboxylic acid; Phenylbenzene alkane dicarboxylic acid such as ditan dicarboxylic acid, diphenylethane dicarboxylic acid; Diphenylketone dicarboxylic acid etc.) etc. or derivatives thereof]; Alicyclic dicarboxylic acid's (for example, ester ring type dicarboxylic acid of carbon numbers such as cyclohexane cyclohexanedimethanodibasic, hexahydro-phthalic acid, hexahydro-m-phthalic acid, hexahydroterephthalic acid, nadic acid about 8～12 etc.) or derivatives thereof; Aliphatic dicarboxylic acid (for example, the aliphatic dicarboxylic acid of carbon numbers about 2～40 such as succsinic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, decane dicarboxylic acid, dodecanedicarboxylic acid, hexadecane dicarboxylic acid, dimeracid; Preferred carbon number is about 4～14 aliphatic dicarboxylic acid, and more preferably carbon number is about 6～10 aliphatic dicarboxylic acid) or derivatives thereof etc.
Comprise the derivative that can form ester in the described derivative, for example sour halogenide such as lower alkyl esters, acid anhydrides and sour muriate such as dimethyl ester etc.These dicarboxylic acid can use more than 2 kinds alone or in combination.In addition, preferred dicarboxylic acid composition is aromatic dicarboxylic acids such as terephthalic acid, naphthalene dicarboxylic acids.
As described dihydroxyl composition, for example can enumerate aliphatics alkane glycol (for example, ethylene glycol, trimethylene glycol, propylene glycol, 1,3 butylene glycol, 1,4-butyleneglycol, neopentyl glycol, 1, a straight chain shape or a catenate C such as 6-hexylene glycol, ethohexadiol, decanediol
2～12Alkanediol, preferred C
2～10Alkanediol, more preferably C
2～8Alkanediol etc.), alicyclic diol (for example, cyclohexanediol, 1,4-cyclohexanedimethanol, Hydrogenated Bisphenol A etc.), aromatic diol [for example, dihydroxy-benzene such as Resorcinol, Resorcinol, dihydroxyl alkylbenzenes such as orcin, the naphthalene glycol, dihydroxydiphenyl ether, 2, two (4-hydroxyphenyl) propane (dihydroxyphenyl propane) of 2-, bisphenols such as 2,2 '-two (4-hydroxy phenyl) sulfone are for bisphenols (dihydroxyphenyl propane etc.) addition epoxide (C such as oxyethane, propylene oxide
2～4Epoxide) adduct that obtains after (diethyl oxidation dihydroxyphenyl propane etc.) etc.], polyoxyalkylene diols (carbon number of alkylidene group be about 2～4 and glycol with a plurality of oxyalkylene units, for example glycol ether, triglycol, polyoxyethylene glycol, two four support methylene glycols, polytetramethylene ether diol, dipropylene glycol, tripropylene glycol, polypropylene glycol etc.) etc.
In addition, these dihydroxyl compositions for example can be alkyl, alkoxy or halogen substituent etc.These dihydroxyl compositions can use more than 2 kinds alone or in combination.Preferred dihydroxyl composition is alkanediol (C particularly
2～4Alkanediol) or alicyclic diol.
As described hydroxycarboxylic acid composition, for example can enumerate aromatic hydroxyl carboxylic acids such as hydroxyl group aliphatic carboxylic acids such as ε-hydroxycaproic acid or hydroxy-benzoic acid, '-hydroxyethoxy yl benzoic acid, hydroxynaphthoic acid, Hydroxybiphenyl carboxylic acids, and their derivative etc.In addition, the derivative sour halogenide such as lower alkyl esters, acid anhydrides and acyl chlorides such as methyl esters etc. for example that can form ester can be comprised in the carboxyl of described derivative, for example alkyl, alkoxyl group or halides etc. can be comprised in the hydroxyl.These hydroxycarboxylic acids can use more than 2 kinds alone or in combination.
As above-mentioned lactone composition, for example can exemplify C such as propiolactone, butyrolactone, valerolactone, caprolactone (for example 6-caprolactone etc.)
3-12Lactone etc.
In addition, except mentioned component, can also be as required, slightly and with polyvalent alcohols such as polycarboxylic acid such as for example trimellitic acid, trimesic acid, Pyromellitic Acid or glycerine, TriMethylolPropane(TMP), tetramethylolmethanes.These multi-functional monomeric usage quantitys normally below the 1.0mol%, below the preferred 0.5mol%, are more preferably selected below the 0.3mol%.As polyester resin (A), only otherwise damage melt-shaping etc., just also can use the side chain that generates by these multi-functional monomers or the polyester resin of crosslinking structure.In addition, polyester resin (A) can be a liquid crystal polyester.
These polyester resins (A) can use more than 2 kinds alone or in combination.
Comprise saturated polyester resin (particularly aromatic polyester-based resin) in the preferred polyester resinoid (A), for example as principal constituent (for example can enumerate terephthalic acid alkylene ester and/or alkylene naphthalate etc. with alkylidene aryl thing unit, 50～100mol% is about preferred 75～100mol%) homopolymerization or copolyesters [polyalkylene terephthalates (for example polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PPT), polybutylene terephthalate poly terephthalic acid C such as (PBT) for example
2-4Alkylene ester); Poly-alkylene naphthalate (for example, poly-naphthalic acid C such as PEN, PBN
2-4Alkylene ester) equal polyester such as; The copolyesters that contains as principal constituent (more than the 50mol%, preferred 60～98mol% is more preferably about 70～98mol%) with alkylidene aryl thing unit (for example terephthalic acid alkylene ester and/or naphthalic acid alkylidene unit)]; Contain corresponding to the unitary polyester of the ester ring type of above-mentioned homopolymerization or copolyesters [for example, gathering 1,4-hexanaphthene two methylene terephthalate (PCT)]; Dicarboxylic acid composition and diol component are the complete aromatic polyester of aromatics.
