JP2002294050A - Flame-retardant polybutylene terephthalate resin composition and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both a flame-retardant polybutylene terephthalate resin composition having excellent flame retardance, mechanical characteristics, fluidity in injection molding and color tone of molding, hardly causing bleedout, having excellent hydrolysis resistance by compounding a polybutylene terephthalate resin with a nonhalogen-based flame retardant and a molding. SOLUTION: This flame-retardant butylene terephthalate resin composition is obtained by compounding (A) 100 pts.wt. of a polybutylene terephthalate resin or 100 pts.wt. of the total of the polybutylene terephthalate resin and a polyethylene terephthalate resin with (B) 1-100 pts.wt. of a vinyl-based resin, (C) 1-100 pts.wt. of a phosphoric ester, (D) 1-150 pts.wt. of a salt of a triazine- based compound and cyanuric acid or isocyanuric acid and (E) 0.1-10 pts.wt. of an alkaline earth metal compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition in which a non-halogen flame retardant is blended with a polybutylene terephthalate resin, and a molded article. More specifically, it has high flame retardancy, mechanical properties, fluidity during injection molding, excellent molded product color tone and hydrolysis resistance, and is a non-halogen based material suitable for mechanical mechanism parts, electric / electronic parts or automobile parts. The present invention relates to a flame-retardant polybutylene terephthalate resin composition and a molded product using a flame retardant.

[0002]

2. Description of the Related Art Polybutylene terephthalate resin (PB)
T) is utilized in a wide range of fields such as mechanical mechanism parts, electric / electronic parts, and automobile parts by making use of its excellent properties such as excellent injection moldability and mechanical properties.

[0003] Further, by combining PBT with a fiber reinforcing material, it is widely used as a material having further excellent mechanical properties and heat resistance. Among the fiber reinforcements, glass fibers are particularly used.

[0004] Because PBT is inherently flammable, it cannot be used for industrial materials such as mechanical and mechanical parts, electric and electronic parts, and automobile parts in addition to the general balance of chemical and physical properties. Flame safety, that is, flame retardancy is required, and a high degree of flame retardancy that indicates V-0 of the UL-94 standard is often required.

[0005] In addition, there is a demand for a molded article which can have various color tones with pigments and dyes as well as high flame retardancy.

As a method for imparting flame retardancy to PBT,
In general, a method of compounding a resin with a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant aid is used. However, this method tends to generate a large amount of smoke during combustion.

[0007] In addition, there is a movement to raise concerns about the influence of halogen-based flame-retardant materials on the environment due to increasing environmental awareness.

Therefore, in recent years, it has been strongly desired to use a flame retardant containing no halogen at all.

Hitherto, as a method of making a thermoplastic resin flame-retardant without using a halogen-based flame retardant, it has been widely known to add a hydrated metal compound such as aluminum hydroxide or magnesium hydroxide. In order to obtain sufficient flame retardancy, it is necessary to add a large amount of the above-mentioned hydrated metal compound, which has a disadvantage that the inherent properties of the resin are lost.

On the other hand, as a method for making a thermoplastic resin flame-retardant without using such a hydrated metal compound, adding red phosphorus is disclosed in JP-A-51-150553 and JP-A-5-150553.
JP-A-8-108248, JP-A-59-81351, JP-A-5-78560, JP-A-5-2871
No. 19, JP-A-5-295164, JP-A-5-295164
It is disclosed in Japanese Patent Application Laid-Open No. 320486 and Japanese Patent Application Laid-Open No. 5-339417.

[0011] However, although it is a useful flame-retardant resin material that does not use a halogen-based flame retardant, it has a problem in that it is peculiarly colored and its use is restricted because the color tone of the product is restricted. .

Further, JP-A-3-281652, JP-A-5-70671, JP-A-7-233331 and JP-A-8-73713 disclose an aromatic phosphate ester and melamine cyanurate. It is disclosed.

However, although it is a useful flame-retardant resin material that does not use a halogen-based flame retardant, the aromatic phosphate ester bleeds out on the surface of the molded article, greatly impairing the product value, and has a high resistance to hydrolysis. Had a problem inferior.

Further, Japanese Patent Application Laid-Open No. 10-147699,
JP-A-10-182555, JP-A-10-182
No. 956 and JP-A-2000-26710 disclose that a styrene-based resin is added to a composition containing PBT, polyphenylene ether, phosphate ester, and the like.

However, although it is a useful flame-retardant resin material that does not use a halogen-based flame retardant, blending polyphenylene ether lowers mechanical strength, lowers fluidity during injection molding, and causes molded articles to be colored yellow. There were problems such as inferior hydrolysis resistance and limited use.

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

However, although it is a useful flame-retardant resin material which does not use a halogen-based flame retardant, it has a very poor hydrolysis resistance and an extremely low flame-retardant effect, and further contains melamine cyanurate in combination. Thus, although the flame retardancy is improved, the problem of the hydrolysis resistance is not improved, so that the product value and the use are limited.

[0018]

That is, the present invention provides a polybutylene terephthalate resin blended with a non-halogen flame retardant to provide excellent flame retardancy and mechanical properties, fluidity during injection molding, and molded article color tone. It is still another object of the present invention to obtain a flame-retardant polybutylene terephthalate resin composition and a molded article which maintain excellent appearance of the molded article without causing bleed-out and have excellent hydrolysis resistance.

[0019]

Means for Solving the Problems In view of the above situation, the present inventors have made intensive studies and found that a specific amount of vinyl resin is added to polybutylene terephthalate resin (or polybutylene terephthalate resin and polyethylene terephthalate resin). The combination of aromatic phosphates, salts of triazine compounds with cyanuric acid or isocyanuric acid, and alkaline earth metal compounds, while maintaining highly excellent flame retardancy, while maintaining unique mechanical properties and injection It is possible to obtain a flame-retardant polybutylene terephthalate resin composition and a molded article having excellent fluidity during molding, excellent color tone of the molded article, maintaining excellent appearance of the molded article hardly causing bleed-out, and having excellent hydrolysis resistance. This has led to the present invention.

In the present invention, the reduction of the hydrolysis resistance, which is a drawback of the phosphoric ester flame retardant system, has been remarkably improved, and a practical level of hydrolysis resistance has been successfully provided.

That is, the present invention relates to (B) a vinyl resin 1 to 10 parts by weight based on 100 parts by weight of a polybutylene terephthalate resin or a total of 100 parts by weight of a polybutylene terephthalate resin and a polyethylene terephthalate resin.
0 parts by weight, (C) 1 to 100 parts by weight of a phosphoric ester,
Flame-retardant polybutylene terephthalate resin comprising (D) 1 to 150 parts by weight of a salt of a triazine compound and cyanuric acid or isocyanuric acid, and (E) 0.1 to 10 parts by weight of an alkaline earth metal compound. An object of the present invention is to provide a molded article for use in a mechanical mechanism part, an electric / electronic part or an automobile part, comprising the composition and the flame-retardant polybutylene terephthalate resin composition.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant polybutylene terephthalate resin composition and molded article of the present invention will be specifically described below.

The polybutylene terephthalate resin (A) in the present invention is a polymer obtained by a polycondensation reaction between terephthalic acid or its ester-forming derivative and 1,4-butanediol or its ester-forming derivative. , In addition to the acid component, isophthalic acid,
Naphthalenedicarboxylic acid, adipic acid, sebacic acid, dodecandic acid, oxalic acid, etc., as a glycol component,
Ethylene glycol, propylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-
Hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, or the like, or long-chain glycols having a molecular weight of 400 to 6000, ie, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc.
0 mol% or less can be copolymerized. Preferred examples of these polymers or copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate),
Examples thereof include polybutylene (terephthalate / decanedicarboxylate) and polybutylene (terephthalate / naphthalate), which may be used alone or as a mixture of two or more. Here, “/” means copolymerization.

