JP5248724B2 - Flame retardant polybutylene terephthalate resin composition and molded article - Google Patents

Description

  The present invention relates to a flame retardant resin composition and a molded article obtained by blending a polybutylene terephthalate resin with a non-halogen flame retardant. More specifically, a non-halogen flame retardant having high flame retardancy, mechanical properties, fluidity during injection molding, and excellent molded product color tone and suitable for mechanical mechanism parts, electrical / electronic parts or automobile parts was used. The present invention relates to a flame retardant polybutylene terephthalate resin composition and a molded article.

  Polybutylene terephthalate resin (PBT) is used in a wide range of fields such as mechanical mechanism parts, electrical / electronic parts, and automobile parts, taking advantage of its excellent properties such as injection moldability and mechanical properties.

  Further, by combining a fiber reinforcement with PBT, it is widely used as a material that is further excellent in mechanical properties and heat resistance. Among the fiber reinforcements, many glass fibers are used in particular.

  Since PBT is inherently flammable, it is safe for 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. That is, flame retardancy is required, and high flame retardancy that indicates V-0 of the UL-94 standard is often required.

  In addition, there is a demand for molded articles that can have various color tones with high flame retardancy and pigments and dyes.

  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, as a method for making a thermoplastic resin flame retardant without using such a hydrated metal compound, Japanese Patent Application Laid-Open No. 51-150553, Japanese Patent Application Laid-Open No. 58-108248, Disclosure in Japanese Utility Model Laid-Open Nos. 59-81351, 5-78560, 5-287119, 5-295164, 5-320486, and 5-339417 Has been.

  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.

  JP-A-3-281652, JP-A-5-70671, JP-A-7-233311 and JP-A-8-73713 disclose that an aromatic phosphate ester and melamine cyanurate are blended. Has been.

  However, although it is a useful flame-retardant resin material that does not use a halogen-based flame retardant, there is a problem that the aromatic phosphoric acid ester bleeds out on the surface of the molded product and the product value is greatly impaired.

  JP-A-10-147699, JP-A-10-182955, JP-A-10-18295, and JP-A-2000-26710 contain a composition containing PBT, polyphenylene ether, phosphate ester, and the like. On the other hand, blending a styrene resin is disclosed.

  However, although it is a useful flame-retardant resin material that does not use a halogen-based flame retardant, blending polyphenylene ether reduces mechanical strength, fluidity during injection molding, the molded product is colored yellow, and metal It was inferior in corrosivity and had problems such as limited applications.

  Japanese Patent Application Laid-Open No. 2000-212412 discloses blending polyester, an organic phosphorus flame retardant, glass fiber, and styrene resin.

  However, although it is a useful flame retardant resin material that does not use a halogen-based flame retardant, the flame retardant effect is extremely low, but the flame retardancy is improved by combining with a flame retardant aid such as melamine cyanurate. In addition, there is a problem that fluidity is lowered and impact strength is lowered during injection molding.

Problems to be solved by the invention

  That is, the present invention blends a non-halogen flame retardant with polybutylene terephthalate resin, has excellent flame retardancy and mechanical properties, fluidity at the time of injection molding, and molded product color tone. And obtaining a highly reliable flame-retardant polybutylene terephthalate resin composition and a molded product.

Means for solving the problem

  In view of the above situation, the present inventors have made extensive studies, and as a result, polybutylene terephthalate resin has a specific amount of epoxy-modified styrene resin, aromatic phosphate ester, and triazine compound and cyanuric acid or isocyanuric acid. In addition to maintaining a high level of flame retardancy, it has excellent mechanical properties, fluidity during injection molding, and color tone of the molded product, and excellent molded product appearance that prevents bleeding out. The present inventors have found that a resin molded product that maintains the above can be obtained, and have reached the present invention.

That is, the present invention is based on (A) 100 parts by weight of polybutylene terephthalate resin or 100 parts by weight of polybutylene terephthalate resin and polyethylene terephthalate resin, (B) 1 to 100 parts by weight of epoxy-modified styrene resin, (C) 1 to 100 parts by weight of a phosphoric acid ester and (D) a salt of 1 to 150 parts by weight of a triazine compound and cyanuric acid or isocyanuric acid, and (B) an epoxy-modified styrene resin is styrene , Acrylonitrile and glycidyl methacrylate are copolymerized, and the copolymerization amount of glycidyl methacrylate is 0.05% by weight or more and 5% by weight or less in the epoxy-modified styrenic resin, and 5 parts by weight of polyphenylene ether and polyphenylene sulfide No flame retardant The present invention provides a molded product used for a mechanical mechanism part, an electrical / electronic part or an automobile part comprising the ribylene terephthalate resin composition and the flame retardant polybutylene terephthalate resin composition.

  The flame-retardant polybutylene terephthalate resin composition and molded article of the present invention will be specifically described below.

  The (A) polybutylene terephthalate resin in the present invention is a polymer obtained by a polycondensation reaction between terephthalic acid or an ester-forming derivative thereof and 1,4-butanediol or an ester-forming derivative thereof. As an acid component, isophthalic acid, naphthalene dicarboxylic acid, adipic acid, sebacic acid, dodecanedioic acid, oxalic acid and the like are used as glycol components. Ethylene glycol, 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, polytetramethyl Such as glycol to may be copolymerized than 20 mol%. Preferred examples of these polymers or copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene. (Terephthalate / Naphthalate) and the like may be used, and these may be used alone or in combination of two or more. Here, “/” means copolymerization.