Polyester resin (A) can be that amorphism can be a crystallinity also, but from viewpoints such as shaping processability, mechanical characteristicies, preferably crystallinity.In this crystallinity polyester resin, include and contain C
2-4Alkylidene aryl thing unit is the polyester resin etc. of 60mol% above (more than the preferred 70mol%, more preferably more than the 80mol%) at least, for example can enumerate poly-C such as polybutylene terephthalate
2-4The alkylidene aryl thing perhaps contains C
2-4The copolyesters of alkylidene aryl thing unit 60mol% above (for example about 60～98mol%) etc.
In these polyester resins (A), preferred especially polyalkylene arylide resinoid (for example, poly terephthalic acid C such as polybutylene terephthalate
2-4Alkylene ester or with terephthalic acid C such as mutual-phenenyl two acid bromide two alcohol esters
2-4The copolyesters that the alkylene ester unit contains as principal constituent).
In the resinoid copolyesters of described polyalkylene arylide, but, can enumerate C as the monomer of copolymerization
2-6Aklylene glycol (ethylene glycol, propylene glycol, 1, straight chain shape aklylene glycols such as 4-butyleneglycol etc.), to have repeat number be that [glycol ether etc. contain poly-(oxygen-C for the polyoxyalkylene diols of about 2～4 oxyalkylene nuit(s)
2-4Alkylidene group) unitary glycol etc.], C
6-12The aromatic dicarboxylic acid (phthalic acid, m-phthalic acid etc.) of aliphatic dicarboxylic acid (hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid etc.), unsymmetric structure etc.
Described polyalkylene arylide resinoid, can be used in combination with other polyester resin, the ratio (weight ratio) of polyalkylene arylide resinoid and other polyester resin, the former/latter=60/40～95/5, preferred 70/30～95/5, more preferably about 80/20～95/5.
The intrinsic viscosity (IV) of polyester resin (A) for example can be selected from the scope about 0.7～1.2dl/g, and preferred 0.8～1.2dl/g is more preferably about 0.85～1.2dl/g.If it is low that intrinsic viscosity is spent, then can not obtain sufficient characteristic, particularly toughness.Particularly, when being used for illuminace component such as fluorescent lamp socket, the extensibility in the preferred tension test is more than 10%, and from then on viewpoint is set out, also the intrinsic viscosity of preferred described scope (the particularly above intrinsic viscosity of 0.8dl/g).If intrinsic viscosity is excessive, melt viscosity height then, mobile decline, plasticity is impaired.In addition, intrinsic viscosity is, at 35 ℃, with the value of ortho chloro phenol as solvent mensuration.
The number-average molecular weight of polyester resin (A) has no particular limits, for example can be from 0.5 * 10
4～100 * 10
4, preferably from 1 * 10
4～70 * 10
4, more preferably from 1.2 * 10
4～30 * 10
4About scope in select.
The end carboxy concentration of polyester resin (A) is 50meq/kg following (for example about 1～40meq/kg), about preferred 2～40meq/kg, more preferably about 3～30meq/kg.If end carboxy concentration is excessive, then as in melting mixing process etc., have a problem of resin combination gelation.
Polyester resin (A) can utilize customary way, transesterification reaction for example, manufacturings such as direct esterification method.
[halogenation bisphenol-type epoxy resin (B)]
The number-average molecular weight of halogenation bisphenol-type epoxy resin (B) is (for example 1000～8000) below 8000, preferred below 7000 (for example 1000～7000), more preferably 2000～6000 about (particularly 3000～6000).If the number-average molecular weight of halogenation bisphenol-type epoxy resin is excessive, then in the processing that is shaped, the flowability of resin combination descends, or dimensional stability descends.
Halogenation bisphenol-type epoxy resin (B) has more than 60% (60%～100%) of terminal epoxy groups, and preferred more than 70% (70～100%), more preferably about 70～95% by end capped structure, and in the practicality, about 60～95% just can.If too small to the end-blocking rate of terminal epoxy groups, then the thermostability of fused resin combination descends, and gelation takes place, and rises in shaping course of processing medium viscosity.In addition, described end-blocking rate can be obtained according to following note formula (a).
End-blocking rate (%)=(E
0-E
1)/E
0* 100 (a)
[in the formula, E
0Epoxy content (eq/kg) before the expression end-blocking, E
1Epoxy content (eq/kg) behind the expression end-blocking.In addition, described epoxy content is, according to the inverse of perchloric acid-epoxy equivalent (weight) that the tetraethylammonium bromide method obtains.]
As the bisphenol-type epoxy resin in the halogenation bisphenol-type epoxy resin, can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, dihydroxyphenyl propane D type Resins, epoxy, bisphenol-s epoxy resin etc.Usually use bisphenol A type epoxy resin.As the halogenation bisphenol-type epoxy resin, can enumerate the bisphenol-type epoxy resin that (for example 2～6, preferred 2～4) halogen atom that has 1～8 on the bis-phenol skeleton replaces.As halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom.Preferred chlorine or bromine atom, normally bromine atoms.As preferred halogenation bisphenol-type epoxy resin, can enumerate dibromo bisphenol A type epoxy resin, tribromo bisphenol A type epoxy resin, tetrabromo-bisphenol type Resins, epoxy etc.
The compound of the terminal epoxy groups of the described Resins, epoxy of end-blocking (end-capping reagent), there is no particular limitation, for example can use to contain the functionality compound bearing active hydrogen.Contain the functionality compound bearing active hydrogen and can be alcohols Fatty Alcohol(C12-C14 and C12-C18) such as () trimethyl carbinols or acids (aromatic carboxylic acids such as aliphatic carboxylic acid such as acetic acid or phenylformic acid etc.), but consider, preferably phenols from reactive and stable aspect.As phenols, for example can enumerate hydroxy arene classes such as phenol or naphthols, induced by alkyl hydroxybenzene (C such as cresols, p-tert-butylphenol
1-10Induced by alkyl hydroxybenzene), halogenation phenols [monobromophenol, dibromophenol, tribromophenol, tetrabromo phenol, pentabromophenol, Trichlorophenol etc. have the benzene halide phenols of 1～5 halogen atom (particularly chlorine atom or bromine atoms) on phenyl ring] etc.As particularly preferred end-capping reagent,, can enumerate halogenation phenols (particularly brominated phenols) from the viewpoint of the content of halogen that improves the halogenation bisphenol-type epoxy resin.
