JP5720778B2 - Flame retardant polyester resin composition and molded article thereof - Google Patents

Description

  The present invention relates to a flame retardant resin composition comprising a polyester resin and a non-halogen flame retardant, and a molded product thereof.

  Polyester resins are used in a wide range of fields such as mechanical mechanism parts, electrical / electronic parts, and automobile parts, taking advantage of their excellent properties such as injection moldability and mechanical properties.

  Polyester resins are inherently flammable, so they can be used against industrial flames in addition to the balance of general chemical and physical properties for use as industrial materials such as mechanical mechanism parts, electrical / electronic parts, and automotive parts. Safety, that is, flame retardancy is required. In this case, a high degree of flame retardancy showing V0 of the UL-94 standard is often required.

  As a method for imparting flame retardancy to a polyester resin, a method in which a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant aid are compounded with the resin is common. However, this method has a tendency to generate a large amount of smoke during combustion. In addition, due to increased environmental awareness, there is a concern about the environmental impact of halogen-based flame retardant materials. Therefore, in recent years, it has been strongly desired to use a flame retardant containing no halogen.

  Until now, as a method for flame-retarding a thermoplastic resin without using a halogen-based flame retardant, adding a hydrated metal compound such as aluminum hydroxide or magnesium hydroxide is widely known. In order to obtain flame retardancy, it is necessary to add a large amount of a hydrated metal compound, which has the disadvantage that the original properties of the resin are lost.

  On the other hand, Patent Documents 1 to 8 disclose that red phosphorus is added as a method for making a thermoplastic resin flame-retardant without using such a hydrated metal compound. Although these are useful flame-retardant resin materials that do not use a halogen-based flame retardant, they have a problem that their use is limited due to the unique coloration and the color tone of the product.

  Patent Documents 9 to 13 disclose that a styrene resin is blended with a composition containing a resin such as PBT or polyphenylene ether, and a phosphate ester. These are useful flame-retardant resin materials that do not use halogen-based flame retardants, but blending resins such as polyphenylene ether reduces mechanical strength, fluidity during injection molding, and the molded product turns yellow. However, it has a problem that it is poor in hydrolysis resistance and metal contamination and has limited applications. Patent Document 14 discloses a composition containing polyester, an organic phosphorus flame retardant containing a phosphate ester, glass fiber, and a vinyl resin. These are useful flame retardant resin materials that do not use a halogen-based flame retardant, but have problems of degradation of hydrolysis resistance and metal contamination due to the organophosphorus flame retardant.

  Patent Document 15 discloses that a phosphorus-containing compound containing a phosphate ester in a resin component containing a polyester resin and a styrene resin, a specific aromatic resin, an aromatic nylon, a polycarbonate resin, a polyarylate resin, a polyepoxy resin, and It is disclosed that a flame retardant composed of a polyphenylene ether resin is blended. The resin component containing the polyester resin and the styrene resin is a resin component useful for improving moldability such as warping, and the flame retardant is a useful flame retardant not using a halogen flame retardant. However, it had the problem of degradation of hydrolysis resistance and metal contamination due to phosphorus-containing compounds.

  Patent Documents 16 to 21 disclose that an aromatic phosphate ester and melamine cyanurate are blended. Although these are useful flame retardant resin materials that do not use a halogen-based flame retardant, there is a problem that it is difficult to obtain a balance between mechanical properties and flame retardancy.

JP 51-150553 A JP 58-108248 A JP 59-81351 A JP-A-5-78560 JP-A-5-287119 JP-A-5-295164 JP-A-5-320486 JP-A-5-339417 JP-A-10-77396 Japanese Patent Laid-Open No. 10-147699 Japanese Patent Laid-Open No. 10-182955 Japanese Patent Laid-Open No. 10-18295 JP 2000-26710 A Japanese Patent Laid-Open No. 2000-212412 JP 2001-49096 A Japanese Patent Laid-Open No. 3-281652 Japanese Patent Laid-Open No. 5-70671 Japanese Patent Laid-Open No. 7-233311 JP-A-8-73713 Japanese Patent Laid-Open No. 10-120881 WO2004 / 029154

  An object of the present invention is to provide a flame retardant polyester resin composition and a molded article excellent in a balance between flame retardancy and mechanical properties without using a halogen-based flame retardant.

That is, the present invention relates to a composition comprising (A) a polyester resin and (B) a salt of a triazine compound and cyanuric acid or isocyanuric acid, wherein (B) A flame retardant polyester resin composition comprising 35 to 70 parts by weight of the component, and the number of particles having a maximum diameter exceeding 15 μm of the component (B) in the composition is 0.5 or less per 100 μm × 100 μm cross section, and the composition It is a molded article comprising a flame retardant polyester resin composition.

  The molded article made of the flame-retardant polyester resin composition of the present invention uses a non-halogen flame retardant that is said to have little influence on the environment, and is highly safe against electric flames inside the equipment and highly resistant to fire of the molded article itself. Since it has flame retardancy, it is useful for electrical / electronic parts, mechanical mechanism parts, and automobile parts. Specifically, circuit breakers, electromagnetic switches, focus cases, flyback transformers, molded products for copiers and printer fixing machines, general home appliances, OA equipment housings, coil bobbins, connectors, relays, disk drive chassis , Transformers, switch parts, outlet parts, motor parts, sockets, plugs, capacitors, various cases, resistors, electrical / electronic parts with built-in metal terminals and conductors, computer-related parts, audio parts, laser parts, etc. , Lighting parts, telegraph / telephone equipment parts, air conditioner parts, home appliance parts such as VTRs and TVs, parts for copying machines, parts for facsimiles, parts for optical equipment, parts for automobile ignition devices, connectors for automobiles, and various automobile electrical equipment Examples include parts.

  In the present invention, since a highly reliable molded product having excellent performance against flame retardancy, hydrolysis resistance, and metal contamination can be obtained, relays, breakers, electromagnetic switches, focus cases, fly It is particularly useful for electrical and electronic parts such as molded parts for back transformers, copiers and printer fixing machines.

  In the resin composition of the present invention, the polyester resin as component (A) is selected from dicarboxylic acid or an ester-forming derivative thereof, diol or an ester-forming derivative thereof, hydroxycarboxylic acid or an ester-forming derivative thereof, and a lactone. A polymer or copolymer having one or more structural units as main structural units. A commercial item can also be used as a polyester resin. Among them, polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / terephthalate, polybutylene Aromatic polyester resins such as isophthalate / terephthalate, polyethylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, and polybutylene terephthalate / naphthalate are preferred. Further, a polyester resin selected from polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate and polycyclohexanedimethylene terephthalate is preferable from the balance of mechanical properties, flame retardancy and cost, and particularly a polyester resin selected from polyethylene terephthalate and polybutylene terephthalate is preferable. . It is also preferable to use these two or more types of aromatic polyester resins in any amount.