  A polymer or copolymer having an intrinsic viscosity measured at 25 ° C. using an o-chlorophenol solvent is 0.36 to 1.60, particularly 0.42 to 1.25. It is suitable from the viewpoint of impact strength and moldability of the composition. Moreover, (A) polybutylene terephthalate resin may use together polybutylene terephthalate resin from which intrinsic viscosity differs. It is preferable to use a polybutylene terephthalate resin having an intrinsic viscosity in the range of 0.36 to 1.60 as the polybutylene terephthalate resin having a different intrinsic viscosity.

  Further, those polybutylene terephthalate resins and those having 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) are durable. From the point of anisotropy suppressing effect, it can be preferably used. Furthermore, those having particularly few COOH end groups can be preferably used since they are excellent in hydrolysis resistance.

  In the present invention, instead of (A) polybutylene terephthalate resin, a polybutylene terephthalate resin and a polyethylene terephthalate resin can be used in combination. The polyethylene terephthalate resin refers to a polymer obtained by polycondensation using terephthalic acid as an acid component and ethylene glycol as a glycol component. In addition to this, as an acid component, isophthalic acid, adipic acid, oxalic acid, etc. As a component, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, or the like having a molecular weight of 400 to 6000 A chain glycol, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like can be copolymerized in an amount of 20 mol% or less. In addition, the polyethylene terephthalate resin has a composition having an intrinsic viscosity measured at 25 ° C. using an o-chlorophenol solvent of 0.36 to 1.60, particularly 0.45 to 1.15. It is suitable from the point of impact strength and moldability.

  The polybutylene terephthalate resin and polyethylene terephthalate resin are used in proportions of 1 to 99% by weight of polybutylene terephthalate resin and polyethylene terephthalate based on the total of polybutylene terephthalate resin and polyethylene terephthalate resin from the viewpoint of flame retardancy and crystallinity. The resin is preferably 99 to 1% by weight, more preferably 10 to 95% by weight of the polybutylene terephthalate resin and 90 to 5% by weight of the polyethylene terephthalate resin.

  Also, (A) Polybutylene terephthalate resin, or a mixture of polybutylene terephthalate resin and polyethylene terephthalate resin, polyester elastomer, polyarylate resin, wholly aromatic liquid crystal polyester, semi-aromatic liquid crystal polyester, polycyclohexanedimethylene terephthalate resin, etc. One or more polyester resins may be blended. In addition, a compounding quantity is the quantity of the range in which the effect of this invention does not fall large.

  The (B) epoxy-modified styrene resin in the present invention is one in which an epoxy group is introduced into a styrene resin. As a method for introducing the epoxy group, any conventionally known method can be used. Specifically, a styrene resin obtained by graft polymerization or copolymerization of an epoxy group-containing vinyl monomer is preferably used. Epoxy group-containing vinyl monomers are compounds that share both radically polymerizable vinyl groups and epoxy groups in one molecule. Specific examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and itaconic acid. Examples thereof include glycidyl esters of unsaturated organic acids such as glycidyl, glycidyl ethers such as allyl glycidyl ether, and the aforementioned derivatives such as 2-methylglycidyl methacrylate. Among them, glycidyl acrylate and glycidyl methacrylate are preferably used. Moreover, these can be used individually or in combination of 2 or more types.

  As a method for producing a styrene resin obtained by graft polymerization or copolymerization of an epoxy group-containing vinyl monomer, a generally known method can be adopted. In particular, styrene or styrene and other single monomers copolymerizable therewith can be used. A method of copolymerizing a monomer with an epoxy group-containing vinyl monomer, styrene, or (co) polymer obtained by copolymerizing styrene and other monomers copolymerizable therewith The method of graft-polymerizing a vinyl monomer is mentioned. Such copolymerization and graft polymerization can also be performed by known methods.

  Examples of the other monomer copolymerizable with styrene include aromatic vinyl compounds other than styrene, vinyl cyanide compounds, (meth) acrylic acid alkyl esters, maleimide monomers, and the like. Examples of the aromatic vinyl compound other than styrene include α-methylstyrene, vinyltoluene, and divinylbenzene. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and (meth) acrylic acid. Examples of the alkyl ester include (meth) acrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and stearyl acrylate. Examples of the maleimide monomer include N-substituted maleimides such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and derivatives thereof. Other examples include diene compounds, maleic acid dialkyl esters, allyl alkyl ethers, unsaturated amino compounds, and vinyl alkyl ethers. These can be used alone or in combination of two or more.

  Preferable specific examples of the styrene resin used as a base for graft polymerization or copolymerization of an epoxy group-containing vinyl monomer include polystyrene resins, resins such as high impact polystyrene resins, mainly styrene resins, and acrylonitrile / styrene copolymers. (AS resin), styrene copolymers such as styrene / (meth) acrylate, styrene / butadiene resin, styrene / butadiene / styrene resin, styrene / isoprene / styrene resin, styrene / ethylene / butadiene / styrene resin, etc. Examples thereof include block copolymers containing styrene, ABS resins such as acrylonitrile / butadiene / styrene resins, acrylonitrile / butadiene / methyl methacrylate / styrene resins, and the like. Among these, a resin mainly composed of polystyrene and a styrene copolymer are preferable, and an acrylonitrile / styrene copolymer is most preferable.