The polymer or copolymer has an intrinsic viscosity of 0.36 to 1.60, particularly 0.42 to 1.25, measured at 25 ° C. using an o-chlorophenol solvent. Is suitable from the viewpoints of impact strength and moldability of the composition obtained. Further, the polybutylene terephthalate resin (A) may be a combination of polybutylene terephthalate resins having different intrinsic viscosities. As such polybutylene terephthalate having different intrinsic viscosities, intrinsic viscosities of 0.36 to
It is preferable to use a polybutylene terephthalate resin in the range of 1.60.

Further, those polybutylene terephthalate resins having a COOH terminal group content of 1 to 50 eq / t (terminal group amount per ton of polymer) obtained by potentiometric titration of the m-cresol solution with an alkaline solution. Can be preferably used in terms of durability and anisotropy suppressing effect. Further, those having a small number of COOH terminal groups can be preferably used because they have excellent hydrolysis resistance.

In the present invention, a polybutylene terephthalate resin and a polyethylene terephthalate resin can be used in combination instead of the polybutylene terephthalate resin (A). Such a 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, as an acid component, isophthalic acid, adipic acid, oxalic acid, etc. Propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, or the like, or a long chain having a molecular weight of 400 to 6,000 Glycols, 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, polyethylene terephthalate resin is prepared by using o-chlorophenol solvent as a solvent.
It is suitable from the viewpoints of impact strength and moldability of a composition that can be obtained having an intrinsic viscosity measured at 5 ° C. in the range of 0.36 to 1.60, particularly 0.45 to 1.15.

The ratio of the polybutylene terephthalate resin to the polyethylene terephthalate resin is determined based on the total of the polybutylene terephthalate resin and the polyethylene terephthalate resin in view of flame retardancy and crystallinity.
The content of the polybutylene terephthalate resin is preferably 1 to 99% by weight, and the content of the polyethylene terephthalate is preferably 99 to 1% by weight.
More preferably, the content is 5 to 90% by weight of the polyethylene terephthalate resin.

In addition, (A) polybutylene terephthalate, and a mixture of polybutylene terephthalate resin and polyethylene terephthalate resin, are mixed with polyester elastomer, polyarylate resin, wholly aromatic liquid crystal polyester, semi-aromatic liquid crystal polyester and polycyclohexane dimethylene terephthalate. One or more polyester resins such as resins may be blended, and the blending amount is within a range that does not greatly reduce the effects of the present invention.

The vinyl resin (B) in the present invention is not limited, but may be an aromatic vinyl compound,
A resin obtained by polymerizing one or more monomers selected from a vinyl cyanide compound, an alkyl (meth) acrylate, and a maleimide-based monomer, or a rubber-based component such as a polybutadiene-based rubber, Examples thereof include those obtained by graft polymerization or copolymerization of the polymer (hereinafter, these may be collectively referred to as “(co) polymer”). Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene, and divinylbenzene. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Is methyl methacrylate, ethyl methacrylate,
Examples include alkyl (meth) acrylates such as n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and stearyl acrylate. Examples of the maleimide-based monomer include maleimide and N-methylmaleimide. , N-ethylmaleimide, N
N-substituted maleimides such as -phenylmaleimide, N-cyclohexylmaleimide, and derivatives thereof. The present invention also includes a vinyl resin having the following components which can be copolymerized with the above vinyl resin. Specific examples of such copolymerizable components include diene compounds, dialkyl maleates, allyl alkyl ethers, unsaturated amino compounds, and vinyl alkyl ethers.

(B) Examples of preferred (co) polymers of vinyl resin include polymethyl methacrylate, methyl methacrylate / acrylonitrile, polystyrene resin, acrylonitrile / styrene resin (AS resin), styrene /
Vinyl (co) polymers such as butadiene resin, styrene / N-phenylmaleimide resin, styrene / acrylonitrile / N-phenylmaleimide resin, acrylonitrile / butadiene (which may contain an acrylonitrile component or a styrene component) / styrene resin (ABS resin), acrylonitrile / butadiene / methyl methacrylate / styrene resin (MABS resin), styrene resin modified with a rubbery polymer such as high impact-polystyrene resin, and styrene / styrene as a block copolymer.
Butadiene / styrene resin, styrene / isoprene / styrene resin, styrene / ethylene / butadiene / styrene resin, and the like. In particular, polystyrene resin and acrylonitrile / styrene resin are preferable, and copolymers obtained by copolymerizing acrylonitrile and styrene are preferable. Acrylonitrile / styrene resin which is a polymer is more preferable (/ indicates copolymerization). The copolymerization amount of styrene and acrylonitrile in the acrylonitrile / styrene resin is not particularly limited, but is preferably 50 to 99% by weight of styrene and 50 to 1% by weight of acrylonitrile based on the total of both.

The vinyl resin may further include unsaturated monocarboxylic acids in the above (co) polymer,
A vinyl copolymer obtained by graft polymerization or copolymerization of an unsaturated dicarboxylic acid, an unsaturated acid anhydride or an epoxy group-containing vinyl monomer may be used. Among them, a vinyl copolymer obtained by graft polymerization or copolymerization of an unsaturated acid anhydride or an epoxy group-containing vinyl monomer is preferable.

Such an epoxy group-containing vinyl monomer includes:
Glycidyl esters of unsaturated organic acids such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconate are compounds that share both a vinyl group and an epoxy group that can be radically polymerized in one molecule. And glycidyl ethers such as allyl glycidyl ether and the above-mentioned derivatives such as 2-methylglycidyl methacrylate. Among them, glycidyl acrylate and glycidyl methacrylate can be preferably used. These can be used alone or in combination of two or more.

Unsaturated acid anhydrides are compounds that share both a radically polymerizable vinyl group and an acid anhydride in one molecule, and specific examples include maleic anhydride.

As a method for producing a vinyl copolymer obtained by graft-polymerizing or copolymerizing the above-mentioned unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides, or epoxy group-containing vinyl monomers, A known method can be employed. In particular, an aromatic vinyl monomer (preferably styrene), or an aromatic vinyl monomer (preferably styrene) and another monomer copolymerizable therewith, and an unsaturated monomer A method of copolymerizing a carboxylic acid, an unsaturated dicarboxylic acid, an unsaturated acid anhydride or an epoxy group-containing vinyl monomer, wherein the (co) polymer has an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated A method of graft-polymerizing an acid anhydride or an epoxy group-containing vinyl monomer is exemplified. Such copolymerization and graft polymerization can also be performed by a known method.

The amount of the unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated acid anhydride or epoxy group-containing vinyl monomer used in the graft polymerization or copolymerization is as follows. Although it is not particularly limited as long as it is effective for improving the compatibility, it is preferably 0.05% by weight or more based on the vinyl resin. Copolymerization in a large amount tends to lower the fluidity and cause gelation, preferably 20% by weight or less, more preferably 10% by weight or less.
% By weight, more preferably 5% by weight or less.

In addition, peroxides,
A vinyl (co) polymer that is epoxy-modified with an epoxidizing agent such as formic acid, peracetic acid, and perbenzoic acid may be used.