  Moreover, it is preferable to use PET and PBT together because the balance of moldability, flame retardancy and mechanical properties of the resin composition is excellent. In particular, PET / PBT = 0/100 to 80/20 wt% is preferable from the balance of moldability and flame retardancy, and 0/100 to 60/40 wt% is more preferable.

  In the resin composition of the present invention, the salt of the triazine compound as component (B) and cyanuric acid or isocyanuric acid is preferably an adduct of cyanuric acid or isocyanuric acid and triazine compound, usually 1 An adduct having a composition of 1 to 1 (molar ratio), optionally 1 to 2 (molar ratio). Of the triazine compounds, those that do not form a salt with cyanuric acid or isocyanuric acid are excluded. Of the salts of triazine compounds with cyanuric acid or isocyanuric acid, melamine, benzoguanamine, acetoguanamine, 2-amido-4,6-diamino-1,3,5-triazine, mono (hydroxymethyl) melamine Di (hydroxymethyl) melamine and tri (hydroxymethyl) melamine salts are preferred, and melamine, benzoguanamine and acetoguanamine salts are particularly preferred. These salts are produced by a known method. For example, a mixture of a triazine compound and cyanuric acid or isocyanuric acid is made into an aqueous slurry and mixed well to form both salts in the form of fine particles, and then the slurry is filtered and dried. A salt is obtained. Further, the above-mentioned salt does not need to be completely pure, and some unreacted triazine compound, cyanuric acid, or isocyanuric acid may remain. Moreover, the average particle diameter of the salt before being blended with the resin is preferably 0.01 to 100 μm from the viewpoint of flame retardancy, mechanical strength, heat and humidity resistance, residence stability and surface properties of the molded product. 80 μm is more preferable. In addition, when the dispersibility of the salt is poor, a dispersant such as tris (β-hydroxyethyl) isocyanurate, a known surface treatment agent, or the like may be used in combination. Further, the blending amount of the triazine compound and the salt of cyanuric acid or isocyanuric acid is preferably 1 to 70 parts by weight with respect to 100 parts by weight of the polyester resin in terms of flame retardancy and mechanical properties, and is 35 to 70 parts by weight. More preferably. When the salt content is more than 70 parts by weight, the flame retardancy and mechanical properties of the resin composition are not sufficient, which is not preferable.

  In the resin composition of the present invention, it is necessary that the average particle size of a salt of a triazine compound and cyanuric acid or isocyanuric acid having a maximum diameter of more than 15 μm is 1 or less per 100 μm × 100 μm cross section. The smaller the number of salt particles, the better the mechanical properties and flame retardancy of the resin composition and its molded product. Therefore, the average is preferably 0.5 or less, more preferably 0.2 or less. Here, the average means the average of the cross-sectional observation results of at least five places per one type of resin composition. The maximum diameter of the salt means the maximum length of the salt particles observed in a cross-sectional photograph. For example, if the particle is elliptical, it means the major axis, and if the particle is square, it means a long diagonal. The cross section is observed with an optical microscope or a transmission electron microscope. The optical microscope or transmission electron microscope apparatus used for observation is not particularly limited as long as it is a commonly used apparatus. The pretreatment of the sample of the cross-sectional photograph is not particularly limited, and dyeing or the like can be performed for easy observation. Observation with an optical microscope or a transmission electron microscope requires preparation of an ultrathin section, but it is also possible to embed it with a resin depending on the state of the sample. The observation magnification with an optical microscope or a transmission electron microscope is 200 to 1,000 times because observation of particles becomes difficult if the magnification is too small, and local observation occurs if the magnification is too large. In order to increase the accuracy of the observation result, it is also preferable to combine the observation result with the low magnification and the high magnification at the same observation site.

  In an X-ray diffraction spectrum of a salt of a triazine compound and cyanuric acid or isocyanuric acid, a strong diffraction line exists at 2θ = 11.0 ± 0.5 °. The inventors have found that this diffraction line greatly affects the dispersion of a salt of a triazine compound and cyanuric acid or isocyanuric acid in the resin. The full width at half maximum of the peak is preferably 0.5 ° or less, more preferably 0.4 ° or less, and further preferably 0.35 ° or less. A small half-value width of the peak of the diffraction line means that the crystal structures of the salts are complete. The inventors have found that although the reason is not clear, the salt is particularly difficult to aggregate and easily disperse in the resin when the half width of the peak is 0.4 ° or less. If the full width at half maximum is greater than 0.4 °, the salt is agglomerated in the resin due to agglomeration of the salt, and the mechanical properties are not sufficient.

  In addition, low molecular weight components and impurities are extracted from a salt of a triazine compound and cyanuric acid or isocyanuric acid with an organic solvent (such as methanol, benzene, or chloroform). In order to suppress uneven distribution in the resin due to aggregation of the salt, it is preferable that the amount of the extract is small. The amount of the extract with a mixed solvent of 80% methanol / 20% benzene is preferably 0.1% by weight or less, more preferably 0.06% by weight or less, and further preferably 0.05% by weight or less. If the amount of the extract exceeds 0.1% by weight, it is not preferable because it causes uneven distribution in the resin due to aggregation of the salt and the mechanical properties are not sufficient.

  In the resin composition of the present invention, it is possible to add one or more non-halogen flame retardants other than the component (B) as the component (C), shortening the combustion time during combustion or reducing the generated gas during combustion. Can be expected. Such other non-halogen flame retardants include, but are not limited to, for example, phosphate esters, phosphinates, aluminum hydroxide, hydrotalcite, boric acid, calcium borate, calcium borate hydrate, zinc borate, boric acid Examples thereof include zinc hydrate, zinc hydroxide, zinc hydroxide hydrate, zinc tin hydroxide, zinc tin hydroxide hydrate, red phosphorus, heat-expanded graphite, and dawsonite. Further, a thermosetting resin such as a thermosetting melamine resin, a thermosetting phenol resin, or a thermosetting epoxy resin may be mixed or coated on the surface. In addition, a coupling agent, an epoxy compound, or an oil and fat such as stearic acid may be mixed or coated on the surface. Among them, a compound selected from phosphoric acid esters and phosphinates is preferably used because of a good balance between mechanical properties and flame retardancy. Further, it is preferable to use a phosphoric acid ester and a phosphinic acid salt because the effect is further enhanced. The content of the component (C) is preferably 1 to 100 parts by weight and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the polyester in consideration of flame retardancy, hydrolysis resistance and metal contamination. . Exceeding 100 parts by weight is not preferable because it causes mold contamination.

