JP2005325215A - Molded article having welded region - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a molded article which has a welded region excellent in high flame retardancy, injection moldability, strength of the welded region and heat resistance and is useful for machine mechanism parts, electric/electronic parts and automobile parts by blending a specific non-halogen flame retardant and a fiber reinforcement with a polyalkylene terephthalate resin. <P>SOLUTION: The molded article having a welded region is made of a flame retardant resin composition comprising (A) 100 pts.wt. of a polyalkylene terephthalate resin, (B) 1-50 pts.wt. of a phosphate, (C) 1-70 pts.wt. of a salt of a triazine-based compound surface-treated with a metal oxide and cyanuric acid or isocyanuric acid and (D) 1-150 pts.wt. of a fiber reinforcement. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention includes a polyalkylene terephthalate resin and a specific non-halogen flame retardant and a fiber reinforcing material, and a molded product having a weld part excellent in high flame resistance, injection moldability, weld part strength and heat resistance. It is a molded product useful for mechanical mechanism parts, electrical / electronic parts, and automobile parts.

  Polyalkylene terephthalate resins (PAT) such as polybutylene terephthalate resin (PBT), polytrimethylene terephthalate (PTT), polyethylene terephthalate resin (PET), polyethylene naphthalate resin (PNT), and polycyclohexanedimethylene terephthalate resin (PCT) Is utilized in a wide range of fields such as mechanical mechanism parts, electrical / electronic parts, and automobile parts, taking advantage of its excellent mechanical properties.

  Since PAT is flammable in nature, it is safe against 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 automobile parts. That is, flame retardancy is required, and high flame retardancy that indicates V-0 of the UL-94 standard is often required.

  As a method for imparting flame retardancy to PBT, a method in which a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant aid are compounded into a 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 the hydrated metal compound, which has the disadvantage of losing the original properties of the resin.

  On the other hand, the addition of red phosphorus as a method of making a thermoplastic resin flame retardant without using such a hydrated metal compound is disclosed in many publications such as Patent Document 1, Patent Document 2, and Patent Document 3. ing.

  However, although it is a useful flame-retardant resin material that does not use a halogen-based flame retardant, it has a problem that its use is limited because it has unique coloring and the color tone of the product is limited.

  Patent Document 4, Patent Document 5, and Patent Document 6 describe a method for producing surface-treated melamine cyanurate and a resin composition.

  Patent Literature 7, Patent Literature 8, Patent Literature 9, and Patent Literature 10 disclose blending an aromatic phosphate and melamine cyanurate.

  Further, in Patent Document 11, flame retardancy and molding are obtained by blending a rubber-modified styrene resin and a thermoplastic resin such as polyphenylene ether with a phosphate ester and a triazine skeleton-containing compound such as melamine having a particle size of 0.01 to 10 μm. A composition excellent in product appearance is disclosed.

  Further, Patent Document 12 discloses that a thermoplastic ester and a melamine cyanurate having a particle size of 60 to 250 μm are blended with thermoplastic polyester.

Many of electric / electronic parts and automobile parts are formed by injection molding, but the thickness tends to be reduced for weight reduction. In addition, the thinner the flow, the slower the flow of molten resin during injection molding. In many cases, injection molding is performed with a multipoint gate (flow path) to cover the flow. The problem with injection molding with the above-mentioned multipoint gate is that the flow path of the molten resin is increased, so a portion where the molten resin and the molten resin are joined (weld portion) always occurs, and the strength of the weld portion is generally large. Therefore, a material having excellent weld strength is required. The flame retardant resin composition obtained by the above-mentioned known method has a problem that the weld part has a low strength due to the blending of a large amount of flame retardant, so that the weld part of the obtained molded product is easily damaged, that is, the weld strength. Inferior to that. In addition, the flame retardant resin composition containing a fiber reinforcing material has a problem that warp is likely to occur, and there has been a demand for a molded product in which the decrease in weld strength is small and warpage is unlikely to occur.
JP 51-150553 A JP 58-108248 A JP-A-5-78560 Japanese Patent Laid-Open No. 7-224049 Japanese Patent Application Laid-Open No. 11-292861 JP-A-11-310577 Japanese Patent Laid-Open No. 3-281652 Japanese Patent Laid-Open No. 5-70671 Japanese Patent Laid-Open No. 7-233311 Japanese Patent Laid-Open No. 10-120881 JP-A-5-287119 Japanese Patent Laid-Open No. 10-316843

  That is, the present invention blends a specific non-halogen flame retardant and a fiber reinforcing material with a polyalkylene terephthalate resin, and has a weld part excellent in high flame resistance, injection moldability, weld part strength and heat resistance. It is an object to obtain a molded product useful for mechanical mechanism parts, electric / electronic parts, and automobile parts.

That is, the present invention
(A) (A) 100 parts by weight of polyalkylene terephthalate resin, (B) 1-50 parts by weight of a phosphate ester, (C) a triazine compound surface-treated with a metal oxide and cyanuric acid or isocyanuric acid A molded article having a weld site made of a flame retardant resin composition comprising 1 to 70 parts by weight of salt and (D) 1 to 150 parts by weight of a fiber reinforcing material;
(B) The molded product having a weld part made of the flame retardant resin composition according to (a), wherein the (A) polyalkylene terephthalate resin is a polyethylene terephthalate resin,
(C) The molded article having a weld site comprising the flame retardant resin composition according to claim 1 or 2, wherein the phosphate ester of (B) is an aromatic phosphate ester of the following formula (1):

(In the above formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ represent the same or different aromatic groups that do not contain halogen. X is 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 ) ₂ , CH ₂ , CHPh, Ph represents a phenyl group, and n in the formula (1) represents a degree of polymerization and is an integer of 0 or more. And 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.)

(D) A molded article having a weld part according to any one of (a) to (c) that meets the V-0 standard of the UL-94 combustion test at a thickness of 1/64 "(about 0.4 mm). ,
(E) The weld comprising the flame-retardant resin composition according to any one of (a) to (d), further comprising 0.1 to 10 parts by weight of an epoxy compound (E) Molded article having a part,
(F) The molded article having a weld site made of the flame retardant resin composition according to (e), wherein the epoxy compound (E) is a monofunctional glycidyl ester having an epoxy equivalent of less than 400;
(G) The flame-retardant resin composition according to any one of (a) to (f), further comprising 0.1 to 10 parts by weight of an alkaline earth metal compound (F). A molded article having a weld site consisting of
(H) a weld site comprising the flame retardant resin composition according to (g), wherein the (F) alkaline earth metal compound is one or more alkaline earth metal compounds selected from magnesium, calcium, and barium; Molded article having,
(I) (G) The flame retardant resin composition according to any one of (A) to (H), further comprising 0.05 to 10 parts by weight of a fluorine-based compound. A molded article having a weld site,
(Nu) The molded article having the weld part according to any one of (a) to (l), wherein the molded article is a mechanical mechanism part, an electric / electronic part, or an automobile part,
It is.

  The present invention blends a specific non-halogen flame retardant and a fiber reinforcement with a polyalkylene terephthalate resin, and has a weld part that has high flame resistance, injection moldability, weld part strength, and heat resistance. It is a molded product useful for machine mechanism parts, electrical / electronic parts, and automobile parts.

  Hereinafter, the present invention will be described in detail.

  The (A) polyalkylene terephthalate resin in the present invention is a polymer obtained by a polycondensation reaction between terephthalic acid or an ester-forming derivative thereof and a glycol component or an ester-forming derivative thereof. , Isophthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, dodecanedioic acid, oxalic acid and the like. Examples of the glycol component include ethylene glycol, 1,4-butanediol, propylene glycol, neopentyl glycol, 1,5- Pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, etc., or a long chain glycol having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-propylene Glycol, polytetramethylene glycol and the like, can also be used with one or more. Examples of typical polyalkylene terephthalate resins include polybutylene terephthalate resin (PBT), polytrimethylene terephthalate (PTT), polyethylene terephthalate resin (PET), polyethylene naphthalate resin (PNT), and polycyclohexanedimethylene terephthalate resin. (PCT) and the like may be used, and may be used in combination.