  The amount used in graft polymerization or copolymerization of the epoxy group-containing vinyl monomer is not particularly limited as long as it is effective for improving the compatibility between the component (A) and the epoxy-modified styrene resin. However, it is preferable that it is 0.05 weight% or more with respect to an epoxy-modified styrene resin. Copolymerization in a large amount tends to decrease fluidity and gelation, and is preferably 20% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less.

  Examples of the polymer obtained by another epoxy group introduction method include epoxy-modified styrene resins obtained by epoxy-modifying styrene resins with epoxidizing agents such as peroxides, performic acid, peracetic acid, and perbenzoic acid. It is done. In this case, it is preferable that a diene monomer is randomly copolymerized or block copolymerized with the styrene resin in order to effectively perform the epoxy modification. As examples of diene monomers, butadiene, isoprene and the like are preferably used. Examples of suitable production methods for these epoxy-modified styrenic resins are disclosed in JP-A-6-256417, JP-A-6-220124 and the like. Preferred styrenic resins include copolymers such as styrene / butadiene resins, acrylonitrile / butadiene (which may contain an acrylonitrile component or styrene component) / styrene resins (ABS resins), acrylonitrile / butadiene / methyl methacrylate / Examples thereof include ABS resins such as styrene resins (MABS resins), block copolymers such as styrene / butadiene / styrene resins, styrene / butadiene resins, styrene / isoprene / styrene resins, and styrene / ethylene / butadiene / styrene resins. Of these, block copolymers such as styrene / butadiene / styrene resin, styrene / isoprene / styrene resin, and styrene / ethylene / butadiene / styrene resin are preferably used.

  The amount of epoxy group introduced into the epoxy-modified styrene resin in such an epoxy group introduction method is not particularly limited as long as it is effective for improving the compatibility between the component (A) and the epoxy-modified styrene resin. The epoxy equivalent is preferably 100 g / equivalent to 10,000 g / equivalent, more preferably 200 to 5000 g / equivalent, and still more preferably 250 to 3000 g / equivalent. The epoxy equivalent of these resins can be measured by the method described in JP-A-6-256417.

  One or more of these epoxy-modified styrene resins can be used. Of these, a styrene resin obtained by graft polymerization or copolymerization of an epoxy group-containing vinyl monomer is preferably used because of its good compatibility with the component (A).

  In the present invention, the content of the styrene component (styrene residue) of the epoxy-modified styrene resin is preferably 50% by weight or more, more preferably 70% by weight in the case of the styrene resin mainly composed of the above styrene. In the case of a styrene copolymer, it is preferably 30% by weight or more, more preferably 50% by weight or more, more preferably 60% by weight or more, and in the case of an ABS resin, 30% by weight or more. More preferably, it is 40% by weight or more, and in the case of a block copolymer, it is 10% by weight or more, more preferably 20% by weight or more.

  Examples of the epoxy-modified styrene resin obtained by graft polymerization or copolymerization of the epoxy group-containing vinyl monomer include styrene, styrene and other monomers copolymerizable therewith, and epoxy group-containing vinyl monomers. A copolymerized polymer is preferably used.

Among these, an epoxy-modified AS resin obtained by copolymerizing styrene, acrylonitrile and glycidyl methacrylate is particularly preferably used. The amount of glycidyl methacrylate copolymerized in such an epoxy-modified AS resin is not particularly limited as long as it is effective for improving the compatibility with the component (A), but is 0.05% by weight in the epoxy-modified AS resin. The above is preferable. Large amount tends liquidity reduction and gelling the copolymerization, good Mashiku is 5 wt% or less. The copolymerization amount of styrene and acrylonitrile is not particularly limited, but is preferably 50 to 99.9% by weight of styrene, 0.05 to 49.95% by weight of acrylonitrile, 70 to 99.9% by weight of styrene, Acrylonitrile is preferably 0.05 to 29.95% by weight.

  In addition, the amount of the epoxy-modified styrenic resin added is preferably 1 to 100 parts by weight with respect to 100 parts by weight of component (A) from the viewpoint of the appearance and flame retardancy of the obtained flame-retardant resin composition. Particularly preferred is 2 to 90 parts by weight.

  Although it does not limit as (C) phosphate ester in this invention, 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 not containing halogen. X is selected from the following formulas (2) to (4): In the formulas (2) to (4) below, 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 (5) and (6) are preferable, and the compound (5) is particularly preferable.

  As commercially available phosphoric acid esters, one or more selected from Daihachi Chemical Co., Ltd. PX-200, PX-201, PX-130, CR-733S, TPP, CR-741, CR747, TCP, TXP, CDP Preferably, one or more selected from PX-200, TPP, CR-733S, CR-741, CR747, particularly preferably PX-200, CR-733S, CR-741 are used. Among them, PX-200 is particularly preferable.