In the method of introducing an epoxy group using an epoxidizing agent, the amount of the epoxy group introduced into the vinyl resin is as follows:
The component (A) is not particularly limited as long as it is effective for improving the compatibility between the component and the vinyl resin, but the epoxy equivalent is preferably 100 g / equivalent to 10,000 g / equivalent, and more preferably 200 to 5000 g / equivalent. Equivalent or less, more preferably 250 to 3000
g / equivalent or less. The epoxy equivalent of these resins can be measured by the method described in JP-A-6-256417.

The vinyl resin used in the present invention includes a vinyl resin obtained by graft polymerization or copolymerization of an epoxy group-containing vinyl monomer, a styrene / butadiene / styrene resin epoxy-modified with an epoxidizing agent, and styrene / isoprene. / Styrene resin, styrene / ethylene /
A block copolymer such as butadiene / styrene resin is preferably used because of its good compatibility with the component (A). Further, a vinyl resin obtained by graft polymerization or copolymerization of glycidyl methacrylate is more preferably used.
Among them, those obtained by copolymerizing glycidyl methacrylate are preferred, and particularly, copolymers obtained by copolymerizing styrene, acrylonitrile and glycidyl methacrylate are preferred. The preferable copolymerization amount of glycidyl methacrylate in the copolymer obtained by copolymerizing styrene, acrylonitrile and glycidyl methacrylate is preferably an amount effective for improving the compatibility with the component (A), and is preferably 0% based on the copolymer. It is preferably at least 0.1% by weight.
If copolymerized in large amounts, there is a problem of decreased fluidity and gelation,
It is preferably at most 20% by weight, more preferably at most 10% by weight, further preferably at most 5% by weight. Also,
The copolymerization amount of styrene and acrylonitrile is not particularly limited, but is preferably 50 to 99% by weight of styrene and 50 to 1% by weight of acrylonitrile based on the total of styrene and acrylonitrile.

The amount of the vinyl resin to be added depends on the appearance of the molded article of the flame-retardant resin composition and the flame retardancy (A).
It is 1 to 100 parts by weight, preferably 2 to 90 parts by weight, per 100 parts by weight of the component.

The phosphoric ester (C) in the present invention is not particularly limited, but commercially available ones and synthesized phosphoric esters 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 Phosphates, 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 phosphoric esters of the following formula (1) are preferably used.

[0041]

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(In the above formula, Ar ¹ , Ar ² , Ar ³ ,
Ar ⁴ represents the same or different aromatic groups containing no halogen. X represents a structure selected from the following formulas (2) to (4), and in formulas (2) to (4), R ¹ to
R ⁸ is the same or different hydrogen atom or C 1-5
Y represents a direct bond, O, S, SO ₂ ,
Represents C (CH ₃ ) ₂ , CH ₂ , CHPh, and Ph represents a phenyl group. Further, n in the expression (1) is an integer of 0 or more. In the formula (1), k and m are each an integer of 0 or more and 2 or less, and (k + m) is an integer of 0 or more and 2 or less. Note that such aromatic phosphates have different n
Alternatively, a mixture of aromatic phosphates having different structures may be used.

[0043]

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[0044]

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[0045]

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In the above 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, especially preferably 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 and m are each an integer of 0 or more and 1 or less;
Particularly preferably, k and m are each 1.

In the formulas (2) to (4), R ¹ to
R ⁸ represents the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Here, specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
tert-butyl group, n-isopropyl, neopentyl,
Examples include a tert-pentyl group, 2-isopropyl, neopentyl, tert-pentyl group, 3-isopropyl, neopentyl, tert-pentyl group, neoisopropyl, neopentyl, and tert-pentyl group, with hydrogen, methyl, and ethyl being preferred. , Especially hydrogen is preferred.

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

Of these, the following compounds (5) and (6) are preferred, and compound (5) is particularly preferred.

[0051]

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[0052]

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Commercially available phosphoric esters include PX-200, PX-201, PX-130, and CR-130 manufactured by Daihachi Chemical Co., Ltd.
733S, TPP, CR-741, CR747, TC
One, two or more selected from P, TXP and CDP can be used, preferably PX-200, TP
One or more selected from P, CR-733S, CR-741 and CR747, particularly preferably PX-20
0, CR-733S and CR-741 can be used, and among them, PX-200 is particularly preferable.

The addition amount of the phosphoric ester (C) is from 1 to 100 parts by weight, preferably from 2 to 90 parts by weight, based on 100 parts by weight of the component (A) in view of flame retardancy and mechanical properties. Preferably it is 3-80 parts by weight.

In the present invention, (D) a salt of a triazine compound and cyanuric acid or isocyanuric acid includes:
An adduct of cyanuric acid or isocyanuric acid with a triazine-based compound is preferred, usually 1 to 1 (molar ratio),
In some cases, it is an adduct having a composition of 1: 2 (molar ratio). Of the triazine compounds, those that do not form a salt with cyanuric acid or isocyanuric acid are excluded. (D) Among salts of a triazine compound and cyanuric acid or isocyanuric acid, in particular, melamine, benzoguanamine, acetoguanamine, 2-amide-4,6-
Diamino-1,3,5-triazine, mono (hydroxymethyl) melamine, di (hydroxymethyl) melamine,
Tri (hydroxymethyl) melamine salts are preferred, and melamine, benzoguanamine, and acetoguanamine salts are particularly preferred, and are produced by known methods.
A mixture of a triazine-based compound and cyanuric acid or isocyanuric acid is made into a water slurry, mixed well to form both salts into fine particles, and then the slurry is filtered and dried, and then generally obtained in powder form. Further, the above-mentioned salt does not need to be completely pure, and a somewhat unreacted triazine-based compound, cyanuric acid, or isocyanuric acid may remain. In addition, the average particle size of the salt before being mixed with the resin is preferably 100 to 0.01 μm, more preferably 100 to 0.01 μm, from the viewpoint of flame retardancy, mechanical strength and wet heat resistance of the molded product, retention stability, and surface properties. Is 80 to 1 μm. If the salt has poor dispersibility, a dispersant such as tris (β-hydroxyethyl) isocyanurate or a known surface treatment agent may be used in combination.

The compounding amount of the (D) triazine compound and the salt of cyanuric acid or isocyanuric acid is determined based on 100 parts by weight of the component (A) in view of flame retardancy and mechanical properties.
It is 1 to 150 parts by weight, preferably 2 to 140 parts by weight, more preferably 3 to 130 parts by weight.

The alkaline earth metal in the alkaline earth metal compound (E) used in the present invention is magnesium,
Calcium and barium are preferred. Examples of the alkaline earth metal compound include hydroxides, oxides, carbonates, sulfates, and the like of these alkaline earth metals.
Inorganic acid salts such as acetates and phosphates, acetates, lactates, and organic acid salts such as oleic acid, 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, and phosphorus. Barium acid, magnesium acetate, calcium acetate, barium acetate, magnesium lactate, calcium lactate, barium lactate, and also magnesium, calcium, and barium salts of organic acids such as oleic acid, palmitic acid, stearic acid, and montanic acid. Among them, magnesium hydroxide and calcium carbonate are preferably used, and calcium carbonate is more preferably used. One or more of such alkaline earth metals can be used. In addition, the above calcium carbonate is produced according to a manufacturing method, such as calcium chloride carbonate, light calcium carbonate, heavy calcium carbonate,
Wet-milled fine powder heavy calcium carbonate, wet heavy calcium carbonate (chalk) and the like are known, and both are included in the present invention. Further, the above-mentioned calcium carbonate and alkaline earth metal salt may be treated with one or more surface treatment agents such as silane coupling agents, organic substances and inorganic substances, and may be in the form of powder, plate or fiber. It may be used, but it is preferable to use it in a powder form of 10 μm or less from the viewpoint of dispersibility.