上式において、Ａｒ^ｌ、Ａｒ^２、Ａｒ^３、Ａｒ^４は、同一または相異なる、ハロゲンを含有しない芳香族基を表す。また、Ｘは下記の（２）〜（４）式から選択される構造を示す。下記（２）〜（４）式中、Ｒ^１〜Ｒ^８は同一または相異なる水素原子または炭素数１〜５のアルキル基を表し、Ｙは直接結合、Ｏ、Ｓ、ＳＯ_２、Ｃ（ＣＨ_３）_２、ＣＨ_２およびＣＨＰｈから選ばれる基を表し、Ｐｈはフェニル基を表す。また、（１）式のｎは０以上の整数である。また、（１）式のｋ、ｍはそれぞれ０以上２以下の整数であり、かつ（ｋ＋ｍ）は０以上２以下の整数である。なお、かかる芳香族燐酸エステルは、異なるｎや、異なる構造を有する芳香族燐酸エステルの混合物であってもよい。

Although it does not specifically limit as phosphate ester, What is generally marketed and the synthesized phosphate ester can be used. Specific examples include tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tris-isopropylbiphenyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, octyl diphenyl Phosphate, orthophenylphenol phosphate, pentaerythritol phosphate, neopentyl glycol phosphate, substituted neopentyl glycol phosphonate, nitrogen-containing phosphate, and aromatic phosphate of the following formula (1) Can be mentioned. Of these, an aromatic phosphate is preferable, and an aromatic phosphate represented by the following formula (1) is particularly preferably used.

In the above formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ represent the same or different aromatic groups containing no halogen. X represents a structure selected from the following formulas (2) to (4). In the following formulas (2) to (4), R ^{1 to} R ⁸ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, Y represents a direct bond, O, S, SO ₂ , C (CH ₃ ) A group selected from ₂ , CH ₂ and CHPh, and Ph represents a phenyl group. Moreover, n of (1) Formula is an integer greater than or equal to 0. In the formula (1), k and m are each an integer of 0 or more and 2 or less, and (k + m) is an integer of 0 or more and 2 or less. The aromatic phosphate ester may be a mixture of aromatic phosphate esters having different n or different structures.

  More specifically, n in the formula (1) is an integer of 0 or more, and the upper limit is preferably 40 or less from the viewpoint of flame retardancy. n is preferably 0 to 10, particularly preferably 0 to 5.

  K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less. Preferably, k and m are each an integer of 0 or more and 1 or less, and particularly preferably, k and m are each 1.

In the formulas (2) to (4), R ^{1 to} R ⁸ represent the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-isopropyl and neopentyl. Tert-pentyl group, 2-isopropyl, neopentyl, tert-pentyl group, 3-isopropyl, neopentyl, tert-pentyl group, neoisopropyl, neopentyl, tert-pentyl group and the like. Among them, a group selected from hydrogen, a methyl group and an ethyl group is preferable, and hydrogen is particularly preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different aromatic groups containing no halogen. Examples of the aromatic group include an aromatic group having a skeleton selected from a benzene skeleton, a naphthalene skeleton, an indene skeleton, and an anthracene skeleton. Among them, those having a benzene skeleton or a naphthalene skeleton are preferable. These may be substituted with an organic residue containing no halogen, preferably an organic residue having 1 to 8 carbon atoms. When it has a substituent, the number of substituents is not particularly limited, but is preferably 1 to 3. Specific examples of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ include aromatic groups such as phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, naphthyl group, indenyl group and anthryl group. Of these, a group selected from a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group is preferable, and a group selected from a phenyl group, a tolyl group, and a xylyl group is particularly preferable.

As specific examples of the aromatic phosphate ester, the following compound (6) or (7) is preferable, and (6) is particularly preferable.

  As commercially available phosphoric acid esters, one or more selected from PX-200, PX-201, PX-130, CR-733S, TPP, CR-741, CR747, TCP, TXP and CDP manufactured by Daihachi Chemical Co., Ltd. Can be used. Preferably one or more selected from PX-200, TPP, CR-733S, CR-741 and CR747, particularly preferably selected from PX-200, CR-733S and CR-741 Can do. Among them, PX-200 is most preferable because it has a large effect of improving hydrolysis resistance and contact contamination when used in combination with a vinyl resin and an alkaline earth metal compound.

式中のＲ^９とＲ^１０は、同じかまたは異なり、Ｃ１〜Ｃ６のアルキル基もしくはアリール基である。Ｒ^９とＲ^１０は、直鎖であっても分岐であってもよく、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、およびフェニル基などが挙げられる。また、Ｒ^１１は、直鎖状または枝分かれしたＣ１〜Ｃ１０のアルキレン基もしくはＣ６〜Ｃ１０のアリーレン基、アルキルアリーレン基またはアリールアルキレン基であり、例えば、メチレン基、エチレン基、プロピレン基、イソプロピレン基、ｎ−ブチレン基、ｔｅｒｔ−ブチレン基、ペンチレン基、オクチレン基、ドデシレン基、フェニル基、ナフチレン基、メチルフェニレン基、エチルフェニレン基、メチルナフチレン基、エチルナフチレン基、ｔｅｒｔ−ブチルフェニレン基、およびｔｅｒｔ−ブチルナフチレン基などが挙げられる。Ｍは、カルシウム、アルミニウムまたは亜鉛である。Ｍとしては、アルミニウムが好ましい。また、ｐは１〜４、ｑは１〜４、ｒは１〜４である。 The phosphinic acid salt in the present invention is preferably a flame retardant comprising at least one selected from phosphinic acid salts, diphosphinic acid salts and polymers thereof. The phosphinic acid salt is preferably a metal salt selected from calcium, aluminum and zinc. Particularly preferred are flame retardants comprising a phosphinic acid salt of the following formula (8), a diphosphinic acid salt of the following formula (9) and one or more of these polymers.

R ⁹ and R ¹⁰ in the formula are the same or different and are a C1-C6 alkyl group or an aryl group. R ⁹ and R ¹⁰ may be linear or branched. For example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, and phenyl group Etc. R ¹¹ is a linear or branched C1-C10 alkylene group or a C6-C10 arylene group, an alkylarylene group, or an arylalkylene group, such as a methylene group, an ethylene group, a propylene group, or an isopropylene group. , N-butylene, tert-butylene, pentylene, octylene, dodecylene, phenyl, naphthylene, methylphenylene, ethylphenylene, methylnaphthylene, ethylnaphthylene, tert-butylphenylene, and tert -A butyl naphthylene group etc. are mentioned. M is calcium, aluminum or zinc. As M, aluminum is preferable. P is 1-4, q is 1-4, and r is 1-4.