  In addition, isophthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, dodecanedioic acid, oxalic acid and the like may be copolymerized or used in combination of two or more.

  The (A) polyalkylene terephthalate resin or copolymer has an intrinsic viscosity of 0.36 to 1.60, particularly 0.42 measured at 25 ° C. using a 1: 1 mixed solvent of phenol / tetrachloroethane. It is suitable from the viewpoint of impact strength and moldability of the composition obtained in the range of 1.25. The (A) polyalkylene terephthalate resin may be used in combination with the same type of polyalkylene terephthalate resin having different intrinsic viscosities, and the (A) polyalkylene terephthalate resin having an intrinsic viscosity in the range of 0.36 to 1.60. It is preferable to use it.

  Furthermore, these (A) polyalkylene terephthalate resins have a COOH end group amount determined by potentiometric titration of an m-cresol solution with an alkaline solution in the range of 1 to 50 eq / t (end group amount per ton of polymer). A thing can be preferably used from a durable point. In particular, those having a COOH end group of 45 eq / t or less, more preferably 30 eq / t or less, and even more preferably 20 eq / t or less can be preferably used since they have excellent hydrolysis resistance.

  Moreover, flame retardance is excellent by using a polyethylene terephthalate resin among (A) polyalkylene terephthalate resin in this invention, and high flame retardance is obtained with a small flame retardant amount.

  In addition, (A) one or more polyester resins such as polyarylate resin, wholly aromatic liquid crystal polyester, and semi-aromatic liquid crystal polyester may be blended with polyalkylene terephthalate resin, and the blending amount has the effect of the present invention. The amount is in a range that does not greatly decrease.

  Although (B) phosphate ester in this invention is not limited, 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 phosphates, pentaerythritol phosphates, neopetyl glycol phosphates, substituted neopetyl glycol phosphonates, nitrogen-containing phosphates, and aromatic phosphates of the following formula (1) In particular, aromatic phosphates of the following formula (1) are preferably used.

(In the above formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ represent the same or different aromatic groups that do not contain halogen. X is 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 ) ₂ , CH ₂ , CHPh, Ph represents a phenyl group, n in the formula (1) is an integer of 0 or more, and k and m in the formula (1) are Each is 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 is a mixture of aromatic phosphate esters having different n or different structures. May be.

  In the formula of the formula (1), n is an integer of 0 or more, and the upper limit is preferably 40 or less from the viewpoint of flame retardancy. Preferably it is 0-10, Most preferably, it is 0-5.

  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 or m is an integer of 0 or more and 1 or less, particularly preferably k or m. Is 1 respectively.

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, etc., but hydrogen, methyl group, ethyl group are 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 aromatic groups having a benzene skeleton, a naphthalene skeleton, an indene skeleton, and an anthracene skeleton, and among them, those having a benzene skeleton or a naphthalene skeleton are preferable. These may be substituted with a halogen-free organic residue (preferably an organic residue having 1 to 8 carbon atoms), and the number of substituents is not particularly limited, but may be 1 to 3. preferable. Specific examples include phenyl groups, tolyl groups, xylyl groups, cumenyl groups, mesityl groups, naphthyl groups, indenyl groups, anthryl groups and the like, but phenyl groups, tolyl groups, xylyl groups, cumenyl groups, A naphthyl group is preferable, and a phenyl group, a tolyl group, and a xylyl group are particularly preferable.

  Of these, the following compounds (6) and (7) are preferable, and the compound (6) is particularly preferable.

  As commercially available phosphoric acid esters, PX-200, PX-201, PX-202, PX-130, CR-733S, TPP, CR-741, CR747, TCP, TXP, CDP, manufactured by Daihachi Chemical Industry Co., Ltd. One or more selected from SH-0890 can be used, preferably one or more selected from PX-200, PX-202, TPP, CR-733S, CR-741, CR747, In particular, PX-200, PX-202, CR-733S, and CR-741 are preferably used from the viewpoints of hydrolyzability and metal contamination of molded articles obtained.

  The blending amount of (B) phosphate ester is 1 to 50 parts by weight, preferably 100 parts by weight of (A) polyalkylene terephthalate resin, preferably from the viewpoint of flame retardancy and heat resistance of the molded product having a weld site. It is 2-45 weight part, More preferably, it is 3-40 weight part.

  Examples of the metal oxide in the salt of the triazine compound surface-treated with the metal oxide (C) and cyanuric acid or isocyanuric acid in the present invention include metals such as silica, aluminum oxide, antimony oxide, titanium oxide, and tin oxide. It is one or more of oxides, and is surface-treated by fixing the metal oxide to the surface of particles of a triazine compound and a salt of cyanuric acid or isocyanuric acid.

  The surface treatment of triazine compounds and cyanuric acid or isocyanuric acid salts includes methods of adding polyvinyl alcohol and cellulose ethers in addition to metal oxides, methods of surface treatment with water-soluble polymers, and nonionics. Although surface treatment with a surfactant or the like is also known, there are problems such as a decrease in hydrolyzability and easy coloring of the flame-retardant polyethylene terephthalate resin composition.

  Further, the triazine compound surface-treated with a metal oxide, the triazine compound in the salt of cyanuric acid or isocyanuric acid, and the salt of cyanuric acid or isocyanuric acid include cyanuric acid or isocyanuric acid and triazine compound. Adducts are preferred, which are usually one-to-one (molar ratio) and optionally one-to-two (molar ratio) compositions, and do not form salts with cyanuric acid or isocyanuric acid among triazine compounds. Things 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 and are prepared by known methods. For example, triazine compounds and cyanuric acid or isocyanate A mixture of nouric acid is made into an aqueous slurry, and mixed well to form both salts in the form of fine particles, and then mixed with a metal oxide sol, and this slurry is generally filtered and dried. The 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 blending with the resin is preferably 50 to 0.01 μm, more preferably in terms of flame retardancy, mechanical strength, heat and humidity resistance, retention stability, and surface properties of the molded product. Is 45 to 1 μm. In addition, when the dispersibility of the salt is poor, a dispersant such as tris (β-hydroxyethyl) isocyanurate may be used in combination. The particle diameter is an average particle diameter measured with a 50% cumulative distribution particle diameter by the laser micron sizer method.

  The amount of (C) the triazine compound surface-treated with the metal oxide and the salt of cyanuric acid or isocyanuric acid is 1 to 70 parts by weight, preferably 2 to 65 parts by weight, more preferably 3 to 60 parts by weight. Parts by weight.

  Examples of the (D) fiber reinforcing material in the present invention include glass fibers, aramid fibers, and carbon fibers. The above glass fiber is a chopped strand type or roving type glass fiber, such as a silane coupling agent such as an aminosilane compound or an epoxysilane compound, and / or urethane, vinyl acetate, bisphenol A diglycidyl ether, a novolac epoxy compound, or the like. Glass fibers treated with a sizing agent containing one or more epoxy compounds are preferably used. The silane coupling agent and / or sizing agent may be used as an emulsion.

  Further, (D) the fiber reinforcing material has a great effect on improving the mechanical strength of the flame retardant resin composition of the present invention, and the blending amount thereof is the fluidity at the time of injection molding of a molded product having a weld site. From the viewpoint of the durability of the injection molding machine or the mold, it is 1-150 parts by weight, preferably 2-145 parts by weight, more preferably 3-140 parts by weight with respect to 100 parts by weight of the (A) polyalkylene terephthalate resin. .