  Moreover, the addition amount of (C) phosphate ester is 1-100 weight part with respect to 100 weight part of (A) component from the point of a flame retardance and a mechanical characteristic, Preferably it is 2-90 weight part, More preferably, it is 3 ~ 80 parts by weight.

  As the salt of (D) triazine-based compound and cyanuric acid or isocyanuric acid in the present invention, cyanuric acid or an adduct of isocyanuric acid and triazine-based compound is preferable, usually 1 to 1 (molar ratio). An adduct having a composition of 1 to 2 (molar ratio). Of the triazine compounds, those that do not form a salt with cyanuric acid or isocyanuric acid are excluded. Among the salts of (D) triazine compounds with cyanuric acid or isocyanuric acid, melamine, benzoguanamine, acetoguanamine, 2-amido-4,6-diamino-1,3,5-triazine, mono (hydroxy) Methyl) melamine, di (hydroxymethyl) melamine, and tri (hydroxymethyl) melamine salts are preferred, and melamine, benzoguanamine, and acetoguanamine salts are preferred, and are prepared by known methods. For example, triazine compounds and cyanurates An acid or isocyanuric acid mixture is made into a water slurry and mixed well to form both salts in the form of fine particles, and the 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 100 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 80-1 μm. 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.

  In addition, the blending amount of the (D) triazine compound and the salt of cyanuric acid or isocyanuric acid is 1 to 150 parts by weight, preferably 100 parts by weight of component (A) from the viewpoint of flame retardancy and mechanical properties, It is 2-140 weight part, More preferably, it is 3-130 weight part.

  In the present invention, (E) a fiber reinforcing material can be blended. Examples of the (E) fiber reinforcement include glass fiber, aramid fiber, and carbon fiber. The above glass fiber is a chopped strand type or roving type glass fiber used for a normal PBT reinforcement, and is a silane coupling agent such as an aminosilane compound or an epoxysilane compound 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. The silane coupling agent and / or sizing agent may be used as an emulsion.

  In addition, the blending amount when blending the (E) fiber reinforcing material is preferably 1 to 250 parts by weight, particularly preferably 100 parts by weight of the component (A) from the viewpoint of flame retardancy and fluidity during molding. 2 to 230 parts by weight.

  Further, in the present invention, an inorganic filler can be further blended, and the crystallization characteristics, arc resistance, anisotropy, mechanical strength, flame retardancy or heat distortion temperature of the composition of the present invention are improved. Such inorganic fillers 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 whisker, calcium sulfate whisker, wollastonite, silica, kaolinite, talc, smectite clay mineral (montmorillonite, hectorite), vermiculite, mica, fluorine teniolite, zirconium phosphate, titanium phosphate, calcium phosphate, dolomite, barium carbonate , And calcium carbonate, etc. That. The inorganic filler may be subjected to a surface treatment such as a coupling agent treatment, an epoxy compound, or an ionization treatment. 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. Moreover, the compounding quantity of an inorganic filler has the preferable quantity which does not exceed the compounding quantity of the (E) fiber reinforcement of this invention.

  In this invention, by mix | blending a fluorine resin further, it can suppress that the flame-retardant resin composition at the time of combustion melts and falls, and can further improve a flame retardance. The above-mentioned fluororesin is a resin containing fluorine in a substance molecule. Specifically, polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetra (Fluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer, etc. Among them, polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer , Polyvinylidene fluoride are preferable, polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer are preferable. Moreover, the compounding quantity in the case of mix | blending a fluorine resin is 0.02-20 weight part with respect to 100 weight part of (A) component from the point of a flame retardance and a mechanical characteristic, Preferably it is 0.1-18 weight. Parts, more preferably 0.2 to 16 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 usually has a viscosity average molecular weight in the range of 10,000 to 1,000,000. If the viscosity average molecular weight is in the range of 10,000 to 1,000,000, polycarbonate resins having different viscosity average molecular weights are used in combination. Also good. Here, as the dihydric phenol compound, 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. In addition, the blending amount when the polycarbonate resin is blended is preferably 1 to 100 parts by weight, particularly preferably 2 to 90 parts by weight with respect to 100 parts by weight of component (A) from the viewpoint of flame retardancy and mechanical properties. is there.

  In the present invention, a flame retardant aid that helps flame retardancy such as a silicone compound, a phenol resin, a phosphonitrile compound, ammonium polyphosphate, and melamine phosphate can be blended and used in one or more kinds. In addition, the blending amount when blending the flame retardant aid is preferably 1 to 100 parts by weight, particularly preferably 2 to 100 parts by weight of component (A) from the viewpoint of flame retardancy and mechanical properties. 90 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 metacle 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 metacle 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.

  The above-mentioned 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, a novolak type phenol resin which is not added with a curing agent and is non-thermally reactive is preferable 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 Sugawara “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, ammonium melamine-modified polyphosphate, and ammonium carbamyl polyphosphate, and thermosetting phenol resin, urethane resin, melamine resin, urea resin, epoxy resin, and urea resin. It may be covered with a thermosetting resin such as, and may be used alone or in combination of two or more.