(E) By adding an alkaline earth metal compound, the hydrolysis characteristics can be remarkably improved. Phosphate ester-based compounds that are effective as non-halogen flame retardants have the disadvantage that their phosphate bonds are easily hydrolyzed and therefore have poor hydrolysis resistance. In the present invention,
It is presumed that the hydrolysis resistance was greatly improved by the synergistic action of bleed-out prevention by the vinyl resin and acid trap by the alkaline earth metal compound.

The amount of the alkaline earth metal compound (E) is preferably 10% from the viewpoint of mechanical properties and hydrolysis resistance.
The amount is 0.1 to 10 parts by weight, preferably 0.2 to 9 parts by weight, more preferably 0.3 to 8 parts by weight with respect to 0 parts by weight.

In the present invention, (F) an epoxy compound can be further blended. Such epoxy compounds include glycidyl ester compounds, glycidyl ether compounds, and glycidyl ester ether compounds, and one or more of these can be used.

In order to exhibit the effect of improving the hydrolysis resistance of PBT, an epoxy compound having an epoxy equivalent of less than 500 is preferable, and an epoxy compound having an epoxy equivalent of less than 400 is particularly preferable. Here, the epoxy equivalent is an epoxy compound in which the number of grams of the epoxy compound containing 1 gram equivalent of epoxy group is less than 500, and the epoxy equivalent is obtained by dissolving the epoxy compound in pyridine,
After adding 0.05N hydrochloric acid and heating at 45 ° C., a mixed solution of thymol blue and cresol red was used as an indicator,
It can be determined by a method of back titration with N caustic soda.

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. In particular, the viscosity stability of the obtained composition is improved. Monofunctional glycidyl ester compounds are more preferred from the balance of hydrolysis resistance.

Examples of the glycidyl ester compound include, but are not limited to, glycidyl benzoate, glycidyl tBu-benzoate, glycidyl P-toluate, glycidyl cyclohexanecarboxylate, and the like. Glycidyl pelargonate, glycidyl stearate, glycidyl laurate, glycidyl palmitate, glycidyl behenate, glycidyl versatate, glycidyl oleate, glycidyl linoleate, glycidyl linoleate, glycidyl behenol, Glycidyl stearate, diglycidyl terephthalate, diglycidyl isophthalate, jig phthalate Sidyl ester, diglycidyl naphthalene dicarboxylate, diglycidyl bibenzoate, diglycidyl methyl terephthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, diglycidyl cyclohexanedicarboxylate, diglycidyl adipate Esters, diglycidyl succinate, diglycidyl sebacate, diglycidyl dodecandionate, diglycidyl octadecanedicarboxylate, triglycidyl trimellitate, tetraglycidyl pyromellitic ester, and the like. Alternatively, two or more kinds can be used.

The glycidyl ether compound is not limited, but specific examples include phenylglycidyl ether, O-phenylphenylglycidyl 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-ethoxy Ethane, 1- (β, γ-epoxypropoxy) -2-benzyloxyethane, 2,2-bis- [р- (β, γ-epoxypropoxy) phenyl] propane and bis- (4-hydroxyphenyl) methane Diglycidyl ether obtained by the reaction of other bisphenol and epichlorohydrin, and the like,
One or more of these can be used.

The compounding amount of the epoxy compound (F) is preferably 0.05 to 10 parts by weight, particularly preferably 0.1 to 100 parts by weight, based on 100 parts by weight of the component (A) from the viewpoint of mechanical properties and hydrolysis resistance. ９9 parts by weight.

In general, it is known that the use of an epoxy compound blocks a terminal carboxyl group of a polybutylene terephthalate resin, thereby improving the hydrolysis resistance of the polybutylene terephthalate resin.
When a vinyl resin, an alkaline earth metal compound, and the present epoxy compound are used in combination, hydrolysis resistance is synergistically improved, and a high degree of hydrolysis resistance that cannot be attained by simply adding an epoxy compound can be provided. Becomes possible.

In the present invention, a high-strength resin can be obtained by further blending a fiber reinforcing material. Examples of the fiber reinforcing material include glass fiber, aramid fiber, and the like.
And carbon fiber. The above-mentioned glass fiber is a chopped strand type or roving type glass fiber used for an ordinary PBT reinforcing material, 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 novolak epoxy compounds are preferably used. Further, the above silane coupling agent and / or sizing agent may be used in an emulsion liquid.

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

Further, in the present invention, an inorganic filler can be further blended, and the composition of the present invention has one or more properties such as crystallization characteristics, arc resistance, anisotropy, mechanical strength, flame retardancy or heat deformation temperature. The inorganic filler includes, but is not limited to, acicular, granular, powdered and layered inorganic fillers, and specific examples include glass beads, milled fiber, Glass flakes, potassium whisker, titanite, silica, kaolinite, talc, smectite clay minerals (montmorillonite, hectorite), vermiculite, mica, fluorine teniolite, zirconium phosphate,
Titanium phosphate, dolomite, and the like are used, and one or more kinds are used. The inorganic filler may have been subjected to a surface treatment such as a coupling agent treatment, an epoxy compound, or an ionization treatment. Further, the average particle size of the granular, powdery and layered inorganic filler is preferably from 0.1 to 20 μm, particularly preferably from 0.2 to 10 μm from the viewpoint of impact strength. Further, the amount of the inorganic filler is preferably not more than the amount of the fiber reinforcing agent.

In the present invention, by further blending a fluorine-based resin, the flame-retardant resin composition at the time of combustion can be prevented from melting and falling, and the flame retardancy can be further improved. The above-mentioned fluororesin is a resin containing fluorine in a substance molecule, and specifically, polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (Fluoroethylene / perfluoroalkylvinyl ether) copolymer, (tetrafluoroethylene / ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer, etc. Among them, polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer , Polyvinylidene fluoride are preferable, polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer are preferable. The amount of the fluorine-based resin is 0.1 to 100 parts by weight of the component (A) in view of flame retardancy and mechanical properties.
The amount is from 02 to 20 parts by weight, preferably from 0.1 to 18 parts by weight, more preferably from 0.2 to 16 parts by weight.

In the present invention, flame retardancy can be further improved by further blending a polycarbonate resin. Examples of the polycarbonate resin include an aromatic homo- or copolycarbonate obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester. The aromatic homo- or copolycarbonate resin has a viscosity-average molecular weight usually in the range of 10,000 to 1,000,000, and if the viscosity-average molecular weight is in the range of 10,000 to 1,000,000, a polycarbonate resin having a different viscosity-average molecular weight is used in combination. Is 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 and the like can be used, and these can be used alone or as a mixture. Further, the blending amount of the polycarbonate resin is preferably 1 to 100 parts by weight based on 100 parts by weight of the component (A) from the viewpoint of flame retardancy and mechanical properties.
Particularly preferably, it is 2 to 90 parts by weight.

In the present invention, a flame retardant aid such as a silicone compound, a phenol resin, a phosphonitrile compound, ammonium polyphosphate, and melamine phosphate, which aids in flame retardancy, can be further used. Also,
The compounding amount of the above flame retardant aid is preferably 1 to 100 parts by weight, particularly preferably 2 to 90 parts by weight, based on 100 parts by weight of the component (A) from the viewpoint of flame retardancy and mechanical properties.

Examples of the above-mentioned silicone compound include silicone resin, silicone oil and silicone powder.