These halogenation bisphenol-type epoxy resins (B) can use more than 2 kinds alone or in combination.
Manufacture method as halogenation bisphenol-type epoxy resin (B), there is no particular limitation, for example can enumerate (1) and make halogenation bis-phenol and epichlorohydrin reaction, generate the halogenation bisphenol-type epoxy resin, make this Resins, epoxy then and as the method that contains simple function active dydrogen compounds reaction of end-capping reagent, (2) make halogenation bis-phenol and epichlorohydrin reaction, generate the halogenation bisphenol diglycidyl, make this Resins, epoxy and halogenation bis-phenol and the described method that contains the reaction of simple function active dydrogen compounds then, (3) make halogenation bis-phenol and epichlorohydrin reaction, generate the halogenation bisphenol diglycidyl, then with this Resins, epoxy and the reaction of halogenation bis-phenol, generate the halogenation bisphenol-type epoxy resin, then, with this Resins, epoxy and the described method that contains the reaction of simple function active dydrogen compounds etc.
In each method of described (1)～(3),, can adjust end-blocking rate, number-average molecular weight and the polymerization degree of halogenation bisphenol-type epoxy resin by adjusting the usage ratio of each composition of raw material.
The ratio of halogenation bisphenol-type epoxy resin (B) with respect to polyester resin (A) 100 weight parts, is 5～60 weight parts, and preferred 10～30 weight parts are more preferably about 15～30 weight parts.
In addition, described Resins, epoxy (B) can and be used with habitual other halogenated resin halogenation bisphenol type polycarbonate resins such as (for example, etc.) brominated bisphenol A type polycarbonate resins as required.By with other halogenated resin and usefulness, can improve the extensibility in the tension test.The softening temperature of other halogenated resin changes with molecular weight and molecular weight distribution, but from the viewpoint of mechanical properties, preferred 150～300 ℃ of left and right sides scopes.
And during with other halogenated resin, both ratios (weight ratio) are described Resins, epoxy (B)/other halogenated resin=90/10～50/50, preferred about 80/20～60/40.The ratio of other halogenated resin with respect to polyester resin (A) 100 weight parts, is 1～20 weight part, about preferred 1～10 weight part.If the ratio of halogenated resin is too much, then produce foaming by the interaction between the antistatic agent, plasticity descends.
[antimony compounds (C)]
Antimony compounds (C), so long as by and described Resins, epoxy between synergy flame retardant resistance compound that improve, that play the flame retardant function is just had no particular limits, for example can use weisspiessglanz (ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide etc.) or stibnate (metaantimmonic acid metal-salt, ammonium antimonates etc. such as sodium antimonate, metaantimmonic acid magnesium) etc.In these antimony compoundss, preferred ANTIMONY TRIOXIDE SB 203 99.8 PCT Sb
2O
3And/or xNa
2OSb
2O
5YH
2O weisspiessglanzs such as (x=0～1, y=0～4).
The median size of antimony compounds (C) for example can be selected from the scope about 0.02～5 μ m, is generally about 0.1～3 μ m.In addition, as required, also can use and carry out the surface-treated antimony compounds with surface treatment agents such as epoxy compounds, silane compound, isocyanate compound, titanate compounds.
These antimony compoundss (C) can be used singly or in combination.
The ratio of antimony compounds (C) with respect to polyester resin (A) 100 weight parts, is 1～20 weight part, preferred 3～15 weight parts, more preferably 4～10 weight parts.In order to give flame retardant resistance effectively, with respect to described Resins, epoxy (B) 100 weight parts, with antimony compounds (C) 5～70 weight parts, preferred 10～70 weight parts (for example, 20～70 weight parts), more preferably the ratio about 15～60 weight parts (for example, 30～60 weight parts) cooperates.
[antistatic agent (D)]
Antistatic agent (D) comprises low molecule-type antistatic agent such as anionic property antistatic agent, cationic antistatic agent, nonionic antistatic agent, both sexes antistatic agent or polymer antistatic agent etc.
As the anionic property antistatic agent, for example can enumerate sulfonated alkane (C such as dodecane sulfonic acid sodium
2-40C such as alkansulfonic acid an alkali metal salt or dodecane sulfonic acid 4-butyl-phosphonium
2-40Chain alkane sulfonic acid phosphonium salt etc.), arene sulfonate (C such as formaldehyde condensation products of sodium naphthalene sulfonate
6-20The polycondensate of aromatic hydrocarbons sulfonic acid alkali metal salts etc.), alkylated aromatic sulfonic acid salt (C such as Sodium dodecylbenzene sulfonate
4-20Alkyl C
6-20C such as aromatic hydrocarbons sulfonic acid alkali metal salts, Witco 1298 Soft Acid 4-butyl-phosphonium
4-20Alkyl C
6-20Virtue hydrocarbon sulfonic acid phosphonium salt etc.), alkyl phosphate (polyoxyethylene C such as polyoxyethylene dodecylphosphoric acid or polyoxyethylene dodecylphosphoric acid sodium
4-20Polyoxyethylene C such as alkyl ether phosphate, polyoxyethylene dodecylphenyl phosphoric acid
2-40C such as alkyl phenyl ether phosphate, 1-isobutyl-3,5-dimethylhexylphosphoric acid or Potassium dodecyl phosphate
2-40Alkylphosphonic etc.) etc.
As the cationic antistatic agent, for example can enumerate tetraalkylammonium salt (C such as dodecyl trimethyl ammonium muriate
4-20Alkyl methyl ammonium salt etc.), triakyl benzyl ammonium salt (Benzalkonium Chloride ammonium salt etc.), Benzethonium Chloride etc.
