JP2002294052A - Flame-retardant resin composition and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both a flame-retardant resin composition and a molding, having excellent flame retardance, mechanical characteristics, fluidity in injection molding and color tone of molding, hardly causing bleedout, having excellent hydrolytic resistance by compounding a polyalkylene terephthalate resin with a nonhalogen-based flame retardant. SOLUTION: This flame-retardant resin composition is obtained by compounding (A) 100 wt.% of the polyalkylene terephthalate resin having <=40 eq/ton carboxy terminal group amount with (B) 1-100 pts.wt. of a styrenic resin, (C) 1-100 pts.wt. of a phosphoric ester, (D) 1-50 pts.wt. of a salt of a triazine- based compound and cyanuric acid or isocyanuric acid and (E) 0-250 pts.wt. of a fiber-reinforced material.

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 and a molded product obtained by blending a polyalkylene terephthalate resin having a carboxyl terminal group content of 40 eq / ton or less with a non-halogen flame retardant. More specifically, it has high flame retardancy, mechanical properties, fluidity during injection molding, excellent molded product color tone and hydrolysis resistance, and is suitable for mechanical mechanism parts, electric / electronic parts or automotive parts. The present invention relates to a resin composition and a molded article.

[0002]

2. Description of the Related Art Polyalkylene terephthalate resins are:
Utilizing its excellent properties such as excellent injection moldability and mechanical properties, it is used in a wide range of fields such as mechanical parts, electric / electronic parts, and automobile parts.

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

Since polyalkylene terephthalate resins are inherently flammable, they have general chemical and physical properties when used as industrial materials such as the above mechanical parts, electric / electronic parts, and automobile parts. In addition to balance, safety against flame, that is, flame retardancy is required, and UL-94
In many cases, a high degree of flame retardancy that indicates the standard V-0 is 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, as environmental consciousness has increased, there has been a move to worry about the effects of halogen-type flame-retardant materials on the environment.

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 particular coloring and has a problem that its use is limited 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, it has a problem that bleed-out of an aromatic phosphate on the surface of a molded article occurs, greatly impairing the product value. .

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, the addition of polyphenylene ether causes a decrease in mechanical strength, a decrease in fluidity during injection molding, and a molded article is colored yellow. In addition, there is a problem that the metal corrosion is poor and the use is limited.

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

However, although it is a useful flame-retardant resin material that does not use a halogen-based flame retardant, it has problems that the flame-retardant effect is extremely low and the hydrolysis resistance is poor. In addition, flame retardancy is improved by combining with flame retardant aids such as melamine cyanurate, but hydrolysis resistance is not improved, and there is a problem in long-term use under high temperature and high humidity. Was.

[0018]

That is, the present invention provides a polyalkylene terephthalate resin mixed with a non-halogen flame retardant to provide excellent flame retardancy and mechanical properties, fluidity during injection molding, and molded article color tone. An object of the present invention is to obtain a flame-retardant resin composition and a molded article which are less likely to cause 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 as a result, a polyalkylene terephthalate resin having a carboxyl terminal group content of 40 eq / ton or less, a specific amount of a styrene resin, The combination of aromatic phosphate, triazine compound and cyanuric acid or isocyanuric acid salt and fiber reinforced material, while maintaining high excellent flame retardancy, specific mechanical properties and flow during injection molding It has been found that a resin molded article having excellent properties and color tone of the molded article, hardly causing bleed-out, and having excellent hydrolysis resistance can be obtained, and has reached the present invention.

That is, the present invention relates to (B) 1 to 100 parts by weight of a styrene-based resin, (C) phosphoric ester 1 per 100 parts by weight of a polyalkylene terephthalate resin having a carboxyl terminal group content of 40 eq / ton or less. ~ 100
Parts by weight, (D) 1 to 150 parts by weight of a salt of a triazine compound and cyanuric acid or isocyanuric acid, and (E) 0 to 250 parts by weight of a fiber reinforcing material, and a flame-retardant resin composition. Another object of the present invention is to provide a molded article for a mechanical mechanism part, an electric / electronic part, or an automobile part comprising the above flame-retardant resin composition.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant resin composition and the molded article of the present invention will be specifically described below. Examples of the (A) polyalkylene terephthalate resin in the present invention include polyalkylene terephthalate, copolyesters of alkylene terephthalate, and mixtures of polyalkylene terephthalate.