The above-mentioned silicone resin includes a saturated or unsaturated monovalent hydrocarbon group, a hydrogen atom, a hydroxyl group,
Polyorganosiloxane in which a group selected from an alkoxyl group, an aryl group, a vinyl or allyl group and a siloxane are chemically bonded, and at room temperature, about 200 to 300
Although it is preferable to have a viscosity of 000000 centipoise, as long as it is the above-mentioned silicone resin, it is not limited thereto, and the product shape may be oil-like, powder-like and gum-like.
A methacle group and an amino group may be introduced,
It may be a mixture with at least one kind of silicone resin.

As the silicone oil, a polysiloxane 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 or allyl group and a siloxane are chemically bonded is used. Organosiloxanes, at room temperature of about 0.65 to
A resin having a viscosity of 100,000 centistokes is preferred, but is not limited to the above silicone oil resin, and the product may be in the form of an oil, powder, or gum, and may have an epoxy group as a functional group. A group, a methacle group and an amino group may be introduced, or a mixture with two or more silicone oils or silicone resins may be used.

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

The above-mentioned phenol resin is not particularly limited as long as it is a polymer having a plurality of phenolic hydroxyl groups, and examples thereof include novolak type, resol type and heat reaction type resins.
Alternatively, a resin obtained by modifying these may be used. These may be an uncured resin, a semi-cured resin, or a cured resin without a curing agent added. Above all, a novolak type phenol resin which is non-thermally reactive without the addition of a curing agent is preferred in terms of flame retardancy, mechanical properties, and economy.

The shape is not particularly limited, and any of pulverized products, granules, flakes, powders, needles, liquids and the like can be used, and if necessary, one or more kinds can be used. The phenolic resin is not particularly limited, and a commercially available phenolic resin is used. For example,
In the case of a novolak-type phenol resin, the phenols and the aldehydes are charged into the reaction tank at a molar ratio of 1: 0.7 to 1: 0.9, and oxalic acid, hydrochloric acid, sulfuric acid, toluenesulfonic acid and the like are further charged. After adding the catalyst of the above, heating,
The reflux reaction is performed for a predetermined time. Vacuum dehydration or static dehydration to remove generated water, and further, a method of removing remaining water and unreacted phenols can be obtained. 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 1: 1 to 1: 2
After charging into a reaction tank at such a ratio as follows and adding a catalyst such as sodium hydroxide, aqueous ammonia, or another basic substance, the same reaction and treatment as for the novolak type phenol resin can be performed.

Here, phenols include phenol, o-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, te
rt-butylcatechol, catechol, isoeugenol, o-methoxyphenol, 4,4'-dihydroxyphenyl-2,2-propane, isoamyl salicylate,
Benzyl salicylate, methyl salicylate, 2,6-di-
tert-butyl-p-cresol and the like. One or more of these phenols can be used. On the other hand, examples of aldehydes include formaldehyde, paraformaldehyde, polyoxymethylene, and trioxane. One or more of these aldehydes can be used as needed.

The molecular weight of the phenolic resin is not particularly limited, but is preferably 200 to 2,000 in number average molecular weight.
In particular, those having a range of 400 to 1,500 are preferable 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 above-mentioned phosphonitrile compound include phosphonitrile compounds having a phosphonitrile linear polymer and / or a cyclic polymer as a main component, and may be any of linear or cyclic or a mixture thereof. The phosphonitrile linear polymer and / or cyclic polymer can be synthesized by a known method described in the author, “Synthesis and Application of Phosphazene Compounds”. For example, phosphorus pentachloride or trichloride is used as a phosphorus source. It can be synthesized by reacting ammonium chloride or ammonia gas as a phosphorus or nitrogen source by a known method (a cyclic substance may be purified), and substituting the obtained substance with alcohol, phenol and amines. .

Examples of the above ammonium polyphosphate include ammonium polyphosphate, melamine-modified ammonium polyphosphate, and ammonium carbamyl polyphosphate, and include phenol resins and urethane resins having thermosetting properties.
It may be coated with a thermosetting resin such as a melamine resin, a urea resin, an epoxy resin, and a urea resin, 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, and 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 the toughness such as impact strength of the composition of the present invention. And ethylene copolymers such as low-density polyethylene and ultra-low-density polyethylene, and / or ethylene copolymers. The above-mentioned ethylene copolymer is obtained by copolymerizing ethylene and a monomer copolymerizable therewith. And copolymerizable monomers include propylene, butene-1, vinyl acetate,
Monocarboxylic acids such as isoprene, butadiene, acrylic acid, and methacrylic acid, and ester acids thereof, and dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid are included. 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. Further, a copolymer obtained by graft-polymerizing or copolymerizing the above-mentioned ethylene (co) polymer with an unsaturated acid anhydride or glycidyl methacrylate is also preferably used.
These may be used alone or in combination of two or more, and may be used by mixing with one or more of the above ethylene (co) polymers. Further, among ethylene (co) polymers, a copolymer obtained by graft polymerization or copolymerization of an unsaturated acid anhydride or glycidyl methacrylate with polyethylene is preferred because of its good compatibility with PBT. The amount of the ethylene (co) polymer is 1 to 100 parts by weight of the component (A) in view of the flame retardancy and impact strength of the obtained composition.
The amount is preferably 100 parts by weight, particularly preferably 2 to 90 parts by weight.

In the present invention, for the purpose of further improving the hydrolysis resistance, a phenoxy resin, an oxazoline compound,
And a carbodiimide compound, and a phenoxy resin is particularly preferably used. The amount of the hydrolysis resistance improving material to be added is 0.1 to 20 parts by weight based on 100 parts by weight of the component (A) from the viewpoint of hydrolysis resistance and flame retardancy of the resulting composition. Preferably, it is particularly preferably 0.2 to 18 parts by weight.

Examples of the phenoxy resin include a phenoxy resin obtained by reacting an aromatic dihydric phenol compound with epichlorohydrin at various mixing ratios. The molecular weight of the phenoxy copolymer is not particularly limited, but the viscosity average molecular weight is 1000 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 or the like can be used, and these can be used alone or as a mixture. Also, the shape is not particularly limited,
Any of pulverized products, granules, flakes, powders, and liquids can be used. One or more of these phenoxy resins can be used as necessary.

In the present invention, a hindered phenol-based antioxidant and / or a phosphite-based antioxidant are further used as stabilizers which provide extremely good heat aging resistance even when the composition of the present invention is exposed to high temperatures for a long period of time. The amount of the hindered phenol-based antioxidant and / or the phosphite-based antioxidant is from 0.1 to 100 parts by weight based on 100 parts by weight of the component (A) from the viewpoint of heat aging resistance and flame retardancy. The amount is preferably 15 parts by weight, particularly preferably 0.2 to 10 parts by weight.

Specific examples of the above hindered phenol antioxidants include triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6 -Hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-)
Hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-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 '
-Hexamethylenebis (3,5-di-t-butyl-4-
Hydroxy-hydrocinnamide), N, N'-trimethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) and the like.

Examples of the phosphite-based stabilizer include tris (2,4-di-t-butylphenyl).
Phosphite, 2,2-methylenebis (4,6-di-t
-Butylphenyl) octyl phosphite, trisnonylphenyl phosphite, alkyl allyl phosphite, trialkyl phosphite, triallyl phosphite, pentaerythritol phosphite compound and the like.

In the present invention, it is possible to improve fluidity and mold release during molding by further adding one or more lubricants. Examples of such a lubricant include metal soaps such as calcium stearate and barium stearate, fatty acid esters, salts of fatty acid esters (including partially salted forms), fatty acid amides such as ethylenebisstearamide, ethylenediamine and stearic acid. And fatty acid amides comprising polycondensates of sebacic acid or polycondensates of phenylenediamine with stearic acid and sebacic acid, polyalkylene waxes, acid anhydride-modified polyalkylene waxes and the above lubricants and fluororesins or fluorine compounds. Mixtures include, but are not limited to. The amount of the lubricant to be added is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the component (A).