  Further, in the present invention, (D) an inorganic filler other than the fiber reinforcement can be blended, and the crystallization characteristics, arc resistance, anisotropy, mechanical strength of the molded article having the weld portion of the present invention, This is to improve a part of flame retardancy or heat distortion temperature, and in particular, since it is effective in anisotropy, a molded product having a weld portion with less warpage can be obtained. Specific examples of inorganic fillers other than fiber reinforcement include, but are not limited to, needle-like, granular, powdery and layered 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, and dolomite And used in one or more types. In particular, when gas beads, glass flakes, kaolin, talc and mica are used, a molded product having a weld portion with little warp can be obtained because of its effect on anisotropy.

  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 1 to 5 in combination with the blending amount of the fiber reinforcing agent from the viewpoint of the fluidity at the time of molding of the molded product having the weld part and the durability of the molding machine and the mold. An amount not exceeding 150 parts by weight is preferred.

A molded article having a screw or terminal insertion portion that meets the V-0 standard of the UL-94 combustion test at a thickness of 1/64 "(about 0.4 mm) of the present invention.
(A) Polyethylene terephthalate which is easy to obtain high flame retardancy among polyalkylene terephthalate resins as a main component of the component (A) and a large amount of the components (B), (C) and (D) Alternatively, it is obtained when a flame retardant aid described later is further blended. For example, as a case where (A) polyethylene terephthalate contains a large amount of components (B), (C) and (D), (A) (B), (C), and (B) with respect to 100 parts by weight of polyethylene terephthalate D) When the total amount of the components exceeds 50 parts by weight, and at least the component amounts of (B) and (C) both satisfy 10 parts by weight or more,
At a thickness of 1/64 "(about 0.4 mm) according to the present invention, a molded article having a weld portion that meets the V-0 standard of the UL-94 combustion test is obtained.

  Further, when (A) other polyalkylene terephthalate such as a combined polymer of polyethylene terephthalate and polybutylene terephthalate or polybutylene terephthalate is used as the polyalkylene terephthalate resin, more (B) and (C) components than the above are used. It is necessary to mix. In addition, when (G) a fluorine compound, a polycarbonate resin, a silicone compound, a phenol resin, a phosphonitrile compound, an ammonium polyphosphate, a melamine polyphosphate, and a vinyl resin, which are components to improve flame retardancy described later, Can reduce the components (B) and (C), and at a 1/64 "(about 0.4 mm) thickness with preferred weld strength, a weld site that meets the V-0 standard of the UL-94 combustion test Can be obtained.

  Examples of the (E) epoxy compound in the present invention include glycidyl ester compounds, glycidyl ether compounds, and glycidyl ester ether compounds, and these can be used singly or in combination.

  Moreover, in order to express the outstanding improvement effect with respect to the hydrolysis resistance of (A) polyalkylene terephthalate, an epoxy compound with an epoxy equivalent of less than 500 is preferable, and an epoxy compound with an epoxy equivalent of less than 400 is particularly preferable. Here, the epoxy equivalent is an epoxy compound in which the number of grams of the epoxy compound containing 1 gram equivalent of the epoxy group is less than 500, and the epoxy equivalent is obtained by dissolving the epoxy compound in pyridine and adding 0.05N hydrochloric acid to 45 ° C. After heating, a mixture of thymol blue and cresol red is used as an indicator and back titration with 0.05N caustic soda can be used.

  In addition, as the above-mentioned epoxy compound, an epoxy compound in which a monofunctional glycidyl ester compound and a glycidyl ether compound are used in combination or a monofunctional glycidyl ester compound is preferably used, and in particular, viscosity stability and hydrolysis resistance of the resulting composition are used. From the balance of property, a monofunctional glycidyl ester compound is more preferable.

  Further, the glycidyl ester compound is not limited, but as specific examples, glycidyl benzoate, tBu-glycidyl benzoate, P-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, pelargonic acid glycidyl Ester, glycidyl stearate, glycidyl laurate, glycidyl palmitate, glycidyl behenate, glycidyl bersate, glycidyl oleate, glycidyl linoleate, glycidyl linolein, glycidyl behenol, stearolic acid Glycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester Naphthalene dicarboxylic acid diglycidyl ester, bibenzoic acid diglycidyl ester, methyl terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester , Succinic acid 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. Two or more kinds can be used.

  The glycidyl ether compound is not limited, but specific examples include phenyl glycidyl ether, P-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 Others such as-(β, γ-epoxypropoxy) -2-benzyloxyethane, 2,2-bis- [р- (β, γ-epoxypropoxy) phenyl] propane and bis- (4-hydroxyphenyl) methane Examples include diglycidyl ether obtained by the reaction of bisphenol and epichlorohydrin. These can be used alone or in combination of two or more. .

  Moreover, the compounding quantity of (E) epoxy compound is 0.1-10 weight part with respect to 100 weight part of (A) polyalkylene terephthalate resin from the point of the weld strength and hydrolysis resistance of the molded article which has a weld part. , Preferably 0.2-9 parts by weight, more preferably 0.3-8 parts by weight.

  As the (F) alkaline earth metal compound in the present invention, preferred are alkaline earth metal compounds such as magnesium, calcium, and barium. In addition, as alkaline earth metal compounds, these alkaline earth metal hydroxides, oxides, carbonates, sulfates, acetates, phosphates and other inorganic acid salts, acetates, lactates, oleic acids, Organic acid salts such as palmitic acid, stearic acid and montanic acid are preferred. Specific examples include magnesium hydroxide, calcium hydroxide, barium hydroxide, magnesium oxide, calcium oxide, barium oxide, magnesium carbonate, calcium carbonate, barium carbonate, magnesium sulfate, calcium sulfate, barium sulfate, magnesium phosphate, calcium phosphate, phosphorus Barium acid, magnesium acetate, calcium acetate, barium acetate, magnesium lactate, calcium lactate, barium lactate, and magnesium, calcium and barium salts of organic acids such as oleic acid, palmitic acid, stearic acid and montanic acid Can be mentioned. Among these, hydroxides and carbonates of alkaline earth metals are preferably used. In particular, magnesium hydroxide and calcium carbonate are preferably used, and calcium carbonate is more preferably used. Such alkaline earth metals can be used alone or in combination of two or more. In addition, calcium carbonate, light calcium carbonate, heavy calcium carbonate, wet-pulverized fine powder heavy calcium carbonate, wet heavy calcium carbonate (chalk), etc. are known depending on the production method. In the invention, it is included in (F) alkaline earth metal compound. These alkaline earth metal compounds may be treated with one or more surface treatment agents such as silane coupling agents, organic substances and inorganic substances, and the shape may be powder, plate or fiber. It is preferable from a dispersibility etc. to use in the powder form of 10 micrometers or less. Further, if the particle size is fine, the effect of improving hydrolyzability is large and preferable.

In addition, phosphoric acid esters that are effective as non-halogen flame retardants have the disadvantage that the phosphoric acid ester bond is easily hydrolyzed, and thus the hydrolysis resistance is poor, but by adding (F) an alkaline earth metal compound, It is presumed that the hydrolyzability is improved by trapping the acid generated from the hydrolyzed phosphate ester bond. In general, it is known that hydrolysis of polyester is accelerated by acid or alkali as a catalyst. Addition of an alkali metal compound is not preferable because it often has alkalinity and usually promotes hydrolysis of the polyester. Accordingly, the alkaline earth metal compound of the present invention is hardly soluble in water in a neutral state, and when the phosphate ester decomposes and the system becomes acidic, it dissolves in an acidic environment and exhibits a neutralizing action. Preferably used. The solubility in the neutral state is described in, for example, the Handbook of Chemistry, published by Maruzen Co., Ltd. (Showa 41), and the solubility in water is preferably 1 g / 100 g or less, more preferably 10 ⁻¹ g / 100 g water, particularly preferably 10 ⁻² g / 100 g water or less. Incidentally, the solubility of calcium carbonate most preferably used in water is not more than 5.2 × 10 ⁻³ g / 100 g water.