  Examples of commercially available products include “Exolit” (registered trademark) OP1230 and OP1240 manufactured by Clariant Japan. In addition, a mixture containing a flame retardant comprising at least one selected from phosphinic acid salts, diphosphinic acid salts and polymers thereof, and a nitrogen-containing compound and / or a boron-containing compound is also commercially available. As such, OP1312 may be mentioned. OP1240 can be preferably used.

  An epoxy compound can be further blended in the polyester resin composition of the present invention. Examples of such epoxy compounds include glycidyl ester compounds, glycidyl ether compounds, and glycidyl ester ether compounds, and one or more of these can be used. In order to express the improvement effect excellent in hydrolysis resistance, an epoxy compound having an epoxy equivalent of less than 500 is preferable, and an epoxy compound having an epoxy equivalent of less than 400 is particularly preferable. Here, the epoxy equivalent is the number of grams of an epoxy compound containing 1 gram equivalent of an epoxy group. The epoxy equivalent can be obtained by dissolving the epoxy compound in pyridine, adding 0.05N hydrochloric acid, heating at 45 ° C, using a mixture of thymol blue and cresol red as an indicator, and back titrating with 0.05N caustic soda. it can. Moreover, as said epoxy compound, the epoxy compound which used the monofunctional glycidyl ester compound and the glycidyl ether compound together, or a monofunctional glycidyl ester compound is used preferably. In particular, a monofunctional glycidyl ester compound is more preferable from the balance of viscosity stability and hydrolysis resistance of the resulting composition. Specific examples of the glycidyl ester compound include, but are not limited to, glycidyl benzoate, glycidyl t-butylbenzoate, glycidyl p-toluate, glycidyl cyclohexanecarboxylic acid, glycidyl pelargonate, stearic acid Glycidyl ester, lauric acid glycidyl ester, palmitic acid glycidyl ester, behenic acid glycidyl ester, versatic acid glycidyl ester, oleic acid glycidyl ester, linoleic acid glycidyl ester, linolenic acid glycidyl ester, behenolic acid glycidyl ester, stearolic acid glycidyl ester, terephthalate Acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, naphthalene Carboxylic acid diglycidyl ester, bibenzoic acid diglycidyl ester, methylterephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, succinic acid Examples include diglycidyl ester, sebacic acid diglycidyl ester, dodecanedioic acid diglycidyl ester, octadecanedicarboxylic acid diglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid tetraglycidyl ester, and the like. Can be used. Further, the glycidyl ether compound is not limited, but specific examples include phenyl glycidyl ether, o-phenylphenyl glycidyl ether, 1,4-bis (β, γ-epoxypropoxy) butane, 1,6- Bis (β, γ-epoxypropoxy) hexane, 1,4-bis (β, γ-epoxypropoxy) benzene, 1- (β, γ-epoxypropoxy) -2-ethoxyethane, 1- (β, γ-epoxy Propoxy) -2-benzyloxyethane, 2,2-bis- [p- (β, γ-epoxypropoxy) phenyl] propane, and bis- (4-hydroxyphenyl) methane and the like obtained by reaction of epichlorohydrin A diglycidyl ether etc. are mentioned, These can use 1 type (s) or 2 or more types. Moreover, 0.1-5 weight part is preferable with respect to 100 weight part of polyester from the surface of a mechanical characteristic and hydrolysis resistance, and, as for the compounding quantity of an epoxy compound, Most preferably, it is 0.3-4 weight part.

  The polyester resin composition of the present invention can be blended with a fiber reinforcing material in order to improve mechanical strength. Examples of such fiber reinforcement include glass fiber, aramid fiber, and carbon fiber. Glass fiber is a chopped strand type or roving type glass fiber that is used as a reinforcing material for ordinary polyester resins. Silane coupling agents such as aminosilane compounds and epoxysilane compounds and / or urethane, vinyl acetate, bisphenol A Glass fibers treated with a sizing agent containing one or more epoxy compounds such as diglycidyl ether and novolac epoxy compounds are preferably used. Moreover, the silane coupling agent and / or sizing agent may be used in an emulsion liquid. In addition, the blending amount in the case of blending the fiber reinforcement is 100 parts by weight of polyester from the viewpoint of fluidity at the time of molding the polyester resin composition, durability of the molding machine and mold, and mechanical properties of the composition. 0 to 100 parts by weight is preferable, and 25 to 90 parts by weight is more preferable.

  Furthermore, the polyester resin composition of the present invention includes an inorganic material other than a fiber reinforcing material in order to improve a part of crystallization characteristics, arc resistance, anisotropy, mechanical strength, flame retardancy, or heat distortion temperature. A filler can be further blended. Examples of the inorganic filler other than the fiber reinforcing material include, but are not limited to, needle-like, granular, powdery, and layer-like inorganic fillers. Specific examples include glass beads, milled fibers, glass flakes, potassium titanate whiskers, calcium sulfate whiskers, wollastonite, silica, kaolin, talc, smectite clay minerals (montmorillonite, hectorite), vermiculite, mica, fluorine teniolite, Zirconium phosphate, titanium phosphate, dolomite and the like can be mentioned, and one or more are used. Moreover, surface treatments such as a coupling agent treatment, an epoxy compound, or an ionization treatment may be performed on the inorganic filler other than the above-described fiber reinforcement. The average particle size of the granular, powdery and layered inorganic fillers is preferably 0.1 to 20 μm, particularly preferably 0.2 to 10 μm from the viewpoint of impact strength. In addition, the blending amount of the inorganic filler other than the fiber reinforcing material is 100 parts by weight of the polyester in total with the blending amount of the fiber reinforcing agent from the viewpoint of fluidity of the composition at the time of molding and durability of the molding machine and the mold. The amount is preferably 0 to 100 parts by weight.

  By adding a fluorine resin to the polyester resin composition of the present invention, the flame retardant resin composition at the time of combustion can be prevented from melting and dropping, and the flame retardancy can be further improved. The fluorine-based resin is a resin containing fluorine in the molecule. Specifically, polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / Perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer, and the like. . Among them, polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer, and polyvinylidene fluoride are preferable. In particular, polytetrafluoroethylene and (tetrafluoroethylene / ethylene) copolymers are preferred. Moreover, the compounding quantity in the case of mix | blending a fluororesin is 0.02-5 weight part with respect to 100 weight part of polyester from the point of a flame retardance and a mechanical characteristic, If it is 0.2-2 weight part More preferred.