In the present invention, the color tone can be improved or toned by blending carbon black, titanium oxide, and one or more pigments or dyes of various colors. From the viewpoint of the mechanical properties of the resulting composition, 0.1 to 30 parts by weight per 100 parts by weight of the component (A)
The amount is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 15 parts by weight.

Further, as the above-mentioned carbon black,
Channel black, furnace black, acetylene black, anthracene black, oil smoke, pine, and, such as graphite and the like, average particle size below 500 nm, dibutyl phthalate absorption 50~400cm ³ / 100g
Is preferably used, and may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, silane coupling agent or the like as a treating agent. As the titanium oxide, carbon black having a rutile form or a crystal form such as an anatase form and 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. Further, the carbon black, titanium oxide, and pigments and dyes of various colors are melted with various thermoplastic resins from the viewpoint of improving dispersibility with the flame-retardant resin composition of the present invention and improving handleability during production. It may be used as a blend or simply as a blended mixed material. In particular, the above-mentioned thermoplastic resin is preferably a polyalkylene terephthalate, a vinyl resin, or an ethylene (co) polymer from the viewpoint of electrical properties such as tracking resistance.

In the present invention, it is possible to further add one or more known non-halogen flame retardants other than the present invention, and it is expected that the combustion time during combustion or the gas generated during combustion can be 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 Zinc, zinc hydroxide hydrate, zinc tin hydroxide,
Examples include zinc-tin hydroxide hydrate, red phosphorus, heat-expanded graphite and dawsonite, and thermosetting resins such as thermosetting melamine resins, thermosetting phenol resins, and thermosetting epoxy resins are mixed or mixed on the surface. It may be coated. Further, a coupling agent, an epoxy compound, or a fat or oil such as stearic acid may be mixed or coated on the surface.

Further, the flame-retardant polybutylene terephthalate resin composition and the molded article of the present invention may be sulfur-based antioxidants, ultraviolet absorbers, plasticizers, and antistatic agents as long as the object of the present invention is not impaired. A material in which one or more known additives such as an agent are blended can also be used.

The flame-retardant polybutylene terephthalate resin composition and molded article of the present invention are produced by a generally known method. For example, (A) polybutylene terephthalate resin or polybutylene terephthalate resin and polyethylene terephthalate resin, (B) vinyl resin, (C) phosphate ester, (D) salt of triazine compound and cyanuric acid or isocyanuric acid, ( E) an alkaline earth metal compound and, if necessary, a fiber-reinforcing agent, a fluorine compound, a polycarbonate resin, a silicone compound, a phenol resin, a phosphonitrile compound, a flame-retardant auxiliary such as ammonium polyphosphate and melamine phosphate, ethylene (Co) polymers, inorganic fillers other than fiber reinforcements, hydrolysis resistance improvers, hindered phenolic antioxidants and / or phosphite antioxidants, and if necessary, other necessary additions Pre-mixed with or without pre-mixing Flame retardant polybutylene terephthalate resin composition is prepared by sufficiently kneading.

As an example of the above premixing, the effect of the present invention can be exhibited only by dry blending, but mixing using a mechanical mixing device such as a tumbler, a ribbon mixer, and a Henschel mixer can be mentioned. Further, the fiber reinforcing material may be added by installing a side feeder in the middle of the base portion and the vent portion of a multi-screw extruder such as a twin-screw extruder. In the case of liquid additives, a liquid addition nozzle is installed in the middle of the vent and the multi-screw extruder, such as a twin-screw extruder, and a plunger pump is added. A method of supplying with a pump may be used. In producing a flame-retardant polybutylene terephthalate resin composition, for example, but not limited to, a single-screw extruder, a twin-screw extruder, a three-screw extruder equipped with a “Unimelt” or “Dalmage” type screw An extruder and a kneader-type kneader can be used.

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

Further, the molded article made of the flame-retardant polybutylene terephthalate resin composition of the present invention provides safety against electric flame inside the equipment, safety against fire of the molded article itself, appearance of the molded article, mechanical characteristics, and resistance to fire. Because of its excellent hydrolytic properties, it is useful for electric / electronic parts, mechanical mechanism parts, and automobile parts. Specifically, housing for general home appliances, OA equipment, coil bobbins, connectors, relays, disk drive chassis, transformers, electromagnetic switches, switch parts, outlet parts, motor parts, sockets, plugs, capacitors, various cases Type, resistors, electrical and electronic parts incorporating metal terminals and conductors, computer-related parts, audio parts, audio parts such as laser disks (registered trademark), lighting parts, telegraph and telephone equipment-related parts, air conditioner parts, VTRs, Examples include home appliance parts such as televisions, copier parts, facsimile parts, optical equipment parts, automobile ignition device parts, automobile connectors, and various automobile electrical parts.

In the present invention, a highly flame-retardant molded article having particularly excellent hydrolysis resistance can be obtained, and thus is particularly useful for electric / electronic parts and electric parts for automobiles.

[0101]

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

Reference Example 1 (A) Polybutylene terephthalate resin <A-1> Polybutylene terephthalate resin (hereinafter referred to as P
BT) (Toray PBT-1100S, manufactured by Toray Industries, Inc.).

Reference Example 2 Polyethylene Terephthalate Resin <A-2> Mitsui PETJ005 (Mitsui Pet Resin Co., Ltd.)
A polyethylene terephthalate resin having an intrinsic viscosity of 0.65 (hereinafter abbreviated as PET) was used.

Reference Example 3 (B) Vinyl Resin <B-1> An AS resin of a styrene / acrylonitrile (74/26% by weight) copolymer was used. The intrinsic viscosity of the AS resin measured at 30 ° C. in a methyl ethyl ketone solvent was 0.52 dl / g.

<B-2> Styrene / acrylonitrile /
A glycidyl methacrylate (74 / 25.5 / 0.5% by weight) copolymer was used (hereinafter abbreviated as epoxy-modified AS resin). The intrinsic viscosity of the epoxy-modified AS resin measured at 30 ° C. in a methyl ethyl ketone solvent was 0.53 dl.
/ G.

<B-3> Epoxy-modified styrene / butadiene copolymer (“Epofriend” manufactured by Daicel Chemical Industries, Ltd.)
A1010) (hereinafter abbreviated as epoxy-modified SBS resin).

Reference Example 4 (C) Phosphate <C-1> Aromatic phosphate "PX" of the following formula (5)
-200 "(manufactured by Daihachi Chemical Co., Ltd.) was used.

[0108]

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

[0110]

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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) Alkaline earth metal compound <E-1> Magnesium hydroxide "Kisuma 6E" (manufactured by Kyowa Chemical Industry Co., Ltd.) was used (hereinafter abbreviated as water mug).

<E-2> Calcium carbonate "KSS100"
0 "(manufactured by Dowa Calfine) (hereinafter abbreviated as charcoal).

Reference Example 7 (F) Epoxy Compound <F-1> A glycidyl ester of versatic acid "Kajura E10" (manufactured by Japan Epoxy Resin Co., Ltd.) was used.

<F-2> Bisphenol A diglycidyl ether “Epicoat 828” (manufactured by Japan Epoxy Resin Co., Ltd.) was used.

<F-3><F-1> 20% by weight and <F-
2> 80% by weight of epoxy compound Reference Example 8 Fiber reinforcement <G-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 9 Fluorinated Compound <H-1> Polytetrafluoroethylene “Teflon 6”
J "(manufactured by Du Pont-Mitsui Fluorochemicals) was used (hereinafter abbreviated as Teflon).