  Furthermore, by using (E) an epoxy compound and (F) an alkaline earth metal compound in combination, an extremely high hydrolysis resistance improvement and metal contamination improvement effect can be obtained.

  The blending amount of (F) alkaline earth metal compound is 0.1 to 10 with respect to 100 parts by weight of (A) polyalkylene terephthalate resin from the viewpoint of weld strength and hydrolysis resistance of the molded product having a weld site. Parts by weight, preferably 0.2 to 9 parts by weight, more preferably 0.3 to 8 parts by weight.

  The (G) fluorine-based compound in the present invention is a compound containing fluorine in a substance molecule. Specifically, polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer Polymer, (tetrafluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) Examples of the copolymer include polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, and (tetrafluoroethylene). Ethylene) copolymer, polyvinylidene fluoride are preferable, polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer are preferable.

  Moreover, (G) As an effect which mix | blends a fluorine-type compound, it can suppress that the flame-retardant resin composition at the time of combustion melts and falls, and can further improve a flame retardance. Further, the blending amount when blending the (G) fluorine-based compound is 0.05 with respect to 100 parts by weight of the (A) polyalkylene terephthalate resin from the viewpoint of flame retardancy and weld strength of the molded product having a weld site. -10 parts by weight, preferably 0.1-9 parts by weight, more preferably 0.2-8 parts by weight.

  In this invention, a flame retardance can be improved further by mix | blending polycarbonate resin further. As said polycarbonate resin, the aromatic homo or copolycarbonate obtained by making an aromatic dihydric phenol type compound, phosgene, or carbonic acid diester react is mentioned. The aromatic homo or copolycarbonate resin has a weight average molecular weight in the range of 10,000 to 1100000, a glass transition temperature of about 150 ° C., and a weight average molecular weight in the range of 10,000 to 1,000,000. Different polycarbonate resins may be used in combination. A polycarbonate resin having a weight average molecular weight in the range of 60000 to 1100000 is particularly preferably used. The weight average molecular weight is obtained by measuring in polystyrene conversion by gel permeation chromatography using tetrahydrofuran as a solvent. A weight average molecular weight of 10,000 or less is preferable because the excellent mechanical properties of the present invention are impaired. If the weight average molecular weight is 110,000 or more, the fluidity during molding is impaired, which is not preferable.

  In addition, the melt viscosity index (melt flow index) measured with a melt indexer according to ASTM D1238 under a load of 1.2 kg at a temperature of 300 ° C. is in the range of 1 to 100 g / 10 min. From this point, a polycarbonate resin of 1 to 15 g / 10 min is preferably used.

  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-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. However, it is not preferable to add more than 50 parts by weight of the polycarbonate resin because the tracking resistance is greatly reduced. A preferable blending amount of the polycarbonate resin is 1 to 50 parts by weight, preferably 2 to 45 parts by weight, with respect to 100 parts by weight of the (A) polyalkylene terephthalate resin, from the weld strength and flame retardancy of the molded product having a weld part. More preferably, it is 3 to 40 parts by weight.

  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.

  In addition, by blending a small amount of acidic phosphoric acid ester when blending the above polycarbonate resin, it is useful for preventing transesterification of (A) polyalkylene terephthalate and polycarbonate resin, especially preventing the heat distortion temperature from decreasing. To do. The acidic phosphoric acid ester is a general term for partial ester compounds of alcohols and phosphoric acid. The low molecular weight is a colorless liquid, the high molecular weight is a white waxy or flaky solid, and the hydrogen of phosphoric acid is an alkyl group. And (B) the phosphoric acid ester substituted with an allyl group or the like.

  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 triacetate And said Mixtures of mono- and di, mono, or a mixture of one or more thereof and the compounds of the di- and tri. Acid phosphates preferably used include long-chain alkyl acid phosphate compounds such as a mixture of mono and distearyl acid phosphates, which are commercially available from Asahi Denka Co., Ltd. under the name “Adekastab” AX-71, and have a melting point of It has a flaky solid.

  Further, the blending amount of the acidic phosphoric acid ester is 0.01 to 5 parts by weight, preferably 100 parts by weight of the (A) polyalkylene terephthalate resin, from the viewpoint of weld strength and heat resistance of the molded product having a weld part. Is 0.02 to 4 parts by weight, more preferably 0.03 to 3 parts by weight.

  In the present invention, a flame retardant aid for improving flame retardancy such as a silicone compound, a phenol resin, a phosphonitrile compound, ammonium polyphosphate, and melamine polyphosphate can be blended and used in one or more kinds. Moreover, the compounding quantity in the case of mix | blending said flame retardant adjuvant is 1-50 with respect to 100 weight part of (A) polyalkylene terephthalate resin from the point of the flame retardance and weld strength of the molded article which has a weld part. Parts by weight, preferably 2 to 45 parts by weight, more preferably 3 to 40 parts by weight.

  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. And those having a viscosity of about 200 to 300,000,000 centipoise at room temperature are preferable. However, as long as the above silicone resin is used, the present invention is not limited thereto, and the product shape may be oil, powder or gum. In addition, 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 group selected from saturated or unsaturated monovalent hydrocarbon group, hydrogen atom, hydroxyl group, alkoxyl group, aryl group, vinyl or allyl group is chemically bonded to siloxane. And those having a viscosity of about 0.65 to 100000 centistokes at room temperature are preferable, but the silicone oil resin is not limited thereto, and the product shape is oily, powdery and gumy. An epoxy group, a methacryl group and an amino group may be introduced as a functional group, or a mixture of two or more kinds of silicone oils or silicone resins may be used.

  Examples of the silicone powder include those obtained by blending an inorganic filler with the above silicone resin and / or silicone oil, and silica or the like is preferably used as the inorganic filler.

  Further, 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 thermal reaction type resins, and resins obtained by modifying these. These may be an uncured resin, a semi-cured resin, or a cured resin to which no curing agent is added. Among these, novolak-type phenolic resins or melamine-modified novolak-type phenolic resins that are non-thermally reactive with no addition of a curing agent are 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. The phenolic resin is not particularly limited, and commercially available ones are 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 further oxalic acid, hydrochloric acid, sulfuric acid, toluenesulfone. After adding a catalyst such as an acid, the mixture is heated and refluxed for a predetermined time. In order to remove the produced water, it can be obtained by a method of vacuum dehydration or standing dehydration and further removing remaining water and unreacted phenols. These resins or co-condensed phenol resins obtained by using 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 singly or in combination. 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 using a tetrahydrafuran solution and 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 linear, cyclic, or a mixture. The phosphonitrile linear polymer and / or the cyclic polymer can be synthesized by a known method described in the author “Harahara”, “Synthesis and Application of Phosphazene Compounds”, for example, phosphorus pentachloride or trichloride as a phosphorus source. It can be synthesized by reacting ammonium chloride or ammonia gas as a phosphorus and nitrogen source by a known method (the cyclic product may be purified) and substituting the obtained substance with alcohol, phenol and amines. .

  Examples of the ammonium polyphosphate include ammonium polyphosphate, melamine-modified ammonium polyphosphate, and carbamyl polyphosphate ammonium, and include thermosetting phenol resin, urethane resin, melamine resin, urea resin, epoxy resin, and It may be coated with a thermosetting resin such as a urea resin, or may be used alone or in combination of two or more.

  Examples of the melamine polyphosphate include melamine polyphosphates such as melamine phosphate and melamine pyrophosphate, which may be used alone or in combination of two or more.