As the nonionic antistatic agent, can enumerate polyoxyethylene deriv (polyoxyethylene C such as polyoxyethylene glycol, polyox-yethylene-polyoxypropylene block copolymer, polyoxyethylene-lauryl ether
4-20Polyoxyethylene C such as alkyl oxide, polyoxyethylene nonylplenyl ether
4-20Alkyl phenyl ether, polyoxyethylene glycerol stearate etc. have the C of the polyvalent alcohol of polyoxyethylene chain
4-20Polyoxyethylene C such as fatty acid ester, polyoxyethylene lauryl amine
4-20Alkylamine etc.), polyol derivative (glycerine C such as Zerol
4-20Sucrose such as fatty acid ester, sucrose monostearate C
4-20Sorbitan such as fatty acid ester, sorbitan monooleate C
4-20Fatty acid ester etc.), alkyl ethanol amine (C such as lauryl thanomin
4-20Alkyl ethanol amine etc.) etc.The number-average molecular weight of polyethylene oxide derivatives (for example polyoxyethylene glycol) is 500～100000, preferred about 1000～50000.
As the both sexes antistatic agent, can enumerate alkyl betaine (dimethyl dodecyl carboxybetaine etc.) or sultaine derivative etc.
As the polymer antistatic agent, for example can enumerate polyepoxide-(methyl) acrylate copolymer (polyethylene oxide-alkylmethacrylate polymer etc.), polyepoxide multipolymer (polyethylene oxide-poly(propylene oxide) multipolymer etc.), polyepoxide-epihalohydrin copolymer (polyethylene oxide-epihalohydrin copolymer etc.), polyethers resin (polyetheramides, polyether ester amides, polyetheramides imide, polyether ester etc.).
In these antistatic agents (D), from keeping the whiteness of molding well, keep sunproof viewpoint and set out, preferably the antistatic agent that constitutes by low molecule-type antistatic agent (for example, anionic property antistatic agent, cationic antistatic agent, nonionic antistatic agent etc.) at least.In addition, preferably constitute the antistatic agent that special preferably combination anionic property antistatic agent and nonionic antistatic agent form at least by the anionic property antistatic agent.
The preferred anionic surfactants antistatic agent is sulfonate, particularly preferably is, sulfonated alkane (C such as dodecane sulfonate
2-40Sulfonated alkane etc.), arene sulfonate (C such as naphthalenesulfonate
6-20Arene sulfonate etc.), alkylated aromatic sulfonic acid salt (C such as dodecylbenzene sulfonate
6-20Arene sulfonate etc.) sulfonate such as.As salt, preferably, an alkali metal salt (), phosphonium salt, Wan Ji phosphonium salt (four C such as 4-butyl-phosphonium such as sodium or potassium
1-10Wan Ji phosphonium salt etc.) etc.
Preferred nonionic antistatic agent is polyoxyalkylene derivative (polyoxyalkylene C such as polyoxyethylene glycol or polyoxyethylene-polyoxypropylene block copolymers
2-4Glycol etc.).
Because of if on illuminace component, there is dust to adhere to, then can damage the value of commodity, so be 5 * 10 for the surface resistivity of resin combination preferably with antistatic agent (D) cooperation
13～1 * 10
10Ω/ (Ω/cm
2), preferred 1 * 10
13～1 * 10
10Ω/ (Ω/cm
2) about.
The ratio of antistatic agent (D), the melt stability viewpoint during from static electricity resistance and shaping with respect to polyester resin (A) 100 weight parts, is 0.1～10 weight part, preferred 0.1～7.5 weight part is more preferably about 0.3～5 weight part.The ratio of the antistatic agent that anionic property antistatic agent and nonionic antistatic agent are combined is with respect to polyester resin (A) 100 weight parts, is 0.1～10 weight part, and preferred 0.1～7.5 weight part is more preferably about 0.3～5 weight part.
The ratio of anionic property antistatic agent and nonionic antistatic agent (weight ratio) is, 90/10～10/90, and preferred about 80/20～20/80, more preferably 70/30～30/70.
[phosphoric acid salt (E)]
As the phosphoric acid in the phosphoric acid salt (E), can enumerate condensed phosphoric acids such as non-condensed phosphoric acids such as phosphoric acid (ortho-phosphoric acid), metaphosphoric acid, phosphorous acid, Hypophosporous Acid, 50 or hypophosphite, pyrophosphate salt, polyphosphate (triphosphate, tetraphosphate etc.), many metaphosphates (trimetaphosphate, tetrametaphosphate, hexametaphosphate etc.), phosphoric anhydride salt etc.In these phosphoric acid, non-condensed phosphoric acid such as preferably phosphoric acid.
As salt, for example (for example can enumerate basic metal, lithium, sodium, potassium etc.), alkaline-earth metal (for example, magnesium, calcium etc.), transition metal (for example, manganese, iron etc.), periodictable 2B and 3B family metal (for example, aluminium, zinc etc.), the salt of ammonia or amine (for example, alkanolamine such as amine, thanomin, guanidine, melamine, Miller amine etc.).In these salt, preferable alloy salt (particularly an alkali metal salt such as sodium).
Particularly, as phosphoric acid salt (E), for example can enumerate, [(phosphate metal salt (for example for phosphoric acid salt, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, phosphoric acid alkali metal salt such as tertiary sodium phosphate or, secondary magnesium phosphate, primary magnesium phosphate, monocalcium phosphate, phosphoric acid-phosphoric acid alkali earth metal salts such as hydrogen calcium, manganese hydrogen phosphate, phosphoric acid hydrogen iron, phosphoric acid hydrogen zinc, phosphoric acid hydrogen aluminium, phosphoric acid hydrogen tin etc.), ammonium phosphate etc.], the tetra-sodium metal-salt (for example, alkali metal pyrophosphate salts such as trisodium phosphate etc.), metaphosphoric acid metal-salt (for example, metaphosphoric acid alkali earth metal salts such as calcium metaphosphate etc.), the tripolyphosphate metal-salt is (for example, tripolyphosphate an alkali metal salts such as tripoly phosphate sodium STPP etc.), the hexa metaphosphoric acid metal-salt (for example, hexa metaphosphoric acid an alkali metal salts such as Sodium hexametaphosphate 99 etc.), phosphoric anhydride metal-salt (for example, phosphoric anhydride alkali earth metal salt such as phosphoric anhydride calcium etc.) etc.