  Examples of the melamine phosphate include phosphates 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 the composition of the present invention. Examples of such ethylene (co) polymer include high-density polyethylene and low-density polyethylene. Examples include ethylene polymers such as polyethylene and ultra-low density polyethylene, and / or ethylene copolymers. 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, ester acids thereof, and dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid. Can be mentioned. 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 the component (A). Further, the blending amount when blending the ethylene (co) polymer is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the component (A) from the viewpoint of flame retardancy and impact strength of the resulting composition. Particularly preferred is 2 to 90 parts by weight.

  In the present invention, a phenoxy resin, an epoxy compound, an oxazoline compound, a carbodiimide compound, or the like, which is a hydrolysis resistance improving material, can be further blended, and a phenoxy resin or an epoxy compound is particularly preferably used. Moreover, the compounding quantity in the case of mix | blending said hydrolysis resistance improving material is 0.1 to 100 weight part of (A) component from the point of hydrolysis resistance and flame retardance of the composition obtained. 20 parts by weight is preferable, and 0.2 to 18 parts by weight is particularly preferable.

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 phenoxy molecular weight of the resin is not particularly limited, the viscosity average molecular weight is not preferable that the range of 1,000 to 100,000. 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.

  Moreover, as said epoxy compound, 1 or more types of epoxy compounds chosen from a glycidyl ester compound, a glycidyl ether compound, and a glycidyl ester ether compound are mentioned, The epoxy compound which has one or more epoxy groups in a molecule | numerator, and an epoxy equivalent of less than 1000 Is preferred. Here, an epoxy equivalent means the gram number of the epoxy compound containing 1 gram equivalent of an epoxy group. Here, the epoxy equivalent is obtained by dissolving an epoxy compound in pyridine, adding 0.05N hydrochloric acid and heating at 45 ° C., then using a mixed solution of thymol blue and cresol red as an indicator, and back titrating with 0.05N caustic soda. It can be determined by a method.

  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 antioxidant and / or phosphite antioxidant added is 0.1 with respect to 100 parts by weight of component (A) from the viewpoint of heat aging resistance and flame retardancy. -15 parts by weight is preferable, and 0.2-10 parts by weight is particularly preferable.

  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 Examples include, but are not limited to, a mixture. When the lubricant is blended, the addition amount is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of component (A).

  In the present invention, it is also possible to improve or adjust the color tone by blending one or more types of carbon black, titanium oxide, and pigments and dyes of various colors. Is preferably from 0.1 to 30 parts by weight, more preferably from 0.1 to 20 parts by weight, still more preferably from 0.1 to 30 parts by weight, based on 100 parts by weight of the component (A) from the viewpoint of mechanical properties of the resulting composition. 15 parts by weight.

  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, magnesium hydroxide, hydrotalcite, boric acid, calcium borate, calcium borate hydrate, zinc borate, zinc borate hydrate. Products, zinc hydroxide, zinc hydroxide hydrate, zinc tin hydroxide, zinc tin hydroxide hydrate, red phosphorus, heat-expanded graphite and dosonite, thermosetting melamine resin, thermosetting A thermosetting resin such as a 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.

  Furthermore, sulfur-based antioxidants, ultraviolet absorbers, plasticizers, antistatic agents and the like are known as long as they do not impair the purpose of the present invention for the flame-retardant polybutylene terephthalate resin composition and molded article of the present invention. A material in which one or more additives are blended can also be used.

  In the present invention, it is preferable not to blend polyphenylene ether or polyphenylene sulfide from the viewpoints of mechanical strength, fluidity, color tone, and color tone change. However, when blended, with respect to 100 parts by weight of component (A), It is necessary not to contain more than 5 parts by weight.

The flame-retardant polybutylene terephthalate resin composition and molded article of the present invention are usually produced by a known method. For example,
(A) polybutylene terephthalate resin, (B) epoxy-modified styrenic resin, (C) phosphoric acid ester, and (D) salt of triazine compound with cyanuric acid or isocyanuric acid, and (E) fiber if necessary Reinforcing materials, fluorine compounds, polycarbonate resins, silicone compounds, phenolic resins, phosphonitrile compounds, ammonium polyphosphate, flame retardant aids such as melamine phosphate, ethylene (co) polymers, (E) inorganic materials other than fiber reinforcing materials Extruded with or without premixing fillers, hydrolysis resistance improvers, hindered phenolic antioxidants and / or phosphite antioxidants, and other necessary additives as required The flame-retardant polybutylene terephthalate resin composition is prepared by supplying it to a machine etc. It is.

  As an example of the above-mentioned premixing, the effect of the present invention can be exhibited only by dry blending, but mixing can be performed using a mechanical mixing device such as a tumbler, a ribbon mixer, and a Henschel mixer. Further, (E) 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, the quantity is determined from the method of adding a plunger pump by installing a liquid addition nozzle in the middle of the intake section and vent section of a multi-screw extruder such as a twin screw extruder, or from the supply section. It may be a method of supplying with a pump. Further, in producing a flame-retardant polybutylene terephthalate resin composition, for example, but not limited to, for example, a single screw extruder, a twin screw extruder, a three screw screw equipped with a “unimelt” or “dalmage” type screw. An extruder, a kneader type kneader, or the like can be used.

  The flame retardant polybutylene terephthalate resin composition thus obtained can be molded by a generally known method, for example, a molded product of any shape by injection molding, extrusion molding, compression molding, sheet molding, film molding, etc. In particular, injection molding is suitable, and a molded product obtained by an injection molding method by insert molding in which a part of a metal part is directly integrated with a molded product may be used.