  In the present invention, an ethylene (co) polymer can be further blended for the purpose of improving toughness such as impact strength of a molded article having a weld site of the present invention. Examples include ethylene polymers and / or ethylene copolymers such as density polyethylene, low density polyethylene, and ultra-low density polyethylene. The above 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, maleic acid, fumaric acid, and itaconic acid. And the like. The ethylene copolymer can be usually 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. These may be used alone or in combination of two or more, and may be used in combination with one or more of the above ethylene (co) polymers. Among ethylene (co) polymers, a copolymer obtained by grafting or polymerizing an acid anhydride or glycidyl methacrylate onto polyethylene is preferably used because of its good compatibility with (A) polyalkylene terephthalate. In addition, “/” in the specific examples of the ethylene copolymer and the following vinyl resin means copolymerization.

  Moreover, the compounding quantity in the case of mix | blending an ethylene (co) polymer is 1-50 with respect to 100 weight part of (A) polyalkylene terephthalate resin from the point of the flame retardance and impact strength of the molded article which has a weld part. Parts by weight, preferably 2 to 45 parts by weight, more preferably 3 to 40 parts by weight.

  In the present invention, a vinyl resin can be further blended for the purpose of improving flame retardancy, impact strength, and weld strength. Specific examples of such vinyl resins include styrene / butadiene resins, styrene / butadiene / styrene resins, styrene / isoprene / styrene resins, styrene / ethylene / butadiene / styrene resins, styrene resins, high impact styrene resins, styrene / acrylonitrile. Resin (AS resin), polymethyl methacrylate acrylate resin (PMMA resin), acrylonitrile / acrylic rubber / styrene resin, acrylonitrile / ethylene rubber / styrene resin and building resin such as AS resin and PMMA resin as shell layer Core-shell rubber with a core layer of rubber such as acrylic rubber, etc., and vinyl that has been epoxy-modified with an epoxy group-containing vinyl resin and an epoxidizing agent. It may be a resin. Among the epoxy-modified vinyl resins, a vinyl resin copolymerized with glycidyl methacrylate is preferably used, and the preferable copolymerization amount of glycidyl methacrylate has (A) compatibility with polyalkylene terephthalate and flame retardancy. An amount effective for improvement is preferable, and it is preferably 0.1% by weight or more based on the vinyl resin. When copolymerized in a large amount, there is a problem of decrease in fluidity and gelation, and it is preferably 20% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less. Among vinyl resins copolymerized with glycidyl methacrylate, AS resins, styrene / butadiene resins, and styrene / butadiene / styrene resins are preferably used.

  Moreover, the compounding quantity of vinyl-type resin is 1-50 weight part with respect to 100 weight part of (A) polyalkylene terephthalate resin from a flame-retardant point, Preferably it is 2-45 weight part, More preferably, it is 3-40. Parts by weight.

  In the present invention, a phenoxy resin, an oxazoline compound, a carbodiimide compound, or the like, which is a hydrolysis resistance improving material, can be further blended, and a phenoxy resin is particularly preferably used. In addition, the blending amount when blending the above-mentioned hydrolysis resistance improving material is from the point of hydrolysis resistance and flame retardancy of the molded product having a weld site, with respect to the flame retardant resin composition specific to the present invention. (A) 1 to 50 parts by weight, preferably 2 to 45 parts by weight, more preferably 3 to 40 parts by weight with respect to 100 parts by weight of the polyalkylene terephthalate resin.

  Moreover, as said phenoxy resin, the phenoxy resin obtained by making an aromatic dihydric phenol type compound and epichlorohydrin react with various compounding ratios is mentioned. Although there is no restriction | limiting in particular in the molecular weight of a phenoxy resin, The thing of the range whose viscosity average molecular weight is 1000-100000 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. Further, the shape 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.

  In the present invention, a hindered phenolic antioxidant and / or a phosphite antioxidant can be added as a stabilizer that gives extremely good heat aging resistance even when the composition of the present invention is exposed to a high temperature for a long period of time. The amount of hindered phenol-based antioxidant and / or phosphite-based antioxidant is a specific difficulty of the present invention from the viewpoint of heat aging resistance and flame retardancy of a molded article having a weld site. 0.01 to 5 parts by weight, preferably 0.02 to 4 parts by weight, more preferably 0.03 to 3 parts by weight, based on 100 parts by weight of the (A) polyalkylene terephthalate resin, relative to the flammable resin composition is there.

  Specific examples of the hindered phenol antioxidant include triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol. -Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-t-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-t-butyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-2 4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis or tris (3-t-butyl-6-methyl-4-hydroxyphenyl) propane, N, N′-hexa Methylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), N, N′-trimethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) ) And the like.

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

  In the present invention, it is possible to improve the fluidity and releasability during molding by further adding one or more lubricants. Such lubricants include metal soaps such as gallium 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 Fatty acid amides, polyalkylene waxes, acid anhydride-modified polyalkylene waxes composed of a polycondensate consisting of sebacic acid or polycondensates of phenylenediamine and stearic acid and sebacic acid, and the above-mentioned lubricants and fluororesins or fluorine compounds Examples include, but are not limited to, a mixture. The blending amount in the case of blending the lubricant is 0.01 to 5 parts by weight, preferably 0.02 to 100 parts by weight of the (A) polyalkylene terephthalate resin from the viewpoint of the weld strength of the molded product having a weld site. 4 parts by weight, more preferably 0.03 to 3 parts by weight.

  In the present invention, the resin is mixed in various colors, weather resistance (light), and electrical conductivity are improved by blending at least one kind of carbon black, titanium oxide, and various color pigments and dyes. The blending amount is 0.1 to 10 parts by weight, preferably 0.2 to 100 parts by weight with respect to 100 parts by weight of the (A) polyalkylene terephthalate resin, from the viewpoint of weld strength of the molded product having a weld part. 9 parts by weight, more preferably 0.3 to 8 parts by weight.

Examples of the carbon black include, but are not limited to, channel black, furnace black, acetylene black, anthracene black, oil smoke, pine smoke, and graphite. The average particle diameter is 500 nm or less, and dibutyl phthalate. carbon black oil absorption 50~400cm 3 ^/ 100g is preferably used, aluminum oxide treatment agent, silicon oxide, zinc oxide, zirconium oxide, polyol, may be treated with a silane coupling agent.

  Further, as the above titanium oxide, titanium oxide having a crystal form such as rutile form or anatase form and having an average particle diameter of 5 μm or less is preferably used, and aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, It may be treated with a polyol, a silane coupling agent or the like. In addition, the above-described carbon black, titanium oxide, and various color pigments and dyes may be used in various thermoplastic resins in order to improve dispersibility with the flame retardant resin composition of the present invention and to improve handling during production. And may be used as a blended material that is melt blended or simply blended. In particular, (A) polyalkylene terephthalate is preferably used as the thermoplastic resin.

  In the present invention, it is possible to add one or more known non-halogen flame retardants other than the present invention, and it can be expected that the combustion time during combustion is shortened or the gas generated during combustion is reduced. Such known non-halogen flame retardants include, but are not limited to, for example, aluminum hydroxide, hydrotalcite, boric acid, calcium borate, calcium borate hydrate, zinc borate, zinc borate hydrate, hydroxide Examples include zinc, zinc hydroxide hydrate, zinc tin hydroxide, zinc tin hydroxide hydrate, red phosphorus, heat-expanded graphite and dosonite, thermosetting melamine resin, thermosetting phenolic resin, heat A thermosetting resin such as a curable 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.