Reference Example 10 Flame retardant aid <I-1> Polycarbonate resin "Iupilon" S3000 (manufactured by Mitsubishi Engineering-Plastics Corporation) was used (hereinafter abbreviated as PC resin).

<I-2> Silicone powder "DC4-7105" (manufactured by Dow Corning Toray Silicone Co., Ltd.) was used as the silicone compound.

<I-3>"Sumiliteresin" PR53195 (manufactured by Sumitomo Durez) was used as a novolak type phenol resin.

<I-4> Phosphonitrile Compound Hexachlorocyclotriphosphazene (cyclic trimer) and phenol were reacted in THF in the presence of triethylamine. The obtained reaction solution was evaporated and dried, and washed with water to remove salts. 95% yield. The phosphonitrile cyclic polymer thus obtained was purified by recrystallization from acetone and used. The number average degree of polymerization n did not change and n
= 3.

Reference Example 11 Ethylene copolymer <J-1> Ethylene ethyl acrylate copolymer "A-7"
09 "(manufactured by Mitsui DuPont Polychemicals).

Reference Example 12 Inorganic filler other than fiber reinforcing material <K-1> Silicate talc "LMS300" (manufactured by Fuji Talc) was used.

Reference Example 13 Hindered phenol 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) <L-2> Phosphite antioxidant "Mark PEP-3 of pentaerythritol phosphite compound
6 "(manufactured by Asahi Denka Co., Ltd.) Examples 1 to 24, Comparative Examples 1 to 12 Using a twin screw extruder (manufactured by Nippon Steel Works, TEX-30α) having a screw diameter of 30 mm and an L / D35 co-rotating vent, (A) PBT, PET, (B) vinyl resin,
(C) Phosphoric acid ester, (D) MC salt, (E) alkaline earth metal compound, (F) epoxy compound, other additives <H-1>, <I-1 to I-4>, <J- 1>, <K-
1>, <L-1> and <L-2> were mixed in the composition shown in Tables 1 and 2 and added from the main filling portion. Also,
In the example of blending GF of <G-1>, except that a GF was added by installing a side feeder in the middle of the filling portion and the vent portion, the formulation having the amount shown in Table 1 was added in the same manner as described above. It was added from the filling part. In addition, melt-mixing was performed under the extrusion conditions of a kneading temperature of 270 ° C. and a screw rotation of 150 rpm.

After drying the obtained pellets, each test piece was 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's IS55EPN injection molding machine, a test piece for flame retardancy evaluation was injection molded at a molding temperature of 270 ° C. and a mold temperature of 80 ° C., and a UL94 vertical test was performed. The flame retardancy was evaluated according to the prescribed evaluation criteria. Flame retardancy is V-0
>V-1> V-2 in order of decreasing flame retardancy. The thickness of the test piece was 1/16 inch (about 1.59 inch).
mm, hereinafter 1/16 ") thickness and 1/32 inch (about 0.79mm, hereafter abbreviated 1/32") thickness, the thinner the thickness, the severer the flame retardancy. Materials which were inferior in flammability and did not correspond to the above-mentioned flame retardancy rank were out of the standard.

(2) Tensile strength Using a Toshiba Machine's IS55EPN injection molding machine, a 3 mm thick AS was used at a molding temperature of 270 ° C. and a mold temperature of 80 ° C.
Performed the injection molding of TM1 dumbbell, ASTM D638
The tensile strength was measured according to the following.

(3) Fluidity In the same manner as in the above flame retardancy, using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., at a molding temperature of 270 ° C. and a mold temperature of 80 ° C., 1/16 inch (about 1.59 mm). Injection molding of the test piece for evaluation of thickness flame retardancy was performed, and a molding lower limit pressure at a 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 Color Tone Change Using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd., injection molding was carried out at a molding temperature of 270 ° C. and a mold temperature of 80 ° C.
A square plate of 0 mm × 80 mm × thickness of 3 mm was used as a sample.
Hot air dryer “HighTe” manufactured by Tabai Co., Ltd.
mpOven "PVH210, and heat-treated for 100 hours.

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

Further, the color difference of the square plate before and after the above-mentioned drying machine was changed was measured for the L, a and b Hunter color differences using an SM color computer manufactured by Suga Test Instruments in the same manner as described above.

The smaller the value of the Hunter color difference, the smaller the change in color tone.

(5) Bleed-out test Using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd., injection molding was performed at a molding temperature of 270 ° C. and a mold temperature of 80 ° C.
A square plate of 0 mm × 80 mm × thickness of 3 mm was used as a sample.
Hot air dryer “HighTe” manufactured by Tabai Co., Ltd.
mpOven "PVH210, and heat-treated for 100 hours.

The appearance of the square plate before and after the dryer was charged 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 article composition is stained on the surface of the molded article.

：: Bleed-out is not observed in the molded product before and after the dryer is input. Δ: Bleed-out is not observed in the molded product before the dryer is input, but bleed-out is observed in the molded product after the dryer is input. : Bleed-out is observed in the molded product before and after the dryer is introduced.
AST obtained by performing injection molding of TM1 dumbbell pieces
After hydrolyzing the M1 dumbbell pieces under the conditions of a temperature of 121 ° C. and a humidity of 100% RH for 100 hours, ASTM D
The tensile strength was measured according to 648, and the measured value was shown as a retention (%) which is a percentage of the value obtained by dividing the tensile strength of the untreated product.

[0138]

[Table 1]

[0139]

[Table 2]

[0140]

[Table 3]

G of Examples 1 to 12 and Comparative Examples 1 to 4 in Table 1
From the evaluation results without F added, the compositions obtained by blending the vinyl resin, the phosphate ester, the MC salt, the alkaline earth metal compound and the epoxy compound with the PBT of the present invention shown in Examples 1 to 4 have a high flame retardancy. Excellent in mechanical properties and fluidity during injection molding while maintaining the properties, no bleed-out is observed on the surface of the molded product, resulting in a molded product with excellent appearance, and reliability with excellent hydrolysis resistance It can be seen that a molded product having a certain quality was obtained. In the above embodiment,
When an epoxy-modified AS resin was used as the vinyl resin, a particularly balanced performance was exhibited. Further, Examples 10 and 12 in which an alkaline earth metal compound and an epoxy compound containing a monofunctional epoxy compound were blended were the most excellent in hydrolysis resistance, and Example 10 in which a monofunctional epoxy compound was blended. Was particularly excellent in the balance between fluidity and hydrolysis resistance.

On the other hand, from Comparative Example 1, bleed-out was observed in the molded product before and after the introduction of the dryer unless the vinyl resin was blended.

From Comparative Examples 2-3, when the composition was not blended with either the phosphate ester or the MC salt, the PB
As with T, the flame retardancy is out of specification, and the flame retardancy does not improve.
No flame retardant composition was obtained.

Further, from Comparative Example 4, when no alkaline earth metal compound was added, the hydrolysis resistance was poor and the use was greatly restricted.

Examples 13 to 15 and Comparative Examples 5 to
From 8, by blending fibrous reinforcement GF,
The tensile strength is dramatically increased, and a high-strength PBT resin composition is obtained.

The P of the present invention shown in Examples 13 to 15 in Table 1
The composition of BT with vinyl resin, phosphate ester, MC salt, alkaline earth metal compound, epoxy compound, and GF has high mechanical properties and fluidity during injection molding while maintaining high flame retardancy. Since no bleed-out was observed on the surface of the molded article, a molded article having an excellent appearance was obtained, and it was found that the molded article was excellent in hydrolysis resistance and reliable.