Examples of the polyalkylene terephthalate include polymers obtained by using a diol component and a terephthalic acid component. Examples of the diol component include ethylene glycol, 1,4-butanediol, propylene glycol, trimethylene glycol, and tetramethylene glycol. Methylene glycol, hexamethylene glycol, neopentyl glycol, diethylene glycol, polyethylene glycol, cyclohexane dimethanol, 2,2-bis (2 ′
-Hydroxyethoxyphenyl) propane and derivatives thereof having an ester-forming ability.
Butanediol, its derivatives having ester-forming ability,
Polybutylene terephthalate and polyethylene terephthalate obtained by polycondensing ethylene glycol or a derivative thereof having an ester-forming ability with terephthalic acid or a derivative thereof having an ester-forming ability are preferably used.

In the present invention, the polyalkylene terephthalate resin has a carboxyl terminal group content of 1 to 40.
Those having a range of eq / ton (amount of terminal group per ton of polymer) are used in view of durability and anisotropy suppressing effect. The amount of the carboxyl terminal group is determined by potentiometric titration of the m-cresol solution with an alkali solution. Furthermore, the amount of carboxyl terminal groups is 1 to 30 eq / ton.
It is preferable to use a polyalkylene terephthalate resin having a hydrolysis resistance of 1 to 20 eq / ton, and most preferably 1 to 10 eq / ton. As the polyalkylene terephthalate having such a carboxyl terminal group amount, a known one can be used.

Polybutylene terephthalate 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. Isophthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, dodecandic acid, oxalic acid, etc., as glycol components, ethylene glycol, propylene glycol, neopentyl glycol, 1,5-
Pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, etc., or a molecular weight of 400 to 60
A long-chain glycol of 00, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol or the like can be copolymerized in an amount of 20 mol% or less. Preferred examples of these polymers or copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decane dicarboxylate), and polybutylene. (Terephthalate / naphthalate) and the like, and may be used alone or as a mixture of two or more. Here, “/” means copolymerization.

The polymer or copolymer has an intrinsic viscosity measured at 25 ° C. using an O-chlorophenol solvent in the range of 0.36 to 1.60, particularly 0.42 to 1.25. Is suitable from the viewpoints of impact strength and moldability of the composition obtained. In addition, polybutylene terephthalate having different intrinsic viscosities may be used in combination. As such polybutylene terephthalate having different intrinsic viscosities, it is preferable to use polybutylene terephthalate having an intrinsic viscosity in the range of 0.36 to 1.60.

The above-mentioned polyethylene terephthalate refers to a polymer obtained by polycondensation using terephthalic acid as an acid component and ethylene glycol as a glycol component. In addition, isophthalic acid, adipic acid, and oxalic acid are also used as acid components. An acid or the like as a glycol component, such as propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, or a molecular weight; Long-chain glycols of 400 to 6000, 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. Further, as the polyethylene terephthalate, it is possible to use polyethylene terephthalate having an intrinsic viscosity of 0.36 to 1.60, particularly 0.45 to 1.15, measured at 25 ° C. using an O-chlorophenol solvent. It is suitable from the viewpoint of impact strength and moldability of the composition. Further, polyethylene terephthalates having different intrinsic viscosities may be used in combination, and the polyethylene terephthalates having different intrinsic viscosities have intrinsic viscosities of 0.36 to 2.30.
Is preferably within the range.

The above-mentioned polybutylene terephthalate and polyethylene terephthalate may be used in combination.
9% by weight, 99-1% by weight of polyethylene terephthalate
It is.

In addition, polybutylene terephthalate, polyethylene terephthalate, and a mixture of polybutylene terephthalate and polyethylene terephthalate, polycyclohexane dimethylene terephthalate resin, polyester elastomer, polyarylate resin, wholly aromatic liquid crystal polyester, semi-aromatic liquid crystal polyester and the like May be blended, and the blending amount is within a range that does not impair the effects of the present invention. The present invention also includes a polyalkylene terephthalate alone or one or more polyalkylene terephthalate resin compositions other than the above polybutylene terephthalate and polyethylene terephthalate.