  Furthermore, a sulfur-based antioxidant, an ultraviolet absorber, a plasticizer, and an antistatic agent for a molded article having a weld site made of the specific flame-retardant resin composition of the present invention within a range that does not impair the object of the present invention. It is also possible to use a material in which one or more known additives such as an agent and one or more other thermoplastic resins are blended. However, in the thermoplastic resin, it is preferable not to blend polyphenylene ether resin and polyphenylene sulfide resin from the viewpoint of tracking resistance, fluidity, color tone, and color tone change. It is preferable not to exceed 5 parts by weight with respect to 100 parts by weight of the flame retardant resin composition.

  The molded article having a weld part of the present invention is a molded article having a part (weld part) where the molten resin and the molten resin are joined, a method of injection molding with two or more gates (flow paths), and a complicated molding. A molded product having a weld site can be obtained by an injection molding method of a product shape and an injection molding method of inserting metal or the like.

  As specific examples of the molded product having a portion (weld part) where the molten resin and the molten resin are joined, many of electric / electronic parts and automobile parts are formed by injection molding. Tends to be thin, and the thinner the wall thickness, the lower the fluidity of the molten resin during injection molding. In order to improve the fluidity, injection molding is performed with two or more multi-point gates (flow paths), and a molded product having a portion (weld portion) where the molten resin and the molten resin are joined is obtained.

  In addition, a molded product having a portion (weld site) where the molten resin and the molten resin are joined can be obtained by a complicated molded product shape or an injection molding method in which a metal or the like is inserted. Further, any injection molding method other than those described above may be used as long as a molded product having a portion (weld portion) where the molten resin and the molten resin are joined is obtained.

  The molded article having a weld portion according to the present invention is used as a mechanical mechanism part, an electric / electronic part, or an automobile part. Specifically, circuit breakers, electromagnetic switches, focus cases, flyback transformers, molded products for copiers and printer fixing machines, general home appliances, OA equipment housings, variable capacitor case parts, various terminal boards, transformers , Printed wiring boards, housings, terminal blocks, coil bobbins, connectors, relays, disk drive chassis, transformers, switch parts, outlet parts, motor parts, sockets, plugs, capacitors, various cases, resistors, metal terminals and conductors Built-in electrical / electronic parts, computer-related parts, sound parts, audio parts such as laser discs, lighting parts, telegraph / telephone equipment-related parts, air conditioner parts, home appliance parts such as VTR and TV, parts for copying machines, parts for facsimiles , Optical equipment parts, automobile ignition device parts, Moving vehicles connectors, and molded articles and the like having a weld portion, such as various electrical components for automobiles.

  In addition, a molded article having a weld part made of the specific flame retardant resin composition of the present invention is excellent in heat resistance (thermal deformation temperature) and is not easily deformed at high temperature. Are also useful, and are particularly useful as, for example, molded articles for fixing machines of the above-mentioned copying machines and printers and parts around automobile ignition devices.

  A molded article having a weld site made of the specific flame-retardant resin composition of the present invention is usually produced by a known method. For example, (A) polyalkylene terephthalate, (B) phosphoric ester, (C) salt of triazine compound and cyanuric acid or isocyanuric acid, and (D) fiber reinforcement such as glass fiber, if necessary (E ) Epoxy compounds, (E) Alkaline earth metal compounds, and (F) Fluorine compounds, and further, if necessary, inorganic fillers other than fiber reinforcements, polycarbonate resins, various flame retardant aids, ethylene (co) heavy Coalescence, vinyl resins, hydrolysis resistance improvers, hindered phenolic antioxidants and / or phosphite antioxidants, and other necessary additives, colorants such as pigments and dyes as needed The specific flame-retardant resin composition of the present invention is prepared by supplying to an extruder or the like with or without premixing and sufficiently melting and kneading.

  As an example of the above-mentioned premixing, it is possible to perform dry blending alone, but mixing can be performed using a mechanical mixing device such as a tumbler, a ribbon mixer, and a Henschel mixer. 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, in producing the specific flame retardant resin composition of the present invention, for example, but not limited to, for example, a single screw extruder, a twin screw extruder equipped with a “unimelt” or “Dalmage” type screw, A triaxial extruder, a conical extruder, a kneader type kneader, or the like can be used.

  The specific flame-retardant resin composition of the present invention thus obtained is a method of injection molding with two or more gates (flow paths), an injection molding method of complex molded product shape, and an injection molding method of inserting metal or the like The injection molding method other than the above may be used as long as a molded product having a weld part is obtained and a molded product having a part (weld part) where the molten resin and the molten resin are joined is obtained.

  Briefly describing the injection molding method, the injection molding machine heats, melts and kneads the plastics, then cools and solidifies the injected plastic parts at a high pressure and the injected molten plastics into a predetermined shape (molded product). It is made up of molds.

  The mold structure used for general injection molding and the method for temperature control of the mold will be briefly described. The mold passes the part of the molded product shape obtained and the medium for cooling and solidifying the molded product. It consists of an extruding pin for releasing the tube and the molded product. A plurality of pipes through which the medium passes are provided so that the temperature of the molded product in the mold can be controlled. Further, as a method for temperature-controlling the mold, a method is generally used in which the temperature is controlled by a mold temperature controller using water as a medium in the pipe through which the medium passes and circulated through the pipe through which the medium passes. It is a technique and is said to be a low temperature mold, and the temperature can be adjusted to around 90 ° C. On the other hand, the high-temperature mold is a mold that can control the temperature even at a temperature exceeding 90 ° C., and a method of controlling the temperature by inserting a metal heater rod equipped with a thermocouple into the mold, or oil or pressurized water. It is a method of adjusting the temperature using a medium such as. However, because of the high temperature, it is necessary to install a heat insulating plate in the mold, a high-temperature mold temperature controller, and a circulating facility that can withstand high temperatures, and special equipment is required.

  In general, in the case of injection molding of polyethylene terephthalate resin (A) polyalkylene terephthalate resin, it is usually molded at a mold temperature of 120 ° C. to 140 ° C. in order to completely crystallize the polyethylene terephthalate resin. It is known that when molded with a low-temperature mold of 30 ° C. to 90 ° C., the outside of the molded product to be rapidly cooled is transparent and the inside is decooled, so that crystallization progresses and becomes opaque.

  In the case of the specific flame-retardant resin composition of the present invention, even when a polyethylene terephthalate resin is used as the (A) polyalkylene terephthalate resin, it can be easily injection-molded with a low-temperature mold. The temperature of the low-temperature mold is preferably 50 ° C. or higher, particularly preferably 60 ° C. or higher. When the temperature is lower than 50 ° C., the heat distortion temperature decreases depending on the wall thickness.

  The effects of the present invention will be described in more detail with reference to the following examples. Here, “%” and “part” represent “% by weight” and “part by weight”, and “/” in the resin name of the reference example means copolymerization. The measuring method of each characteristic is as follows.

Reference example 1
(A) Polyethylene terephthalate resin (hereinafter abbreviated as PET)
<A-1> Mitsui PET “J005” (manufactured by Mitsui Petit Co., Ltd.) PET having an intrinsic viscosity of 0.63 was used.

Reference example 2
(A) Polybutylene terephthalate resin (hereinafter abbreviated as PBT)
<A-2> “Trecon” 1401-X31 (manufactured by Toray Industries, Inc.) PBT having an intrinsic viscosity of 0.80 was used.

Reference example 3
(B) Phosphoric acid ester <B-1> The aromatic phosphoric acid ester “PX-200” (produced by Daihachi Chemical Industry Co., Ltd.) represented by the following formula (5) was used.

<B-2> An aromatic phosphate “CR741” (produced by Daihachi Chemical Industry Co., Ltd.) of the following formula (6) was used.