On the other hand, from Comparative Example 5, in the case of the GF-reinforced composition containing no vinyl resin, bleed-out was observed in the molded product before and after the introduction of the dryer, and the molded product had no commercial value.

Further, from Comparative Examples 6 and 7, in the case of a GF-reinforced composition containing no phosphate ester or MC salt, the flame retardancy was out of specification, and no improvement in flame retardancy was observed. Was.

Further, the material containing the epoxy compound of Comparative Example 8 but not containing the alkaline earth metal compound was a material inferior in hydrolysis resistance and greatly restricted in use. In addition, it is clear from the above fact that the hydrolysis resistance is not significantly improved only by the epoxy compound.

The composition of the present invention in which the amount of the MC salt shown in Example 15 in Table 1 was increased significantly improved the flame retardancy, and
V-0 was exhibited even at a thickness of 2 ", and other excellent performance was maintained.

A composition of 1/32 "thickness V-0 using a general halogen-based flame retardant containing the brominated polycarbonate resin of Comparative Example 7 of Table 1 and antimony trioxide and the composition of Example 15 of the present invention were used. Comparing the composition of 1/32 "thickness V-0, the composition of the present invention has high mechanical strength, fluidity during injection molding,
It is clear that the material has excellent hydrolysis resistance.

The compositions of the present invention shown in Examples 16 to 24 of Table 2 were obtained by comparing the composition of Example 14 with the flame retardancy, hydrolysis resistance,
It is a compound that improves heat aging resistance and the like.

From Examples 16 to 19 shown in Table 3, it can be seen that the incorporation of a PC resin, a silicone compound, a phenol resin and a phosphonitrile compound improves flame retardancy while maintaining other properties.

Further, by blending the ethylene copolymer or talc of Examples 20 to 21, the tracking resistance (according to the test method shown in the IEC Publication 112 standard, the breakdown voltage at which the insulation of the molded product is broken) V), and the higher the breakdown voltage, the better.) Was improved from a breakdown voltage of less than 600 V to a breakdown voltage of 600 V or more, and a molded article having excellent electrical properties was obtained. However, in the case of the ethylene copolymer, the flame retardancy was reduced.

Further, the compositions containing the antioxidants of Examples 22 to 24 and the ASTM No. 1 dumbbell of Example 14 were put into a Taby gear oven (treated at 180 ° C. for 300 hours) to measure the tensile strength. As compared with the composition of Example 6, the tensile strength retention was improved by about 15% or more. Therefore, it can be seen that the addition of the antioxidant improves the heat aging resistance while maintaining other performances.

Comparative Examples 10 to 12 shown in Tables 2 and 3 show that instead of the vinyl-based resin of the composition of the present invention, polyphenylene which is known as a thermoplastic resin having better flame retardancy than vinyl-based resin or PBT resin is used. This is a composition containing 25 parts by weight of an ether resin, a polyphenylene sulfide resin and a nylon 6 resin in the same manner as the vinyl resin.

As shown in Table 3, the polyphenylene ether resin and the polyphenylene sulfide resin have improved flame retardancy, but are significantly inferior in tensile strength, fluidity, color tone, color tone change, and hydrolysis resistance. In particular, since the color tone and the change in color tone are large, it is a material that greatly impairs the commercial value. Further, the nylon 6 resin was a molded article which was significantly inferior in all properties including flame retardancy.

[0158]

According to the present invention, a specific amount of a vinyl resin, a phosphoric acid ester, a salt of a triazine compound and a cyanuric acid or isocyanuric acid, an alkaline earth metal compound, an epoxy compound, and, if necessary, a fiber reinforcement are added to PBT. By blending materials, fluorine compounds, etc., while maintaining high flame retardancy, it has specifically excellent mechanical properties and fluidity during injection molding, hardly bleeds out, and has excellent hydrolysis resistance An excellent and highly reliable non-halogen flame-retardant polybutylene terephthalate resin composition and a resin molded product can be obtained, which can be expected to greatly contribute to market expansion of automobile parts, electric / electronic parts and mechanical parts.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 5/521 C08K 5/521 C08L 101/00 C08L 101/00 F-term (Reference) 4F071 AA22 AA31 AA42 AA45 AA46 AA77 AB18 AB21 AC15 AC19 AF15 AF47 AH07 AH12 AH17 BB05 BC07 4J002 BC033 BC053 BC063 BG053 BG103 BH013 BH023 BN143 BN153 BN163 BP013 CD004 CF06W CF07X DE068 DE078 DE088 DE238 DG038 EG048 EG048 DG048 DG048 DH048

Claims (12)

[Claims] 1. A polybutylene terephthalate resin (A)
(B) 1 to 100 parts by weight of a vinyl resin, (C) 1 to 100 parts by weight of a phosphoric ester, and (D) a triazine compound with respect to 00 parts by weight or 100 parts by weight of a total of polybutylene terephthalate resin and polyethylene terephthalate resin. 1 to 1 with cyanuric acid or isocyanuric acid
50 parts by weight and (E) an alkaline earth metal compound.
A flame-retardant polybutylene terephthalate resin composition containing 1 to 10 parts by weight. 2. The polybutylene terephthalate resin and the polyethylene terephthalate resin are present in an amount of 99 to 1% by weight and a polyethylene terephthalate resin in an amount of 1 to 99% by weight based on the total of the polybutylene terephthalate resin and the polyethylene terephthalate resin.
The flame-retardant polybutylene terephthalate resin composition according to the above. 3. The flame-retardant polybutylene according to claim 1, wherein (E) the alkaline earth metal compound is at least one alkaline earth metal compound selected from magnesium, calcium, and barium. Terephthalate resin composition. 4. The flame-retardant polybutylene terephthalate resin composition according to claim 1, wherein (E) the alkaline earth metal compound is magnesium hydroxide and / or calcium carbonate. 5. The method according to claim 1, wherein the epoxy compound (F) is further added with 0.05 to
The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 4, which is blended in an amount of 10 parts by weight. 6. The epoxy compound (F) having an epoxy equivalent of 5
The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 5, which is an epoxy compound using a glycidyl ester compound and / or a glycidyl ether compound of 00 or less. 7. The epoxy compound (F) having an epoxy equivalent of 5
The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 6, which is a monofunctional glycidyl ester compound having a molecular weight of 00 or less. 8. The flame-retardant polybutylene terephthalate resin composition according to claim 1, wherein the phosphoric ester of (C) is an aromatic phosphoric ester of the following formula (1). Embedded image (In the above formula, Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are the same or different and represent a halogen-free aromatic group. X is selected from the following formulas (2) to (4). In the 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, and Y represents a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ ,
CH ₂ and CHPh are represented, and Ph represents a phenyl group. Further, n in the expression (1) is an integer of 0 or more. Also, (1)
In the formula, 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. Embedded image Embedded image Embedded image 9. The (B) vinyl resin is an AS resin obtained by copolymerizing acrylonitrile and styrene.
9. The flame-retardant polybutylene terephthalate resin composition according to any one of items 8 to 8. (B) The vinyl resin is epoxidized with a vinyl copolymer obtained by graft-polymerizing or copolymerizing an epoxy group-containing vinyl monomer or an unsaturated acid anhydride and / or an epoxidizing agent. The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 9, which is a vinyl (co) polymer. 11. The flame-retardant polybutylene terephthalate resin composition according to claim 1, wherein (B) the vinyl resin is a copolymer obtained by copolymerizing acrylonitrile, styrene and glycidyl methacrylate. 12. 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 11.