When using polybutylene terephthalate, polyethylene terephthalate, or polybutylene terephthalate and polyethylene terephthalate, one or more other polyalkylene terephthalates such as polycyclohexane dimethylene terephthalate resin may be blended. Further, one or more kinds of polyester elastomer, polyarylate resin, wholly aromatic liquid crystal polyester, semi-aromatic liquid crystal polyester and the like may be blended, and the blending amount is within a range not to impair the effects of the present invention.

It goes without saying that polyalkylene terephthalates other than the above-mentioned polybutylene terephthalate and polyethylene terephthalate may be used alone or in combination of two or more.

The (B) styrene-based resin in the present invention is a resin obtained by (co) polymerizing styrene as an essential component, and is not limited, but a styrene homopolymer and styrene are essential. A resin obtained by polymerizing one or more monomers selected from aromatic vinyl compounds, vinyl cyanide compounds, alkyl (meth) acrylates, and maleimide monomers, or
Examples thereof include those obtained by graft-polymerizing or copolymerizing these monomers with rubber-based components such as polybutadiene-based rubber (hereinafter, these may be collectively referred to as “(co) polymer”). Examples of the other aromatic vinyl compounds include α-methylstyrene, vinyltoluene, and divinylbenzene, and examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and the like. Examples of the ester include alkyl (meth) acrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and stearyl acrylate. Examples of the monomer include N-substituted maleimides such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and derivatives thereof. The present invention also includes a styrene-based resin having the following components that can be copolymerized with the above-mentioned styrene-based resin. Specific examples of such copolymerizable components include diene compounds, dialkyl maleates, allyl alkyl ethers, unsaturated amino compounds, and vinyl alkyl ethers. Examples of preferred (co) polymers of (B) styrene-based resin include polystyrene resin, acrylonitrile / styrene resin (AS resin),
Styrene (co) polymers such as styrene / butadiene resin, styrene / N-phenylmaleimide resin, styrene / acrylonitrile / N-phenylmaleimide resin, and acrylonitrile / butadiene (which may contain an acrylonitrile component or a styrene component) / Styrene resin (ABS resin), styrene resin modified with a rubbery polymer such as acrylonitrile / butadiene / methyl methacrylate / styrene resin (MABS resin), high impact polystyrene resin, and styrene / butadiene as a block copolymer / Styrene resin, styrene / isoprene / styrene resin, styrene / ethylene / butadiene / styrene resin, etc., and particularly preferred are polystyrene resin and acrylonitrile / styrene resin. Acrylonitrile / styrene resin acrylonitrile and styrene is a copolymer comprising by copolymerizing more preferably (/ denotes the 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.

As the styrene resin, unsaturated monocarboxylic acids in the above (co) polymer may be further used.
A styrene 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 styrene 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.

The unsaturated acid anhydrides are compounds which share both a radically polymerizable vinyl group and an acid anhydride in one molecule, and specific examples thereof include preferably 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, styrene, or styrene and other monomers copolymerizable therewith, may be used in combination with an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated acid anhydride or an epoxy group-containing vinyl monomer. And a method of graft-polymerizing an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated acid anhydride or an epoxy group-containing vinyl monomer to the (co) polymer. . 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 for graft polymerization or copolymerization depends on the amount of polyalkylene terephthalate and styrene resin. There is no particular limitation as long as it is effective for improving the solubility.
It is preferable that it is above. Copolymerization in a large amount tends to lower the fluidity and cause gelation, and is preferably 20% by weight or less, more preferably 10% by weight or less, and further preferably 5% or less.

In addition, peroxides may be added to the above (co) polymer.
A styrene-based (co) polymer 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 epoxy group introduced into the styrene resin is as follows:
The epoxy equivalent is not particularly limited as long as it is effective for improving the compatibility between the polyalkylene terephthalate and the styrene resin.
It is preferably 0 g / equivalent or less, 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.