Reference example 4
(C) a salt of a triazine compound surface-treated with a metal oxide and cyanuric acid or isocyanuric acid (hereinafter abbreviated as metal oxide-treated MC salt)
<C-1> For 100 parts by weight of a mixture of melamine powder (Mitsubishi Chemical Corporation) and cyanuric acid powder (Cyanuric acid, Shikoku Kasei Co., Ltd.) of the same weight, silica hydrosol (Nissan Chemical Industries ( Snowtex C, Inc.) 10 parts by weight and 500 parts by weight of water were added to form a water slurry, which was heated and mixed at 90 ° C. for 1 hour to form fine particles. This slurry was filtered, dried, and pulverized to obtain a salt of a triazine compound surface-treated with a metal oxide having an average particle size of about 10 μm and cyanuric acid or isocyanuric acid.

Reference Example 5
Salt of triazine compound with cyanuric acid or isocyanuric acid (hereinafter abbreviated as MC salt)
<C-2> 500 parts by weight of water is added to 100 parts by weight of a mixture of melamine powder (Mitsubishi Chemical Co., Ltd.) and cyanuric acid powder (Shikoku Kasei Co., Ltd.) having the same weight. The resulting slurry was heated and mixed at 90 ° C. for 1 hour to form fine particles. The slurry was filtered, dried and pulverized to obtain a salt of a triazine compound having an average particle size of about 10 μm and cyanuric acid or isocyanuric acid.

Reference Example 6
Salt of triazine compound surface-treated with polyvinyl alcohol and cyanuric acid or isocyanuric acid (hereinafter abbreviated as PVA-treated MC salt)
<C-3> For 100 parts by weight of a mixture of melamine powder (Mitsubishi Chemical Co., Ltd.) and cyanuric acid powder (Cyanuric acid, Shikoku Kasei Co., Ltd.) having the same weight, polyvinyl alcohol (Wako Pure Chemical Industries, Ltd.) Reagent manufactured by Co., Ltd.) 2 parts by weight and 500 parts by weight of water were added to form a water slurry, which was heated and mixed at 90 ° C. for 1 hour to form fine particles. The slurry was filtered, dried and pulverized to obtain a salt of a triazine compound having an average particle size of about 10 μm and cyanuric acid or isocyanuric acid.

Reference Example 7
(D) Fiber reinforcement <D-1> Chopped strand glass fiber “CS3J948” (manufactured by Nitto Boseki Co., Ltd.) having a fiber diameter of about 10 μm was used (hereinafter abbreviated as GF).

Reference Example 8
(E) Epoxy compound <E-1> Versatic acid glycidyl ester “Cardura E10” (manufactured by Japan Epoxy Resins Co., Ltd.)
<E-2> Versatic acid glycidyl ester “Cardura E10” (manufactured by Japan Epoxy Resin Co., Ltd.) 30% by weight and bisphenol A diglycidyl ether “Epicoat 828” (manufactured by Japan Epoxy Resin Co., Ltd.) 70% by weight mixture.

Reference Example 9
(F) Alkaline earth metal compound <F-1> Magnesium hydroxide “Kisuma 6E” (manufactured by Kyowa Chemical Industry Co., Ltd.)
<F-2> Calcium carbonate “KSS1000” (manufactured by Dowa Calfine Co., Ltd.)

Reference Example 10
(G) Fluorine compound <G-1> Polytetrafluoroethylene “Teflon (registered trademark) 6-J” (Mitsui DuPont Fluorochemical Co., Ltd.) was used (hereinafter abbreviated as Teflon (registered trademark)). .

Reference Example 11
Polycarbonate resin (hereinafter abbreviated as PC)
<H-1> “A-1900” manufactured by Idemitsu Petrochemical Co., Ltd. was used.

Reference Example 12
Phosphononitrile compound <H-2> hexachlorocyclotriphosphazene (cyclic trimer) and phenol were reacted in THF in the presence of triethylamine. The resulting reaction solution was evaporated to dryness and washed with water to remove salts. The yield was 95%. The phosphonitrile cyclic polymer thus obtained was recrystallized and purified from acetone. The number average polymerization degree n was not changed and n = 3.

Reference Example 13
Vinyl resin <H-3> Styrene / Acrylonitrile / Glycidyl methacrylate = 70 / 29.5 / 0.5 wt% epoxy-modified AS resin

Reference Example 14
<H-4> Polyphenylene ether resin “YPX-100L” (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) (hereinafter abbreviated as PPE).

Reference Example 15
<H-5> Polyphenylene sulfide “Torelina” M2588 (manufactured by Toray Industries, Inc.) (hereinafter abbreviated as PPS).

[Measuring method]
In Examples and Comparative Examples, the characteristics were evaluated by the measurement methods described below.

(1) Injection moldability Using an IS55EPN injection molding machine manufactured by Toshiba Machine, a mold having two gates (flow paths) under a molding temperature of 270 ° C. and a mold temperature of 80 ° C. is used. An injection molded product was obtained. Two gate positions at this time were provided on the left and right in the longitudinal direction of the ASTM No. 1 dumbbell, and a molded product having a weld at the center of the ASTM No. 1 dumbbell was obtained. In addition, injection molding is performed in a molding cycle in which the injection time and holding time during injection molding are 10 seconds in total and the cooling time is 10 seconds. Excellent). In addition, when taking out a molded product, the material that cannot be removed from the mold (unsatisfactory releasability), the material that has a slow solidification speed and causes the molded product to deform with a pin (insufficient crystallization), and poor fluidity Therefore, for a material that is difficult to flow at a predetermined molding temperature and is molded at a molding temperature higher than the predetermined temperature (poor fluidity), the injection moldability is judged as x (poor).

(2) Flame retardance Using Toshiba Machine's IS55EPN injection molding machine, injection molding of the test piece for flame retardancy was performed under conditions of a molding temperature of 270 ° C and a mold temperature of 80 ° C. The flame retardancy was evaluated according to the evaluation criteria. Flame retardancy falls and ranks in the order of V-0>V-1> V-2. The thickness of the test piece is 1/32 inch (about 0.79 mm) (hereinafter abbreviated as about 0.8 mm) and 1/64 inch (about 0.40 mm) (hereinafter abbreviated as about 0.4 mm). As the thickness is thinner, the flame retardancy becomes more severe. Moreover, the material which was inferior in combustibility, did not reach said V-2, and did not correspond to said flame retardance rank was made into the outside of specification.

(3) Weld strength ASTM1 dumbbell injection using a die with two gates (flow channels) at a molding temperature of 270 ° C and a mold temperature of 80 ° C using a Toshiba Machine IS55EPN injection molding machine. A molded product was obtained. Two gate positions at this time were provided on the left and right in the longitudinal direction of the ASTM No. 1 dumbbell, and a molded product having a weld part at the center of the ASTM No. 1 dumbbell was obtained. Using this ASTM No. 1 dumbbell, a tensile test was performed according to ASTM D638, and the value of the tensile strength was defined as the weld strength.

(4) Thermal deformation temperature (heat resistance)
Using an IS55EPN injection molding machine manufactured by Toshiba Machine, a 3 mm thick ASTM No. 1 dumbbell was injection molded under conditions of a molding temperature of 270 ° C. and a mold temperature of 80 ° C., and the high temperature thermal deformation temperature was measured according to ASTM D648.

(5) Hydrolysis property Using an IS55EPN injection molding machine manufactured by Toshiba Machine, injection molding of ASTM No. 1 dumbbell having a thickness of 3 mm under conditions of a molding temperature of 270 ° C. and a mold temperature of 80 ° C. A sample was placed in a pressure cooker tester set at a temperature and humidity of 100% RH for 200 h, the tensile strength was measured according to ASTM D638, and the retention rate (%) relative to the tensile strength before treatment was determined.