In these phosphoric acid salt, preferably phosphoric acid metal-salt, more preferably phosphoric acid alkali metal salt (particularly SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic).
The ratio of phosphoric acid salt (E) with respect to polyester resin (A) 100 weight parts, is 0.01～5 weight part, and 0.05～3 weight part is more preferably about 0.1～2 weight part (particularly 0.1～1 weight part).If phosphatic ratio is very few, then do not have the effect of melt stability, but if too much, effect does not rise significantly, and is unfavorable economically.
[antioxidant (F)]
Antioxidant comprises hindered phenol compound, thio-ether type compounds, phosphate compounds etc.As hindered phenol anti-oxidants, for example can enumerate, 1, the two C such as [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic esters] of 6-hexylene glycol
2-10Alkanediol two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; Triglycol-two hydroxyl C such as [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic esters]
2-4Alkanediol two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; Glycerine three C such as [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic esters]
3-8Alkane triol-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; Tetramethylolmethane four C such as [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic esters]
4-8Alkane tetrol four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; Three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-isocyanuric acid ester etc. three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) pyrrolotriazine derivatives, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 4,4 '-butylidene is two-(3 methy 6 tert butyl phenol) alkylidene group of etc.ing pair-(3 methy 6 tert butyl phenol) etc.In these antioxidants, particularly preferably be, have triazine ring compound [three (and 3,5-di-tert-butyl-hydroxy phenyl C
1-4Alkyl)-triazine etc.].
As thioether class antioxidant, can enumerate dilauryl-3,3 '-thiodipropionate, Er Rou Dou Kou base-3,3 '-thiodipropionate, distearyl-3,3 '-thiodipropionate, lauryl stearyl-3, two C such as 3 '-thiodipropionate
10-22Alkyl-3,3 '-thiodipropionate; Tetramethylolmethane base-four (3-lauryl thiopropionate); Four [methylene radical-3-(dodecyl sulphur) propionic ester] methane etc.Preferred thioether class antioxidant is four propionic acid esters, for example four [methylene radical-3-(C such as four [methylene radical-3-(dodecyl sulphur) propionic ester] methane
10-22Alkyl sulfide) propionic ester] methane.
As the phosphoric acid ester antioxidant, can enumerate three nonyl phenyl phosphate ester, distearyl tetramethylolmethane-bisphosphate, three (2, the 4-di-tert-butyl-phenyl) phosphoric acid ester, four (2, the 4-di-tert-butyl-phenyl)-4,4 '-biphenylene-bisphosphate, two-(2, the 4-di-tert-butyl-phenyl) tetramethylolmethane-bisphosphate, two (2,6-di-tert-butyl-phenyl-4-methyl) tetramethylolmethane-bisphosphate.
These antioxidants can use more than 2 kinds alone or in combination.In these antioxidants, preferably constitute, preferably constitute by hindered phenol anti-oxidants at least especially by being selected from least a in hindered phenol compound and the sulfide compound.In addition, preferred and with hindered phenol anti-oxidants and thioether class and/or phosphate-based antioxidants from improving the viewpoint of heat-resisting discolouration, special preferably combination hindered phenol anti-oxidants and thio-ether type compounds and constitute.The ratio of hindered phenol anti-oxidants and thio-ether type compounds (weight ratio) is 90/10～10/90, and is preferred 80/20～20/80, more preferably about 70/30～30/70.
The ratio of antioxidant (F) with respect to vibrin 100 weight parts, is 0.01～5 weight part (for example, 0.05～5 weight part), preferred 0.02～3 weight part, and more preferably 0.02～1 weight part is generally about 0.5～1.5 weight part.
[additive]
In the polyester resin composition of the present invention, in the scope of not damaging the object of the invention, can add various habitual additives as required, for example stablizer (UV light absorber, fast light stablizer etc.), weighting agent (non-fibrous inorganic fillers such as fibrous inorganic filler such as glass fibre or carbon fiber or sheet glass etc.), lubrication prescription (lubricant), releasing agent, tinting material (dyestuff or pigment etc.), softening agent, white dyes, properties-correcting agent (impact modifying agent, mobile properties-correcting agent etc.) etc.
In addition, in order to give higher flame retardant resistance (for example, the flame retardant resistance of fire-retardant sectional " V-0 " degree of UL specification 94) to illuminace component, prevent agent as drippage (dripping), can and with asbestos or fluorine-type resin (powder shape fluorine-type resin) etc.In the described fluorine-type resin, can comprise tetrafluoroethylene, trifluorochloroethylene, 1, independent or the multipolymer of fluorochemical monomers such as 1-difluoroethylene, R 1216, perfluoroalkyl vinyl ether, the multipolymer of co-polymerized monomers such as described fluorochemical monomer and ethene, propylene, (methyl) acrylate.
As this fluorine-type resin, for example can enumerate homopolymer such as tetrafluoroethylene, voltalef, poly(vinylidene fluoride); Multipolymers such as tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoro-ethylene copolymer etc.These fluorine-type resins can use more than 2 kinds alone or in combination.And, also can be used in combination asbestos and fluorine-type resin.Adding drippage and prevent that the ratio of agent from being, with respect to polyester resin (A) 100 weight parts, for example is 0.5～5 weight part, and preferred 0.7～4 weight part is more preferably about 1～3 weight part.