  The polyester resin composition of the present invention can be further improved in flame retardancy by further blending a polycarbonate resin. Examples of the polycarbonate resin include aromatic homo or copolycarbonates obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester. The aromatic homo or copolycarbonate resin preferably has a weight average molecular weight in the range of 10,000 to 1,100,000, a glass transition temperature of about 150 ° C., and a weight average molecular weight of 10,000 to 1,000. One in the range of 1,000 is more preferred. Polycarbonate resins having different weight average molecular weights may be used in combination. A polycarbonate resin having a weight average molecular weight in the range of 60,000 to 1,100,000 is particularly preferably used. The weight average molecular weight is obtained by measuring in terms of polystyrene by gel permeation chromatography using tetrahydrofuran as a solvent. A weight average molecular weight of less than 10,000 is not preferable because the mechanical properties of the polyester resin composition are reduced, and a weight average molecular weight of more than 110,000 is not preferable because the fluidity of the composition during molding is impaired. Further, those having a melt viscosity index (melt flow index) measured by a melt indexer according to ASTM D1238 under the condition of a load of 1.2 kg at a temperature of 300 ° C. are preferable, particularly mechanical properties. From this point, a polycarbonate resin of 1 to 15 g / 10 min is preferably used.

  As aromatic dihydric phenol compounds, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) ) Methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3,5-diphenyl) butane, 2,2 -Bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1- Phenyl-1,1-bis (4-hydroxyphenyl) ethane or the like can be used, and these can be used alone or as a mixture. Care must be taken because the hydrolysis resistance may be greatly reduced when a polycarbonate resin in an amount exceeding 20 parts by weight is blended with 100 parts by weight of polyester. The blending amount of the polycarbonate resin is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyester because of hydrolysis resistance and flame retardancy. Moreover, you may mix | blend a polycarbonate resin oligomer if it is the quantity of the range which does not impair the characteristic of this invention.

  Further, when a polycarbonate resin is blended, it is useful as a transesterification inhibitor between polyester and polycarbonate resin by blending a small amount of acidic phosphate ester, and particularly prevents a decrease in heat distortion temperature and the like. As the acidic phosphoric acid ester, an alkyl acid phosphate compound of a partial ester of alcohols and phosphoric acid is preferable, a low molecular weight one is a colorless liquid, and a high molecular weight one is a white waxy or flaky solid.

  Specific examples of the acid phosphate ester include, but are not limited to, monomethyl acid phosphate, monoethyl acid phosphate, monoisopropyl acid phosphate, monobutyl acid phosphate, monolauryl acid phosphate, monostearyl acid phosphate, monododecyl acid phosphate , Monobehenyl acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, lauryl acid phosphate, distearyl acid phosphate, didodecyl acid phosphate, dibehenyl acid phosphate, trimethyl acid phosphate, triethyl acid phosphate, triethyl acid phosphate Said thing Mixtures of di-, mono-, or a mixture of one or more thereof and the compounds of the di- and tri. Preferably used acidic phosphate esters include long chain alkyl acid phosphate compounds such as mixtures of mono and distearyl acid phosphates. Such a compound is commercially available from Asahi Denka Co., Ltd. under the name “Adeka Stub (registered trademark)” AX-71, and is a flaky solid having a melting point. Further, the blending amount of the acidic phosphoric acid ester is preferably 0.01 to 0.5 parts by weight, preferably 0.02 to 0.3 parts by weight with respect to 100 parts by weight of the polyester, from the viewpoint of heat distortion temperature and mechanical properties. More preferable.

  The polyester resin composition of the present invention can further contain flame retardant aids that assist in flame retardancy such as silicone compounds, phenol resins, phosphonitrile compounds, ammonium polyphosphate, and melamine phosphate, and one or more are used. The blending amount when blending the flame retardant aid is preferably 0.1 to 10 parts by weight, preferably 0.2 to 7.5 parts by weight, based on 100 parts by weight of the polyester, from the viewpoint of flame retardancy and mechanical properties. Part is more preferable.

  Examples of the silicone compound include silicone resin, silicone oil, and silicone powder. Examples of the silicone resin include polyorganosiloxanes in which a group selected from a saturated or unsaturated monovalent hydrocarbon group, a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryl group, a vinyl group, or an allyl group is chemically bonded to a siloxane. . Although what has the viscosity of about 200-300,000,000 centipoise at room temperature is preferable, it is not limited to it, Product shape may be oil form, powder form, and gum form. An epoxy group, a methacryl group and an amino group may be introduced as a functional group, or a mixture with two or more kinds of silicone resins may be used. Silicone oil includes polyorganosiloxane in which a siloxane is chemically bonded to a group selected from saturated or unsaturated monovalent hydrocarbon group, hydrogen atom, hydroxyl group, alkoxyl group, aryl group, vinyl group or allyl group. Is mentioned. Those having a viscosity of about 0.65 to 100,000 centistokes at room temperature are preferred, but the present invention is not limited thereto, and the product shape may be oily, powdery or gumy, and epoxy as a functional group. Groups, methacrylic groups and amino groups may be introduced. It may be a mixture of two or more kinds of silicone oils or silicone resins. Moreover, as a silicone powder, what mix | blended the inorganic filler with said silicone resin and / or silicone oil is mentioned. Silica or the like is preferably used as the inorganic filler.

  The phenol resin is arbitrary as long as it is a polymer having a plurality of phenolic hydroxyl groups, and examples thereof include novolak-type, resol-type and heat-reactive resins, and resins obtained by modifying these resins. These may be an uncured resin, a semi-cured resin, or a cured resin to which no curing agent is added. Among these, a novolak type phenol resin or a melamine-modified novolak type phenol resin which is non-thermally reactive with no addition of a curing agent is preferred in terms of flame retardancy, mechanical properties and economy. Further, the shape is not particularly limited, and any of pulverized products, granules, flakes, powders, needles, liquids, and the like can be used, and one or more can be used as necessary. Also, commercially available phenolic resins can be used. For example, in the case of a novolak-type phenol resin, the reaction vessel is charged with a molar ratio of phenols to aldehydes of 1: 0.7 to 1: 0.9, and oxalic acid, hydrochloric acid, sulfuric acid, toluenesulfone. After adding a catalyst such as acid, heating, refluxing for a predetermined time, vacuum dehydration or standing dehydration to remove the generated water, and removing remaining water and unreacted phenols Thus, a novolac type phenol resin can be obtained. The cocondensation phenol resin obtained by using these resins or a plurality of raw material components can be used alone or in combination of two or more. In the case of a resol type phenol resin, the molar ratio of phenols to aldehydes is charged into the reaction vessel at a ratio of 1: 1 to 1: 2, and sodium hydroxide, aqueous ammonia, other basic substances, etc. After adding the catalyst, it can be obtained by the same reaction and treatment as the novolak type phenol resin. Here, as phenols, phenol, o-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, isoeugenol, o-methoxyphenol, 4,4′-dihydroxy Examples include phenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, and 2,6-di-tert-butyl-p-cresol. These phenols can be used alone or in combination of two or more. On the other hand, aldehydes include formaldehyde, paraformaldehyde, polyoxymethylene, trioxane and the like. These aldehydes can be used alone or in combination of two or more as required. The molecular weight of the phenolic resin is not particularly limited, but is preferably 200 to 2,000 in terms of number average molecular weight, and particularly preferably in the range of 400 to 1,500 because of excellent mechanical properties, fluidity, and economy. The molecular weight of the phenolic resin can be measured by gel permeation chromatography by using a tetrahydrofuran solution and using a polystyrene standard sample.