  In addition, a molded product comprising the flame-retardant polybutylene terephthalate resin composition of the present invention is excellent in safety against electric flame inside the device, safety against fire of the molded product itself, appearance of the molded product, mechanical properties, and the like. Therefore, it is useful for electric / electronic parts, mechanical mechanism parts, and automobile parts. Specifically, general home appliances, OA equipment housings, coil bobbins, connectors, relays, disk drive chassis, transformers, electromagnetic switches, 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, acoustic parts, audio parts such as laser discs, lighting parts, telegraph / telephone equipment-related parts, air conditioner parts, home appliances such as VTRs and TVs Examples include parts, copier parts, facsimile parts, optical equipment parts, automobile ignition device parts, automobile connectors, and various automotive electrical parts.

  Especially in the present invention, since the appearance of a molded product that is excellent in occurrence of bleed-out is maintained and a highly reliable flame-retardant molded product is obtained, it is particularly useful for electrical / electronic components and automotive electrical components. is there.

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

Reference Example 1 (A) Polybutylene terephthalate resin <A-1> Toray PBT-1100S (manufactured by Toray Industries, Inc.) which is a polybutylene terephthalate resin (hereinafter abbreviated as PBT) was used.

Reference Example 2 Polyethylene terephthalate resin <A-2> Polyethylene terephthalate resin (hereinafter referred to as PET) having an intrinsic viscosity of 0.65 (25 ° C., 1: 1 mixed solvent of phenol / tetrachloroethane) Mitsui PETJ005 (manufactured by Mitsui PET Resin Co., Ltd.) Abbreviated).

Reference Example 3 (B) Epoxy-modified styrene resin <B-1> A styrene / acrylonitrile / glycidyl methacrylate (74 / 25.5 / 0.5 wt%) copolymer (epoxy-modified AS resin) was used. The intrinsic viscosity of the epoxy-modified AS resin measured at 30 ° C. in a methyl ethyl ketone solvent is 0.53 dl / g.

  <B-2> Epoxy-modified styrene / butadiene copolymer (“Epofriend” A1010 manufactured by Daicel Chemical Industries, Ltd.) was used (hereinafter abbreviated as epoxy-modified SBS resin).

  <B-3> AS resin of styrene / acrylonitrile (74/26 wt%) copolymer was used.

Reference Example 4 (C) Phosphoric acid ester <C-1> The following aromatic phosphoric acid ester “PX-200” (produced by Daihachi Chemical Co., Ltd.) of the formula (5) was used.

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

Reference Example 5 (D) Salt of triazine compound and cyanuric acid or isocyanuric acid <D-1> Melamine cyanurate “MCA” (manufactured by Mitsubishi Chemical Corporation) was used (hereinafter abbreviated as MC salt).

Reference Example 6 (E) Fiber Reinforcement Material <E-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 7 Fluorine compound <F-1> Polytetrafluoroethylene “Teflon 6J” (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) was used (hereinafter abbreviated as Teflon).

Reference Example 8 Polycarbonate resin <G-1> “Iupilon” S3000 (manufactured by Mitsubishi Engineering Plastics) was used (hereinafter abbreviated as PC resin).

Reference Example 9 Silicone Compound <H-1> Silicone powder “DC4-7105” (manufactured by Dow Corning Toray, Inc.) was used.

Reference Example 10 Phenolic Resin <H-2> A novolac type phenolic resin “Sumilite Resin” PR53195 (manufactured by Sumitomo Durez) was used.

Reference Example 11 Phosphononitrile compound <H-3> 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. Yield 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 12 Ethylene Copolymer <I-1> Ethylene ethyl acrylate copolymer “A-709” (Mitsui DuPont Polychemical Co., Ltd.) was used.

Reference Example 13 Inorganic fillers other than fiber reinforcement <J-1> Silicate talc “LMS300” (manufactured by Fuji Talc) was used.

Reference Example 14 Hydrolysis resistance improving material <K-1> An epoxy compound “Epicoat 828” (manufactured by Japan Epoxy Resin Co., Ltd.) of bisphenol A diglycidyl ether was used.

Reference Example 15 Hindered phenolic antioxidant and / or phosphite antioxidant <L-1> pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Hindered phenolic antioxidant "IR-1010" (manufactured by Ciba Geigy Japan)
Reference Example 16 Hindered phenolic antioxidant and / or phosphite antioxidant <L-2> Phosphite antioxidant "Mark PEP-36" (made by Asahi Denka) of pentaerythritol phosphite compound
Examples 1 to 19 and Comparative Examples 1 to 12
(A) PBT, PET, (B) epoxy-modified styrenic resin, (C) 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) Phosphate ester, (D) MC salt, and other additives <F - 1>, <G-1>, <H-1>, <H-2>, <H-3>, <I-1>, <J-1>, <K-1>, <L-1>, <L-2> and the like were mixed in the blending composition shown in Tables 1 and 2 and added from the original filling portion. Moreover, in the example which mix | blended GF, the compound of the addition amount shown to Table 1 and Table 2 by the same method as the above except having installed the side feeder in the middle of the original loading part and the vent part, and adding (E) GF Was added from the original storage part. In addition, it melt-mixed on the extrusion conditions of kneading | mixing temperature 270 degreeC and screw rotation 150rpm, discharged in strand shape, let the cooling bath pass, and pelletized with the strand cutter.