[manufacture method]
Polyester resin composition of the present invention, can be according to the customary way manufacturing, for example, by with described constituent with the additive that adds as required etc., (mix with the customary way mixing by dry type, the mixing of blending meanss such as melting mixing such as melt extruded, melting mixing), can be easily as powder shape mixture or molten mixture and modulate.For example, use mixing machine to mix after the constituent equably, use Banbury, warming mill or single shaft or multiple screw extruder etc., (for example 200～360 ℃ of melt temperatures, preferred 230～290 ℃, more preferably about 250～290 ℃), but the method resin composition modulation of melting mixing utilized.In the method, also applicable in advance with a part of composition of resin combination pre-mixing after, the ratio that is adjusted into regulation is carried out mixing method.In addition, if a part of constituent of resin combination is mixed interpolation as the fine powder body with other composition, then can mix constituent equably.Flame retardant resin composition of the present invention except that disk (pellet) shape, also can be Powdered, granular, laminar etc.
Illuminace component of the present invention can use described resin combination to form, for example, and with described resin combination melting mixing, by being shaped with customary ways such as extrusion molding, injection molded, blow molding, compression moldings and easily making.In addition, there is no particular limitation to the manufacturing process of illuminace component of the present invention, preferred injection molded method.
[polyester resin composition]
Polyester resin composition of the present invention is the resin combination that can adapt to the shaping under the severe condition such as hot runner system.Promptly, though resin combination in the past, also can what improve inhibition and melt stability, but can not make the raising of the inhibition (tackify that suppresses resin) of fused gelation or melt stability and become generation frequency practical problems, that follow the black impurity that is shaped and produces the gelation in the melting mixing process.For example, when being formed by hot runner system, compare with the situation of common injection molded by the cold runner system, it is long that composition is heated the fused time, and temporarily be exposed on usually under the high temperature about 290～300 ℃.Under the shaping of this condition, the mechanical characteristics of resin combination (particularly toughness) will descend, and produce black impurity at molding (illuminace component) simultaneously.
The detailed mechanism that produces black impurity at molding it be unclear that, but deducibility and molten resin have much relations to the connecting airtight property of resin of screw rod.That is, can think that the black impurity that is produced by severe condition adheres to, is piled up in screw rod, and thus, in forming process, be blended in the molding.Therefore, as the evaluation method that black impurity takes place, can follow the state of the screw rod that is detained deterioration to carry out by observation.Be specially, (the smart mechanism of Japan is made institute's (strain) system to trier to utilize laboratory plasticity (plasto) to mill, the ME-25 type), from hopper side to mold overflow mould side, cylinder temperature with 180 ℃, 260 ℃, 290 ℃, 290 ℃, 260 ℃, with 1kg/ hour output extrusion resin composition 30 minutes, and, can estimate by observing the state that is detained the screw rod after 1 hour.The result who observes, if screw rod and preliminary phase with or pollute and lack, can think that then the generation of black impurity is few.The black impurity occurrence frequency of this test-results when producing illuminace component (particularly luminescent lamp pipe lamp socket) in batches can be interrelated.
Resin combination of the present invention can be kept mechanical characteristics, particularly toughness well under this molding condition, and can suppress to produce in the molding black impurity.
In addition, to the desired toughness of illuminace component, specifically be, according to the extensibility in ISO (InternationalOrganization for Standardization) 527 tension tests of carrying out is more than 6%, preferred more than 10% (for example, 10～30%), more preferably more than 12% about (for example 12～25%).If have the extensibility in the tension test of this degree, for example when lamp socket time-like such as luminescent lamp pipe lamp socket being installed or using product, be difficult for taking place breakage etc.
In addition, to illuminace component (particularly, light source lamp socket class etc.) desired fast light discolouration, promoting in the test in variable color, being specially under the high voltage mercury lamp at 400W the aberration Δ E of irradiation after 1 hour is (for example 3～25) below 25, preferred below 20 (for example 5～20) is more preferably below 18 about (particularly 10～18).
Have the resin combination of the present invention of this specific character, be suitable for the illuminace component purposes.Comprise approaching or be configured in the various members of light source periphery in the illuminace component with contact or non-contacting state and light source, for example, can enumerate socket class (general incandescent light socket, mogal socket, high-intensity discharge lamp socket, annular socket etc.), lamp socket class (luminescent lamp pipe lamp socket etc. is used to keep the light source of light source to be used to lamp socket that keeps light source cell or lighting unit etc. with lamp socket, illuminator lamp seat etc.), reverberator, stabilizer etc.In these illuminace components, resin combination of the present invention is particularly useful in as the lamp socket class, for example luminescent lamp pipe lamp socket, two pipe (two palook) lamp socket, palook ball lamp socket, twin-lamp socket light sources such as (compact fluorescent lamp lamp sockets) are with lamp socket class or palook ball dividing plate, palook ball box (case) etc.
The present invention can give polyester resin with high flame retardant and static electricity resistance, even be shaped this resin combination simultaneously under harsh molding conditions such as use hot runner system, also is difficult for producing the unacceptable product that is caused by sneaking into of black impurity.In addition, can possess the high toughness and the high level of fast light discolouration simultaneously.Therefore, resin combination of the present invention is useful on shaping illuminace component (particularly light source lamp socket class such as luminescent lamp pipe lamp socket).
[embodiment]
Below, illustrate in greater detail the present invention according to embodiment, but the present invention is not limited to these embodiment.In addition, the following expression of each composition that will in embodiment and comparative example, use, the characteristic of the molding that obtains simultaneously is to utilize note method mensuration down.