  Examples of the phosphonitrile compound include phosphonitrile compounds mainly composed of a phosphonitrile linear polymer and / or a cyclic polymer, and may be either linear or cyclic, or a mixture. The phosphonitrile linear polymer and / or the cyclic polymer can be synthesized by a known method described in the author Sugawara “Synthesis and Application of Phosphazene Compounds”. For example, phosphorus pentachloride or phosphorus trichloride as a phosphorus source, ammonium chloride or ammonia gas as a nitrogen source are reacted in a known manner (the cyclic product may be purified), and the resulting substance is alcohol, phenol and amine. It can be synthesized by substituting with a kind.

  Examples of the ammonium polyphosphate include ammonium polyphosphate, melamine-modified ammonium polyphosphate, and carbamyl polyammonium phosphate. The ammonium polyphosphate may be coated with a thermosetting resin such as a phenol resin, a urethane resin, a melamine resin, a urea resin, an epoxy resin, or a urea resin that exhibits thermosetting properties. More than seeds may be used. Examples of the melamine polyphosphate include melamine polyphosphates such as melamine phosphate and melamine pyrophosphate, and one kind or two or more kinds may be used.

  In the present invention, an ethylene (co) polymer can be further blended for the purpose of improving toughness such as impact strength of the composition. Examples of such ethylene (co) polymers include ethylene polymers such as high density polyethylene, low density polyethylene, and ultra low density polyethylene, and ethylene copolymers. The ethylene copolymer is obtained by copolymerizing ethylene and a monomer copolymerizable therewith. Examples of the copolymerizable monomer include propylene, butene-1, vinyl acetate, isoprene, butadiene, monocarboxylic acids such as acrylic acid and methacrylic acid, or ester acids thereof, and dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid. Is mentioned. The ethylene copolymer can be produced by a known method. Specific examples of the ethylene copolymer include ethylene / propylene, ethylene / butene-1, ethylene / vinyl acetate, ethylene / ethyl acrylate, ethylene / methyl acrylate and ethylene / ethyl methacrylate acrylate. A copolymer obtained by grafting or copolymerizing an acid anhydride or glycidyl methacrylate with the above ethylene (co) polymer is also preferably used. One or more of these are used. Among ethylene (co) polymers, a copolymer obtained by grafting or copolymerizing acid anhydride or glycidyl methacrylate with polyethylene is preferably used because of its good compatibility with the polyester component.

  In addition, the blending amount in the case of blending the ethylene (co) polymer is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the polyester from the viewpoint of flame retardancy and impact strength of the resulting composition. 5 parts by weight is more preferable.

  The polyester resin composition of the present invention can further contain a hydrolysis resistance improving material such as a phenoxy resin, an oxazoline compound, and a carbodiimide compound, and a phenoxy resin is particularly preferably used. In the case of blending the hydrolysis resistance improving material, the blending amount is preferably 0.1 to 7.5 parts by weight with respect to 100 parts by weight of the polyester from the viewpoint of hydrolysis resistance and flame retardancy of the resulting composition. 0.2 to 5 parts by weight is more preferable.

  Moreover, as a phenoxy resin, the phenoxy resin obtained by making an aromatic dihydric phenol type compound and epichlorohydrin react with various compounding ratios is mentioned. The molecular weight of the phenoxy resin is not particularly limited, but a viscosity average molecular weight in the range of 1,000 to 100,000 is preferable. Here, examples of the aromatic dihydric phenol compound include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and bis (4 -Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3,5 diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) methane and the like can be used, and these can be used alone or as a mixture. In addition, the shape of the phenoxy resin is not particularly limited, and any of pulverized products, granules, flakes, powders, liquids, and the like can be used. These phenoxy resins can be used alone or in combination of two or more as required.

  The polyester resin composition of the present invention further includes a hindered phenolic antioxidant and / or phosphine as a stabilizer so that the composition of the present invention provides extremely good heat aging resistance even when exposed to a high temperature for a long period of time. A phyto antioxidant can be blended. In the case of blending a hindered phenolic antioxidant and / or a phosphite antioxidant, the blending amount is 0.1 to 1 part by weight with respect to 100 parts by weight of polyester from the viewpoint of heat aging resistance and flame retardancy. Is preferable, and 0.2 to 0.5 part by weight is more preferable. If the blending amount is less than 0.1 parts by weight, the heat aging resistance is not sufficient, and if it exceeds 1 part by weight, the mechanical properties and flame retardancy are impaired, which is not preferable.

  Specific examples of the hindered phenol antioxidant include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2 -Thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3 , 5-Di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-2,4,6-to (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, bis or tris (3-tert-butyl-6-methyl-4-hydroxyphenyl) propane, N, N′-hexamethylenebis (3 , 5-di-t-butyl-4-hydroxy-hydrocinnamide), N, N′-trimethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) and the like. It is done.

  Examples of phosphite stabilizers include tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, tris Nonylphenyl phosphite, alkylallyl phosphite, trialkyl phosphite, triallyl phosphite, pentaerythritol phosphite compound and the like can be mentioned.

  By adding one or more lubricants to the polyester resin composition of the present invention, it is possible to improve the fluidity and releasability during molding. Examples of such lubricants include metal soaps such as calcium stearate and barium stearate, fatty acid esters, fatty acid ester salts (including partially salted products), fatty acid amides such as ethylene bisstearoamide, ethylenediamine and stearic acid, and Fatty acid amide, polyalkylene wax, acid anhydride-modified polyalkylene wax composed of polycondensate composed of sebacic acid or polycondensate of phenylenediamine and stearic acid and sebacic acid However, it is not limited to this. When the lubricant is blended, the addition amount is preferably 0.05 to 2 parts by weight and more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the polyester.