  After drying the obtained pellets, each test piece was then molded by an injection molding machine, and the physical properties were measured under the following conditions. Tables 1 and 3 show the results.

(1) Flame retardancy Using a Toshiba Machine IS55EPN injection molding machine, the flame retardancy evaluation test piece was injection molded 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 1/16 inch (about 1.59 mm, hereinafter abbreviated as 1/16 ") and 1/32 inch (about 0.79 mm, hereinafter abbreviated as 1/32"). The thinner the value, the more severe the flame retardancy. Moreover, the material which was inferior in combustibility and did not correspond to said flame retardance rank was made into the outside of specification.

(2) Tensile strength 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 tensile strength was measured according to ASTM D638.

(3) Fluidity Similar to the above flame retardancy, 1/16 inch (approx. 1.59 mm) thick flame retardant using IS55EPN injection molding machine manufactured by Toshiba Machine under the conditions of a molding temperature of 270 ° C. and a mold temperature of 80 ° C. The test piece for property evaluation was injection-molded, and the minimum molding pressure at which the test piece was filled was determined.

  The lower the molding lower limit pressure, the better the fluidity during injection molding.

(4) Color tone and change in color tone Using an IS55EPN injection molding machine manufactured by Toshiba Machine, a square plate of 80 mm × 80 mm × thickness 3 mm injection-molded under conditions of a molding temperature of 270 ° C. and a mold temperature of 80 ° C. is used as a sample. The hot air dryer “HighTempOven” PVH210 manufactured by Tabai Co., Ltd., which was temperature-controlled, was heat treated for 100 hours.

  The yellowness (YI) of the color tone of the square plate before the drying machine was measured using an SM color computer manufactured by Suga Test Instruments. Note that the smaller the value of YI, the closer to white and the better the color tone.

  Moreover, the color change of the square plate before the drying machine was introduced and after the heat treatment was measured for the L, a and b Hunter color differences using an SM color computer manufactured by Suga Test Instruments Co., Ltd. in the same manner as described above.

  The smaller the Hunter color difference value, the less the color tone changes.

(5) Bleed-out test Using an IS55EPN injection molding machine manufactured by Toshiba Machine, a square plate of 80 mm × 80 mm × thickness 3 mm, which was injection-molded under conditions of a molding temperature of 270 ° C. and a mold temperature of 80 ° C., was set at 150 ° C. The temperature was adjusted in a hot air dryer “HighTempOven” PVH210 manufactured by Tabai Co., Ltd. and heat-treated for 100 hours.

  The appearance of the square plate before and after the drying machine was visually observed, and the presence or absence of bleed out was determined according to the following criteria.

  Here, the bleed out is a phenomenon in which a part of the compound in the molded product composition is stained on the surface of the molded product.

    ○: Bleed-out is not observed in the molded product before and after the dryer is charged.

    Δ: Bleed-out is not observed in the molded product before the dryer is charged.

        However, bleed-out is observed in the molded product after the dryer is charged.

    X: Bleed-out is observed in the molded product before and after the dryer is charged.

From the evaluation results of Examples 1 to 3 and Comparative Examples 1 to 3 and 9 in Table 1 without addition of GF, the PBT of the present invention shown in Examples 1 to 3 was added to an epoxy-modified styrene resin, a phosphate ester, and an MC salt. The composition with a high degree of flame retardancy is excellent in mechanical properties and fluidity during injection molding, and no bleed-out product is observed on the surface of the molded product. It can be seen that this is a reliable molded product. Further, the above embodiment showed particularly excellent performance is using an epoxy-modified AS resin as the epoxy-modified styrene resin.

  On the other hand, from Comparative Example 1, bleed-out was observed in the molded product before and after the dryer was fed unless an epoxy-modified styrene resin was blended.

  Further, from Comparative Examples 2 to 3, in the case where the phosphoric acid ester or MC salt is an unblended composition, the same flame retardancy as PBT is out of specification, the flame retardancy is not improved, and the flame retardancy A composition could not be obtained.

  Further, from Comparative Example 4, the material blended with AS resin instead of epoxy-modified styrenic resin did not exhibit high flame retardancy and had low mechanical strength and insufficient mechanical properties.

Further, from Examples 4 to 8 and Comparative Examples 5 to 7 and 10 , by adding GF as a fibrous reinforcing material, the tensile strength is remarkably increased, and a high-strength PBT resin composition is obtained. Compared with Comparative Examples 5 to 7, the composition obtained by blending the PBT of the present invention shown in Examples 4 to 8 of Table 1 with an epoxy-modified styrenic resin, phosphate ester, MC salt and GF has high flame retardancy. It has excellent mechanical properties and fluidity during injection molding, and no bleed-out product is observed on the surface of the molded product. Recognize. Further, the above embodiment showed particularly excellent performance is using an epoxy-modified AS resin as the epoxy-modified styrene resin.

  On the other hand, from the comparative example 5, in the case of the GF reinforced composition containing no epoxy-modified styrene resin, bleeding out was observed in the molded product before and after the dryer was charged.