The styrene resin used in the present invention includes:
In particular, in the styrene resin, a styrene resin obtained by graft-polymerizing or copolymerizing an epoxy group-containing vinyl monomer and a styrene / butadiene / styrene resin epoxy-modified with an epoxidizing agent, styrene / isoprene / styrene resin, styrene / Ethylene / butadiene /
A block copolymer such as a styrene resin is preferably used because of its good compatibility with the component (A). Furthermore, a styrene 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 preferred are copolymers obtained by copolymerizing styrene, acrylonitrile and glycidyl methacrylate. 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 a large amount, there is a problem of lowering of fluidity and gelation, preferably 20% by weight or less, more preferably 10% by weight or less,
More preferably, it is at most 5% by weight. The copolymerization amount of styrene and acrylonitrile is not particularly limited.
Preferably, the content is で 99% by weight and acrylonitrile 50５０1% by weight.

The amount of the epoxy-modified styrenic resin to be added is 1 to 1 with respect to 100 parts by weight of the component (A) from the viewpoint of the appearance of the molded article of the flame-retardant resin composition and the flame retardancy.
The amount is preferably 00 parts by weight, particularly preferably 2 to 90 parts by weight.

The phosphoric acid ester (C) in the present invention is not limited, but commercially available ones and synthesized phosphoric acid 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.

[0042]

Embedded image

(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.

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

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.

Among them, the following compounds (5) and (6) are preferred, and particularly preferred is compound (5).

[0052]

Embedded image

[0053]

Embedded image

Commercially available phosphoric esters include PX-200, PX-201, PX-130 and CR-
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 amount of the phosphoric acid 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, the salt of (D) a triazine compound with cyanuric acid or isocyanuric acid is
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.

In the present invention, (E) a fiber reinforcing material can be blended. Examples of the (E) fiber reinforcing material include glass fiber, aramid fiber, and carbon fiber. As the above glass fiber, ordinary PB
Chopped strand type or roving type glass fiber used as a reinforcing material for T, which is a silane coupling agent such as an aminosilane compound or an epoxysilane compound and / or urethane, vinyl acetate, bisphenol A diglycidyl ether, a novolak epoxy compound, etc. Glass fibers treated with a sizing agent containing one or more epoxy compounds are preferably used. Also,
The above silane coupling agent and / or sizing agent may be used in the emulsion liquid.

In the case where (E) a fiber reinforcing material is compounded, the amount of the component (A) is 1 in view of flame retardancy and fluidity during molding.
The amount is preferably from 1 to 250 parts by weight, particularly preferably from 2 to 230 parts by weight, based on 00 parts by weight.

Further, in the present invention, an inorganic filler can be further blended, and the composition of the present invention has one of crystallization characteristics, arc resistance, anisotropy, mechanical strength, flame retardancy and heat distortion 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 titanate, calcium sulphate whiskers, wollastenite, silica, kaolinite, talc,
Examples include smectite clay minerals (montmorillonite, hectorite), vermiculite, mica, fluoroteniolite, zirconium phosphate, titanium phosphate, calcium phosphate, dolomite, barium carbonate, calcium carbonate, and the like. 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. In addition, the compounding amount of the inorganic filler is (E) of the present invention.
An amount not exceeding the compounding amount of the fiber reinforcement is preferable.

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. When the fluorine-based resin is blended, the blending amount is preferably 0.02 to 20 parts by weight, and more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the component (A) in view of flame retardancy and mechanical properties.
18 parts by weight, more preferably 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. When the polycarbonate resin is compounded, the amount 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. is there.

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 amount of the above-mentioned flame retardant aid is 1 to 100 parts by weight of the component (A) in view of flame retardancy and mechanical properties.
The amount is preferably 100 parts by weight, particularly preferably 2 to 90 parts by weight.

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

As the above silicone resin, 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.

The silicone oil may be a polyisomer in which a siloxane is chemically bonded to 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. 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 or the like is preferably used.

The above-mentioned phenolic resin is not particularly limited as long as it is a polymer having a plurality of phenolic hydroxyl groups. Examples thereof include novolak-type, resol-type and heat-reactive 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 resole 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-mentioned ammonium polyphosphate include ammonium polyphosphate, melamine-modified ammonium polyphosphate, and ammonium carbamyl polyphosphate. Thermosetting phenol resins, urethane resins,
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 may be added 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 grafting or copolymerizing the above ethylene (co) polymer with an 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, copolymers obtained by grafting or polymerizing an acid anhydride or glycidyl methacrylate to polyethylene are preferred because they have good compatibility with the component (A). In addition, when the ethylene (co) polymer is compounded, the compounding amount is preferably 1 to 100 parts by weight based on 100 parts by weight of the component (A) from the viewpoint of the flame retardancy and impact strength of the obtained composition. Particularly preferably, it is 2 to 90 parts by weight.