(6) Anisotropy Using an IS55EPN injection molding machine manufactured by TOSHIBA MACHINE, injection molding of a square plate having a length of 80 mm, a width of 80 mm, and a thickness of 3 mm under the conditions of a molding temperature of 270 ° C. and a mold temperature of 80 ° C. The molding shrinkage in the direction perpendicular to the flow direction and flow was measured. The value obtained by subtracting the molding shrinkage in the flow direction from the vertical molding shrinkage in the flow, that is, the difference in the molding shrinkage in different directions was defined as anisotropy. The flow direction of the molten resin and the method of measuring the mold shrinkage in the direction perpendicular to the flow are obtained by measuring the vertical (flow direction) and horizontal (perpendicular to flow) dimensions of the obtained square plate by Nikon Kogyo Co., Ltd. The profile shrinkage was measured with a profile projector V-12 universal projector, and the molding shrinkage was calculated from the vertical and horizontal mold dimensions of the square plate by the following formula.
Mold shrinkage rate (%) = (Mold dimension-Molded product dimension) / Mold dimension x 100

  Among thermoplastic resins, crystalline polymers, especially in the flow direction of the molten resin, have a small mold shrinkage rate, and the mold shrinkage rate in the direction perpendicular to the flow is large. It is known to be. Further, when the difference in anisotropy becomes large, warping occurs in the molded product, and a molded product having a desired shape may not be obtained. For example, in the case of a rectangular plate having a length of 80 mm, a width of 80 mm, and a thickness of 1 mm of a material having an anisotropy value of 1 or more, it is difficult to keep the shape in a plane due to deformation by warping.

[Examples 1 to 17], [Comparative Examples 1 to 7]
(A) PET and / or PBT, (B) Phosphate ester, (C) Metal, using a twin screw extruder with a screw diameter of 30 mm and L / D35 (TEX-30α, manufactured by Nippon Steel Works) Tables 1 to 2 show oxide-treated MC salts, (E) epoxy compounds, (F) alkaline earth metal compounds, (G) fluorine-based compounds and other additives <H-1> to <H-5>. It mixed with the compounding composition shown, and added from the original filling part. (D) GF was added by installing a side feeder in the middle of the original storage part and the vent part.

  Further, the mixture was melt-mixed under the extrusion conditions of a kneading temperature of 270 ° C. and a screw rotation of 150 rpm, discharged into a strand shape, passed through a cooling bath, and pelletized by a strand cutter.

  The pellets obtained were dried with a hot air dryer at 130 ° C. for 3 hours, and then using a Toshiba Machine IS55EPN injection molding machine, two gates (channels) at a molding temperature of 270 ° C. and a mold temperature of 80 ° C. An injection molded product of ASTM No. 1 dumbbell was obtained using a mold having Two gate positions at this time were provided on the left and right in the longitudinal direction of the ASTM No. 1 dumbbell, and a molded product having a weld part at the center of the ASTM No. 1 dumbbell was obtained. Furthermore, various physical properties were measured under the conditions described in the measurement method, and the results are also shown in Tables 1 and 2.

  From Example 1 to Example 6 in Table 1, the molded article having a weld part made of the specific flame retardant resin composition of the present invention has injection moldability, flame retardancy, weld strength, and heat distortion temperature (heat resistance). ).

  From Comparative Example 1, Comparative Example 3 and Comparative Example 4 in Table 1, when MC salt surface-treated with metal oxide is not blended, there is a particular problem in injection moldability, and regarding flame retardancy and weld strength, It became clear that the composition was not expected to have high performance.

  From Comparative Example 5 to Comparative Example 7 in Table 1, the composition containing the MC salt, phosphate ester or GF compounding amount exceeding the specific amount of the present invention was surface-treated with the metal oxide of the present invention. It has been clarified that the composition has problems in one or more of moldability, weld strength and heat distortion temperature (heat resistance).

  From Example 13 to Example 17 in Table 2, when a polycarbonate resin, a phosphonitrile compound, a vinyl resin (epoxy-modified AS resin fat), PPE, and PPS are used in combination, the high performance is maintained and the thickness is about 0.4 mm. It can be said that the flame retardancy is greatly improved up to V-0. In particular, among the above, vinyl resins (epoxy-modified AS resins) are known as materials that are extremely flammable than polyethylene terephthalate resins, and it has not been anticipated that flame retardancy will be greatly improved.

  From Example 7 to Example 12 in Table 2, it can be said that when an epoxy compound and / or an alkaline earth metal salt is added, the hydrolyzability is improved while maintaining high performance, and in particular, the epoxy compound and the alkaline earth metal salt. It can be said that the hydrolyzability is greatly improved in a composition containing both of the above.

[Example 18]
10 parts by weight of mica (manufactured by Yamaguchi Mica Industry Co., Ltd., A-21) is further blended in the same composition as the flame retardant resin composition of Example 12 of the present invention to produce a flame retardant resin composition. did. The weld strength of the flame retardant resin composition of this example was the same as that of Example 12, and the same was true for injection moldability, flame retardancy, and heat distortion temperature. Further, when the anisotropy of this flame retardant resin composition was measured, it showed an anisotropy of 0.38 relative to the anisotropy of 0.72 in Example 12, and the anisotropy was greatly improved, It can be said that it is a molded product having a weld part with little warpage.

The molded article having a weld portion made of the specific flame retardant resin composition of the present invention is blended with a specific non-halogen flame retardant and a fiber reinforcing material in a polyalkylene terephthalate resin, and has high flame resistance and injection molding. It is a molded product having a weld part with excellent properties, strength of the weld part and heat resistance, and can be expected to greatly contribute to the market expansion as a mechanical mechanism part, electrical / electronic part, and automobile part.

Claims (10)

(A) 1 to 50 parts by weight of (B) phosphoric acid ester, 100 parts by weight of polyalkylene terephthalate resin, (C) 1 to 1 salt of triazine compound and cyanuric acid or isocyanuric acid surface-treated with metal oxide A molded article having a weld part made of a flame retardant resin composition comprising 70 parts by weight and (D) 1 to 150 parts by weight of a fiber reinforcing material. The molded article having a weld portion made of the flame retardant resin composition according to claim 1, wherein the (A) polyalkylene terephthalate resin is a polyethylene terephthalate resin. The molded article having a weld part made of a flame retardant resin composition according to claim 1 or 2, wherein the phosphoric acid ester of (B) is an aromatic phosphoric acid ester of the following formula (1).

(In the above formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ represent the same or different aromatic groups that do not contain halogen. X is 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 ) ₂ , CH ₂ , CHPh, Ph represents a phenyl group, and n in the formula (1) represents a degree of polymerization and is an integer of 0 or more. And 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 molded article having a weld part according to any one of claims 1 to 3, which conforms to a V-0 standard of UL-94 combustion test at a thickness of 1/64 "(about 0.4 mm). (E) The molded article which has a weld part which consists of a flame retardant resin composition of any one of Claims 1-4 characterized by mix | blending 0.1-10 weight part of epoxy compounds further. . The molded article having a weld part made of a flame retardant resin composition according to claim 5, wherein the epoxy compound (E) is a monofunctional glycidyl ester having an epoxy equivalent of less than 400. (F) 0.1-10 weight part of alkaline earth metal compounds are further mix | blended, The weld site | part consisting of the flame-retardant resin composition of any one of Claims 1-6 characterized by the above-mentioned. Molded product with. The molded article having a weld part made of a flame retardant resin composition according to claim 7, wherein the alkaline earth metal compound (F) is one or more alkaline earth metal compounds selected from magnesium, calcium, and barium. . (G) 0.05-10 weight part of fluorine-type compounds are further mix | blended, The shaping | molding which has the weld part which consists of a flame-retardant resin composition of any one of Claims 1-8 characterized by the above-mentioned. Goods. The molded article having a weld portion according to any one of claims 1 to 9, wherein the molded article is a mechanical mechanism part, an electric / electronic part, or an automobile part.