  Moreover, from Comparative Examples 6-7, in the case of GF reinforcement | strengthening composition in which either phosphate ester or MC salt is unblended, flame retardance showed the non-standard and the flame retardance improvement was not recognized.

In addition, the composition of the present invention in which the amount of MC salt shown in Example 8 of Table 1 was increased greatly improved the flame retardancy, showed V-0 even at a thickness of 1/32 ", no bleed out, and more It can be seen that a molded article having high flame retardancy can be obtained.

The composition of 1/32 "thickness V-0 using a general halogen flame retardant blended with the brominated polycarbonate resin of Comparative Example 8 in Table 1 and antimony trioxide and 1/32 of Example 8 of the present invention. “Comparison of the composition of thickness V-0, it is clear that the composition of the present invention is a material having high mechanical strength and excellent fluidity during injection molding.

The compositions of the present invention shown in Examples 9 to 19 in Table 2 are blends that improve the flame retardancy, hydrolysis resistance, heat aging resistance, and the like of the composition of Example 5 .

From Examples 9 to 12 shown in Table 3, it can be seen that the flame retardancy is improved while maintaining other performances by blending the PC resin, silicone compound, phenol resin or phosphonitrile compound.

In addition, by blending the ethylene copolymers or talc of Examples 13 to 14 , tracking resistance (with a breakdown voltage (V) at which the insulation of the molded product is broken according to the test method shown in the IEC Publication 112 standard) In other words, the larger the breakdown voltage, the better.) Improved from a breakdown voltage of less than 600 V to a breakdown voltage of 600 V or more, and it was found that a molded product having excellent electrical characteristics can be obtained. However, in the case of an ethylene copolymer, the flame retardancy slightly decreased.

Moreover, after processing the composition which mix | blended the epoxy compound of Example 15 and Example 19 , and ASTM No. 1 dumbbell of Example 5 on the conditions of 121 degreeC and relative humidity 100% using a pressure cooker tester, 100 hours, When the tensile strength was measured, the tensile strength retention was improved by 20% from the composition of Example 5 . Therefore, it turns out that hydrolysis resistance improves by mix | blending an epoxy compound, maintaining other performance.

Moreover, was charged ASTM1 dumbbell of the composition of Example 5 comprising an antioxidant of Examples 16-19 in Tabai made Gya oven, 180 ° C., was treated under conditions of 300 hours, the tensile strength was measured The tensile strength retention was improved by about 15% or more from the composition of Example 5 . Therefore, it can be seen that the addition of the antioxidant improves the heat aging resistance while maintaining other performances.

Comparative Examples 11 to 12 shown in Tables 2 and 3 are compositions in which 6 parts by weight of 5 parts by weight or more of polyphenylene ether resin and polyphenylene sulfide resin are blended with 100 parts by weight of PBT resin in the composition of the present invention. From Table 3, it was a molded product that was greatly inferior in performance in terms of tensile strength, fluidity, color tone, and color tone change, and was a material that greatly impaired commercial value due to large color tone and color tone change.

Effect of the invention

  By blending PBT with a specific amount of epoxy-modified styrene resin, phosphate ester, salt of triazine compound and cyanuric acid or isocyanuric acid, fiber reinforcing material, if necessary, fluorine compound, etc. Highly reliable non-halogen flame retardant polybutylene that retains flame retardancy while maintaining excellent mechanical properties and fluidity during injection molding, maintaining excellent molded product appearance with little bleeding out A terephthalate resin composition and a resin molded product can be obtained, and it can be expected to greatly contribute to the market expansion of automobile parts, electric / electronic parts and mechanical parts.

Claims (5)

(A) 100 parts by weight of polybutylene terephthalate resin or 100 parts by weight of the total of polybutylene terephthalate resin and polyethylene terephthalate resin, (B) 1 to 100 parts by weight of epoxy-modified styrene resin, (C) 1 to 100 phosphates And (D) a composition comprising 1 to 150 parts by weight of a salt of a triazine compound and cyanuric acid or isocyanuric acid, and (B) an epoxy-modified styrenic resin comprising styrene, acrylonitrile and glycidyl methacrylate. The copolymerization amount of glycidyl methacrylate is 0.05 to 5% by weight in the epoxy-modified styrenic resin and does not contain 5 parts by weight or more of polyphenylene ether or polyphenylene sulfide. Polybutylene terephthalate Resin composition.
(B) The epoxy-modified styrene resin has a copolymerization amount of styrene of 50% to 99% by weight and an acrylonitrile copolymerization of 0.05% to 49.95% by weight. The flame-retardant polybutylene terephthalate resin composition according to claim 1.
The flame retardant polybutylene terephthalate resin composition according to claim 1 or 2, further comprising (E) 1 to 250 parts by weight of a fiber reinforcing material, based on 100 parts by weight of the component (A).
The flame retardant polybutylene terephthalate resin composition according to any one of claims 1 to 3, wherein the phosphoric acid ester of (C) is an aromatic phosphoric acid ester of the following formula (1).
[Chemical 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.)
[Chemical 2]

[Chemical Formula 3]

[Formula 4]

A molded article used for a mechanical mechanism part, an electric / electronic part or an automobile part, comprising the flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 4.