[each composition that contains in the composition]
(A) polyester resin
Polybutylene terephthalate (PBT): win branch polymkeric substance (strain) system, IV=0.92, trade(brand)name C7000Z
(B) halogenation bisphenol A type epoxy resin
BrEP fire retardant (B1-1): big Japanese ink chemical industry (strain) system, trade(brand)name ECX-30, number-average molecular weight is about 3000, terminal tribromophenol end-blocking
BrEP fire retardant (B1-2): this pharmaceutical industries of slope (strain) system, trade(brand)name SR-T3040, number-average molecular weight is about 6000, terminal tribromophenol end-blocking
BrEP fire retardant (B2-1): big Japanese ink chemical industry (strain) system, trade(brand)name EXP-261, number-average molecular weight is about 10000, terminal tribromophenol end-blocking
BrEP fire retardant (B2-2): big Japanese ink chemical industry (strain) system, trade(brand)name EC-200, number-average molecular weight is about 20000, terminal tribromophenol end-blocking
(B ') the halogenation bisphenol A polycarbonate
The BrPC fire retardant (B '): Supreme Being people changes into (strain) system, fire guard 7500, polymerization degree n=5
(C) antimony class flame retardant
Flame retardant (ANTIMONY TRIOXIDE SB 203 99.8 PCT): this Jing of Ri Mining (strain) system, trade(brand)name PATOX-M
(D) antistatic agent
Antistatic agent (mixture of Sodium dodecylbenzene sulfonate and polyethylene oxide derivant): this grease of bamboo (strain) system, trade(brand)name TPL-456
(E) phosphoric acid salt
Phosphate metal salt (SODIUM PHOSPHATE, MONOBASIC dihydrate): and the pure medicine of light (strain) system, the reagent superfine
(F) antioxidant
Antioxidant (F1) (hindered phenol anti-oxidants): cibaspecialtychemicals (strain) system, trade(brand)name lrg1010
Antioxidant (F2) (thioether class antioxidant): rising sun electrochemical industry (strain) system, trade(brand)name AO412S
[tensile properties]
Injection molded is according to the test film of ISO3167, and measures intensity (tensile strength) and extensibility (stretching extensibility) in the tension test according to ISO527.
[to the adhesion amount of the black impurity of screw rod]
The ME-25 type laboratory plasticity of using the smart mechanism of Japan to make institute's (strain) system trier (measure head (head) and use a D20-28 type single shaft forcing machine) of milling, the disk that will have the resin combination of aftermentioned composition, from hopper side to mold overflow mould side, cylinder temperature with 180 ℃, 260 ℃, 290 ℃, 290 ℃, 260 ℃, carry out 30 minutes extruding with 1kg/ hour output after, make screw rod stop 1 hour.Then, clean with polyethylene, (Toyo Ink manufacturing (strain) system lioclean) is cleaned further to use cleaner for molding machines.Then, detect by an unaided eye attached to the adhesion amount of the black impurity of the resin combination on the screw surface, and according to the adhesion amount of following benchmark evaluation to the black impurity of screw rod.
(metewand)
A: no dirt settling
B: a spot of dirt settling is arranged
C: dirt settling is arranged
[flame retardant resistance (UL-94)]
According to the method for the subject 94 (UL94) of U.S. Underwriters Laboratories, use 5 test films (thickness: 0.8mm), to flame retardant resistance with follow the resin combination incendiary characteristic of dripping to test, estimate the burning level.
[surface resistivity]
Surface resistivity is to use teraohmmeter (advantest corporation (strain) system, digital ultra-high resistance meter R8340A) to carry out measuring (measuring voltage 500V).This mensuration is, after the damping sample 24 hours, carries out under the atmosphere of 23 ℃ of envrionment temperatures, 50% relative humidity under the atmosphere of 23 ℃ of temperature, 50% relative humidity.
[fast light discolouration]
For the initial stage tone of test film, after L, a of mensuration L*a*b color specification system, the b value, this test film is offered in the high voltage mercury lamp radiation test.In this test, use UV irradiating machine (the Lighting ﹠amp of Toshiba; Technology Corporation (strain) system, TOSCURE401, high voltage mercury lamp 400W), after shining 1 hour, measured the tone of test film.At this moment the temperature of test film central part is 100 ℃.Fast light discolouration is to estimate with the variable color degree (Δ E) before and after the uviolizing.
[physical property measurement method]
Tension test is to measure according to ASTMD638.
Embodiment 1～5 and comparative example 1～3
Described each composition with the mixed shown in the table 1, is used the twin-screw extruder melting mixing, modulated the flaky resin combination of circle.Then, use this disk, utilize injection molded, make test film, and above-mentioned every characteristic is estimated.It the results are shown in the table 1.
By in the table as can be known, composition of the present invention (embodiment 1～5) keeps required flame retardant resistance, static electricity resistance and the fast light discolouration of luminescent lamp pipe lamp socket, the adhesion amount of black impurity is considerably less simultaneously, the incidence of substandard product sharply reduces during batch process.Particularly, the composition of embodiment 1～4, extensibility is more than 10% in tension test, toughness is also excellent.On the other hand, the composition of comparative example 1～3 is many to the adhesion amount of the black impurity of screw rod.