  In the polyester resin composition of the present invention, the resin can be toned in various colors by further blending carbon black, titanium oxide, and one or more pigments and dyes of various colors, It is also possible to improve weather resistance (light) and conductivity. In the case of blending pigments and dyes, the blending amount is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of polyester, and 0.1 to 5 parts by weight from the viewpoint of mechanical properties of the resulting composition. More preferred.

Carbon black includes, but is not limited to, channel black, furnace black, acetylene black, anthracene black, oil smoke, pine smoke, and graphite. Average particle size below 500 nm, carbon black dibutyl phthalate absorption 50~400cm ³ / 100g is preferably used. The treatment agent may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, silane coupling agent or the like. As titanium oxide, titanium oxide having a crystal form such as a rutile form or anatase form and having an average particle diameter of 5 μm or less is preferably used. The treatment agent may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, silane coupling agent or the like. In addition, carbon black, titanium oxide, and pigments and dyes of various colors are melted with various thermoplastic resins in order to improve dispersibility with the flame-retardant resin composition of the present invention and to improve handling during production. It may be used as a blended material or a blended mixed material. In particular, polyalkylene terephthalate is preferably used as the thermoplastic resin.

  Furthermore, known additions such as sulfur-based antioxidants, ultraviolet absorbers, plasticizers, and antistatic agents are added to the flame-retardant polyester resin composition and molded product of the present invention within a range that does not impair the object of the present invention. A material containing one or more kinds of agents can also be used.

  In the present invention, the addition of polyphenylene ether resin and polyphenylene sulfide resin further improves the flame retardancy, but it is preferable not to add it because the tracking resistance, hydrolysis resistance and metal contamination may be reduced. . When blended, it is preferable not to exceed 5% by weight.

  The flame-retardant polyester resin composition and molded article of the present invention are produced by a known method. For example, polyester resin, vinyl resin, phosphate ester, salt of triazine compound with cyanuric acid or isocyanuric acid, alkaline earth metal compound, and if necessary, fiber reinforcement such as epoxy compound, glass fiber, etc. Depending on the type, inorganic fillers other than fiber reinforcements, fluorine compounds, polycarbonate resins, various flame retardant aids, ethylene (co) polymers, hydrolysis resistance improvers, hindered phenolic antioxidants, phosphites Flame retardant polybutylene by premixing system antioxidants and other necessary additives, colorants such as pigments and dyes, or supplying them to a kneader without premixing and melt-kneading them sufficiently A terephthalate resin composition is prepared. Examples of premixing include dry blending and mixing using mechanical mixers such as tumblers, ribbon mixers and Henschel mixers. Further, the fiber reinforcing material may be added by adding a side feeder in the middle of the original loading part and the vent part of a multi-screw extruder such as a twin-screw extruder. In addition, in the case of liquid additives, a method of adding using a plunger pump by installing a liquid addition nozzle in the middle of the main loading part and the vent part of a multi-screw extruder such as a twin screw extruder and the original loading part For example, a method of supplying with a metering pump may be used.

  Further, the kneading machine is not limited. For example, a single-screw extruder, a twin-screw extruder, a tri-screw extruder, a kneader-type kneader equipped with a “unimelt” or “Dalmage” type screw, etc. Can be used.

  The flame retardant polyester resin composition thus obtained can be molded by a known method. For example, a molded article having any shape can be obtained by injection molding, extrusion molding, compression molding, sheet molding, film molding, or the like. In particular, injection molding is suitable, and insert molding in which a part of a metal part is directly integrated with a molded product can also be performed.

  The effects of the present invention will be described in further detail with reference to examples. Here, “%” and “part” all represent “% by weight” and “part by weight”, and “/” in the reference examples means copolymerization.

Reference Example 1 Polybutylene terephthalate resin (hereinafter abbreviated as PBT)
1100S (Toray Industries, Inc.) PBT having an intrinsic viscosity of 0.85 (25 ° C., orthochlorophenol solvent) was used.

Reference Example 2 Polyethylene terephthalate resin (hereinafter abbreviated as PET)
PET having an intrinsic viscosity of 0.65 (25 ° C., 1: 1 mixed solvent of phenol / tetrachloroethane) was used.

Reference Example 3 Salt <B-1> MCA-12 (manufactured by Sichuan Fine Chemical Research Institute) of triazine compound and cyanuric acid or isocyanuric acid
<B-2> MC-15 (Made by Sichuan Fine Chemical Research Institute)
<B-3> MC4000 (manufactured by Nissan Chemical Co., Ltd.)
<B-4> MC4500 (Nissan Chemical Co., Ltd.)
<B-5> MC6000 (Nissan Chemical Co., Ltd.)
The X-ray diffraction spectra of these salts were measured using an X-ray diffraction apparatus (manufactured by Rigaku Corporation, Multiflex). Among the obtained X-ray diffraction spectra, the half width of the diffraction line having the maximum peak intensity among the diffraction lines existing at 2θ = 11.0 ± 0.5 ° was measured. In addition, methanol / benzene extraction was carried out by placing 5 g of a sample in 200 ml of 80% methanol / 20% benzene mixed solvent, extracting by stirring and heating at 70 ° C. for 4 hours, and then cooling and filtering, and the weight of the filtrate dried. I asked more. Table 1 shows the maximum peak half-value width of 2θ = 11.0 ± 0.5 ° diffraction line in the X-ray diffraction spectrum and the amount of methanol / benzene extracted.

Reference Example 4 Phosphate Ester An aromatic phosphate ester of the following formula (10) (PX-200 manufactured by Eighth Chemical Co., Ltd.) was used.

Reference Example 5 Phosphinic Acid salt “Exolit OP1240” manufactured by Clariant was used as the phosphinic acid metal salt.

  Reference Example 6 Polycarbonate resin (hereinafter abbreviated as PC) “Iupilon” S3000 (manufactured by Mitsubishi Engineering Plastics) was used.

  Reference Example 7 Polyphenylene sulfide “Torelina” M2588 (manufactured by Toray Industries, Inc.) (hereinafter abbreviated as PPS) was used.

Reference Example 8 Fiber Reinforcement Material Glass fiber (hereinafter abbreviated as GF) “ECS T-187” (manufactured by Nippon Electric Glass Co., Ltd.) having a fiber diameter of about 13 μm was used.

Reference Example 9 Fluorine compound Polytetrafluoroethylene “Teflon (registered trademark) 6-J” (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) was used (hereinafter abbreviated as Teflon). 0.2 part by weight was added to the resin materials of all Examples.

Reference Example 10 Silicone Compound Silicone powder “DC4-7105” (manufactured by Toray Dow Corning Silicone) was used. 0.2 part by weight was added to the resin materials of all Examples.