Table 1
| Embodiment | Comparative example | ||||||||
| 1 | 2 | 3 | 4 | 5 | 1 | 2 | 3 | ||
| Form (weight portion) | PBT(A) | 74.4 | 74.4 | 74.4 | 74.8 | 74.6 | 74.4 | 74.4 | 76.4 |
| BrEP fire retardant (B1-1) | 15 | 19 | - | 15 | 15 | - | - | 2 | |
| BrEP fire retardant (B1-2) | - | - | 15 | - | - | - | - | - | |
| BrEP fire retardant (B2-1) | - | - | - | - | - | 15 | - | - | |
| BrEP fire retardant (B2-2) | - | - | - | - | - | - | 15 | - | |
| The BrPC fire retardant (B ') | - | - | 4 | 4 | 4 | 4 | 4 | 17 | |
| Flame retardant (C) | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 | |
| Antistatic agent (D) | 2 | 2 | 2 | 2 | 2 | 2 | 2 | - | |
| Phosphate metal salt (E) | 0.2 | 0.2 | 0.2 | 0.2 | - | 0.2 | 0.2 | 0.2 | |
| Antioxidant (F1) | 0.2 | 0.2 | 0.2 | - | 0.2 | 0.2 | 0.2 | 0.2 | |
| Antioxidant (F2) | 0.2 | 0.2 | 0.2 | - | 0.2 | 0.2 | 0.2 | 0.2 | |
| Tensile strength (Mpa) | 62 | 62 | 62 | 61 | 60 | 60 | 59 | 60 | |
| Stretching extensibility (%) | 13 | 12 | 14 | 10 | 8 | 12 | 13 | 7 | |
| Adhesion amount to the black impurity of screw rod | A | A | A | A | A | C | C | B | |
| Incendivity (UL94 level) | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | |
| Surface resistivity (Ω) | 2.3×10 12 | 3.1×10 12 | 3.5×10 12 | 2.3×10 12 | 2.3×10 12 | 2.3×10 12 | 2.1×10 12 | 1.2×10 14 | |
| Initial stage tone L | 93 | 92 | 93 | 90 | 92 | 92 | 93 | 91 | |
| ?????????????????????????a | -0.6 | -0.5 | -0.6 | -0.7 | -0.6 | -0.6 | -0.6 | 1.5 | |
| ?????????????????????????b | 4.7 | 5.4 | 5.1 | 6.1 | 4.7 | 4.3 | 5.3 | -3.1 | |
| L behind the irradiation high voltage mercury lamp | 88 | 87 | 89 | 79 | 88 | 89 | 89 | 89 | |
| ?????????????????????????a | -3.1 | -4.2 | -3.2 | -5.1 | -3.1 | -3 | -3 | -2.9 | |
| ?????????????????????????b | 21 | 23 | 22 | 27 | 20 | 18 | 19 | 13.2 | |
| ???????????????????????ΔE | 17 | 19 | 18 | 24 | 16 | 14 | 14 | 17 | |
Claims (20)
1, a kind of polyester resin composition is that halogenation bisphenol-type epoxy resin (B), antimony class flame retardant (C) and antistatic agent (D) below 8000 constitutes by polyester resin (A), the end capped number-average molecular weight of terminal epoxy groups.
2, resin combination according to claim 1, wherein, polyester resin (A) constitutes by containing the unitary polyester resin of the above alkylidene aryl thing of 50mol% at least.
3, resin combination according to claim 1, wherein, halogenation bisphenol-type epoxy resin (B) is that 1000～7000 chlorination or brominated bisphenol type Resins, epoxy constitute by having 60～100% of terminal epoxy groups by the number-average molecular weight of end capped structure.
4, resin combination according to claim 1, wherein, antimony class flame retardant (C) constitutes by being selected from least a in weisspiessglanz and the stibnate.
5, resin combination according to claim 1, wherein, antistatic agent (D) constitutes by being selected from least a in anionic property antistatic agent, cationic antistatic agent and the nonionic static electricity resistance.
6, resin combination according to claim 1, wherein antistatic agent (D) comprises at least a sulfonate that is selected from alkylsulfonate, alkylaryl sulphonate and the arylsulphonate.
7, resin combination according to claim 1, wherein antistatic agent (D) is made of anionic property antistatic agent and nonionic antistatic agent, and the ratio of anionic property antistatic agent and nonionic antistatic agent with weight ratio count the former/latter=90/10～10/90.
8, resin combination according to claim 1, wherein, with respect to polyester resin (A) 100 weight parts, the ratio of halogenation bisphenol-type epoxy resin (B) is 5～60 weight parts.
9, resin combination according to claim 1 wherein, with respect to polyester resin (A) 100 weight parts, contains antimony class flame retardant (C) with the ratio of 1～20 weight part, and contains antistatic agent (D) with the ratio of 0.1～10 weight part.
10, resin combination according to claim 1, wherein, the ratio of antimony class flame retardant (C) with respect to halogenation bisphenol-type epoxy resin (B) 100 weight parts, is 5～70 weight parts.
11, resin combination according to claim 1, wherein surface resistivity is 5 * 10
13～1 * 10
10Ω/cm
2
12, resin combination according to claim 1 wherein, also contains and is selected from least a in phosphoric acid salt (E) and the antioxidant (F).
13, resin combination according to claim 12, wherein, phosphoric acid salt (E) is made of phosphate metal salt.
14, resin combination according to claim 12, wherein, antioxidant (F) constitutes by being selected from least a in hindered phenol compound or the thio-ether type compounds.
15, resin combination according to claim 1 wherein, with respect to polyester resin (A) 100 weight parts, also contains phosphoric acid salt (E) 0.01～5 weight part and antioxidant (F) 0.01～5 weight part.
16, resin combination according to claim 1 wherein has the extensibility more than 10% in the tension test according to ISO527.
17, the purposes of the described composition of claim 1 is used for being exposed on the shaping system of temperature more than 290 ℃.
18, composition according to claim 1 is used for illuminace component.
19, a kind of illuminace component is formed by the described composition of claim 1.
20, a kind of light source lamp socket class is formed by the described composition of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2003101010229A CN1497014A (en) | 2002-10-10 | 2003-10-10 | Polyester type resin composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002297872 | 2002-10-10 | ||
| CNA2003101010229A CN1497014A (en) | 2002-10-10 | 2003-10-10 | Polyester type resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1497014A true CN1497014A (en) | 2004-05-19 |
Family
ID=34256398
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2003101010229A Pending CN1497014A (en) | 2002-10-10 | 2003-10-10 | Polyester type resin composition |
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| Country | Link |
|---|---|
| CN (1) | CN1497014A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1793226B (en) * | 2004-12-22 | 2010-11-17 | 胜技高分子株式会社 | Fire resistance thermoplastic polyester composite and lighting parts |
| CN101679729B (en) * | 2007-06-13 | 2012-04-25 | 胜技高分子株式会社 | Composite molded article |
-
2003
- 2003-10-10 CN CNA2003101010229A patent/CN1497014A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1793226B (en) * | 2004-12-22 | 2010-11-17 | 胜技高分子株式会社 | Fire resistance thermoplastic polyester composite and lighting parts |
| CN101679729B (en) * | 2007-06-13 | 2012-04-25 | 胜技高分子株式会社 | Composite molded article |
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