Reference Example 11 Alkaline earth metal compound Calcium carbonate “KSS1000” (manufactured by Dowa Calfine Co., Ltd.) was added to 0.2 parts by weight of the resin materials of all Examples.

Reference Example 12 Hindered Phenol Antioxidant Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] hindered phenol antioxidant “IR-1010” ( Ciba Specialty Chemicals) was used. 0.2 part by weight was added to the resin materials of all Examples.

Examples 1 , 3, 5-9 and Comparative Examples 1-8
Using a twin screw extruder with a screw diameter of 30 mm and L / D35 with the same direction rotation vent (manufactured by Nippon Steel Works, TEX-30α), various raw materials are mixed in the composition shown in Tables 2 to 4, Added. Moreover, in the example which mix | blended GF, the side feeder was installed in the middle of the original containing part and the vent part, GF was added, and raw materials other than GF were added from the original containing part. Melting and mixing were performed under extrusion conditions of a kneading temperature of 270 ° C. and a screw rotation of 150 rpm, the molten mixture was discharged in a strand shape, passed through a cooling bath, and pelletized by a strand cutter.

  Using the obtained pellets or drying the obtained pellets, each test piece was molded, and the following physical properties were measured. The results are shown in Tables 2-4. The measuring method of each characteristic is as follows.

(1) Flame retardancy Using a Toshiba Machine IS55EPN injection molding machine, the flame retardancy evaluation test piece was injection molded under the conditions of a molding temperature of 270 ° C and a mold temperature of 70 ° C. The flame retardancy was evaluated according to the evaluation criteria. Flame retardancy decreases in the order of V-0>V-1> V-2. Moreover, the thickness of the test piece used 1/32 inch, 1/16 inch, and 1/8 inch thickness. In general, the flame retardancy of the material is higher when the evaluation standard is satisfied even with the same V-0 rank or with a thin test piece.

(2) Tensile test Using an IS55EPN injection molding machine manufactured by TOSHIBA KIKI, a 4 mm thick ISO527 dumbbell test piece was injection molded under conditions of a molding temperature of 270 ° C and a mold temperature of 70 ° C. Strength and tensile elongation were measured.

(3) Bending test Using an IS55EPN injection molding machine manufactured by TOSHIBA KIKI, 4mm-thick ISO527 dumbbell test pieces were injection-molded under conditions of a molding temperature of 270 ° C and a mold temperature of 70 ° C, and bent according to ISO527-1,2. Strength was measured.

(4) Charpy impact test Using a IS55EPN injection molding machine manufactured by Toshiba Machine, injection molding of a strip-shaped product with a thickness of 4 mm under the conditions of a molding temperature of 260 ° C and a mold temperature of 70 ° C, and Charpy impact strength according to ISO179. (Notched) was measured.

(5) Cross-sectional observation of test piece After cutting an ultra-thin section from the above-mentioned ISO 527 dumbbell test piece, it was magnified 400 times with an optical microscope (Nikon Corporation ECLIPSE LV100), and a cross-section was observed for an arbitrary 300 μm × 300 μm. went. The number of particles having a maximum particle size of more than 15 μm was examined at each observation place, and converted to the number of particles per 100 μm × 100 μm.

(6) Formability Using a Toshiba Machine IS55EPN injection molding machine, a box-shaped product with a side of 30 mm and a thickness of 1 mm is molded under conditions of a molding temperature of 270 ° C and a mold temperature of 70 ° C. The sex was confirmed.

(7) Mold Stain Using a Toshiba Machine IS55EPN injection molding machine, after molding 1000 shots of a box-shaped molded product with a side of 30 mm and a thickness of 1 mm under the conditions of a molding temperature of 270 ° C. and a mold temperature of 70 ° C., the mold The degree of dirt was confirmed.

  The molded article comprising the flame-retardant polyester resin composition of the present invention uses a non-halogen flame retardant that is said to have little impact on the environment, safety against electric flame inside the equipment, against the fire of the molded article itself, Since it has high flame retardancy, it is useful for electrical / electronic parts, mechanical mechanism parts, and automobile parts. Specifically, circuit breakers, electromagnetic switches, focus cases, flyback transformers, molded products for copiers and printer fixing machines, general home appliances, OA equipment housings, coil bobbins, connectors, relays, disk drive chassis , Transformers, switch parts, outlet parts, motor parts, sockets, plugs, capacitors, various cases, resistors, electrical / electronic parts with built-in metal terminals and conductors, computer-related parts, audio parts, laser parts, etc. , Lighting parts, telegraph / telephone equipment parts, air conditioner parts, home appliance parts such as VTRs and TVs, parts for copying machines, parts for facsimiles, parts for optical equipment, parts for automobile ignition devices, connectors for automobiles, and various automobile electrical equipment Examples include parts.

  In the present invention, since a highly reliable molded product having excellent performance against flame retardancy, hydrolysis resistance, and metal contamination can be obtained, relays, breakers, electromagnetic switches, focus cases, fly It is particularly useful for electrical and electronic parts such as molded parts for back transformers, copiers and printer fixing machines.

Claims (8)

A composition comprising (A) a polyester resin and (B) a salt of a triazine-based compound and cyanuric acid or isocyanuric acid, the component (B) 35 to 70 weights per 100 parts by weight of the component (A) And the number of particles having a maximum diameter of more than 15 μm of the component (B) in the composition is 0.5 or less per 100 μm × 100 μm cross section , and in the X-ray diffraction spectrum of the component (B), 2θ = A flame-retardant polyester resin composition in which a half-width of a diffraction line having the maximum peak intensity among diffraction lines existing at 11.0 ± 0.5 ° is 0.35 ° or less. 2. The flame retardant polyester resin composition according to claim 1, wherein the amount of the extract of the component (B) in the 80 vol% methanol / 20 vol% benzene mixed solvent is 0.06 wt% or less. 2. The flame retardant according to claim 1, further comprising (C) a compound selected from phosphoric acid esters and phosphinates, and 1 to 100 parts by weight of the component (C) with respect to 100 parts by weight of the component (A). Polyester resin composition. The flame-retardant polyester resin composition according to claim 1, wherein the component (A) is a polyester selected from polyethylene terephthalate and polybutylene terephthalate. The flame-retardant polyester resin composition according to claim 3 , wherein the component (C) contains a phosphate ester and a phosphinate. The flame-retardant polyester resin composition according to claim 3 , wherein the phosphoric acid ester of the component (C) contains at least one aromatic phosphoric acid ester. The flame retardant polyester resin composition according to claim 3 , wherein the phosphinic acid salt of component (C) contains at least one metal salt selected from calcium, aluminum, and zinc. A molded article comprising the flame retardant polyester resin composition according to any one of claims 1 to 7 .