In the present invention, a phenoxy resin, an alkaline earth metal compound, an epoxy compound, an oxoline compound, a carbodiimide compound, or the like as a hydrolysis resistance-improving material can be further compounded. In particular, an alkaline earth metal compound and / or an epoxy compound Is preferably used. In addition, the amount of the hydrolysis resistance-improving material to be added depends on the hydrolysis resistance and flame retardancy of the resulting composition, and the amount of component (A) is 100%.
The amount is preferably from 0.1 to 20 parts by weight, particularly preferably from 0.2 to 18 parts by weight, based on 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 resin is not particularly limited, but the viscosity average molecular weight is 1,000 to 10,000.
Those in the range of 0 are preferred. 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 and the like can be used, and these can be used alone or as a mixture. The shape is not particularly limited, and any of pulverized products, granules, flakes, powders, and liquids can be used. One or more of these phenoxy resins can be used as necessary.

The alkaline earth metal in the alkaline earth metal compound includes magnesium, calcium, barium and the like. The alkaline earth metal compounds used in the present invention are hydroxides, oxides, carbonates, sulfates, inorganic salts such as phosphates, acetates, lactates, etc. of these metals.
Organic acid salts such as oleic, palmitic, stearic and montanic acids 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. Magnesium, calcium salts of organic acids such as barium acid, magnesium acetate, calcium acetate, barium acetate, magnesium lactate, calcium lactate, barium lactate, and also oleic acid, palmitic acid, stearic acid and montanic acid;
And barium salts, etc., and the like. Magnesium hydroxide and calcium carbonate are preferably used, and calcium carbonate is more preferably used. These are used alone or in combination of two or more. Depending on the production method, the above calcium carbonate is known as calcium chloride carbonate, light calcium carbonate, heavy calcium carbonate, wet-pulverized fine powder heavy calcium carbonate, wet heavy calcium carbonate (chalk), etc. Included in the invention. The calcium carbonate and the alkaline earth metal compound may be treated with one or more surface treatment agents such as a silane coupling agent, an organic substance and an inorganic substance, 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.

Examples of the above epoxy compound include one or more epoxy compounds selected from glycidyl ester compounds, glycidyl ether compounds and glycidyl ester ether compounds. The epoxy compound has at least one epoxy group in the molecule and has an epoxy equivalent of less than 1,000. Are preferred. Here, the epoxy equivalent refers to the number of grams of an epoxy compound containing 1 gram equivalent of epoxy group. Here, the epoxy equivalent is determined by dissolving the epoxy compound in pyridine, adding 0.05N hydrochloric acid and heating at 45 ° C., and then performing a back titration with 0.05N caustic soda using a mixture of thymol blue and cresol red as an indicator. Can be obtained by

Examples of the glycidyl ester compound include, but are not limited to, glycidyl benzoate, tBu-glycidyl 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 acid, and one of these. The above or the glycidyl ether compound can be used in combination.

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.

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 a high temperature for a long period of time. When the hindered phenolic antioxidant and / or the phosphite antioxidant is compounded, the compounding amount of the component (A) is from the viewpoint of heat aging resistance and flame retardancy.
The amount is preferably from 0.1 to 15 parts by weight, particularly preferably from 0.2 to 10 parts by weight, based on 0 parts by weight.

Specific examples of the above hindered phenolic 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 osphite, trisnonylphenyl phosphite, alkyl allyl phosphite, trialkyl phosphite, triallyl phosphite, pentaerythritol phosphite compound and the like.

In the present invention, it is possible to improve the 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. When the lubricant is blended, the amount added is (A)
The amount 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.

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 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 thermoplastic resin is preferably a polyalkylene terephthalate, a styrene-based resin, or an ethylene (co) polymer from the viewpoint of electrical properties such as tracking resistance.

In the present invention, it is possible to 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, magnesium hydroxide, hydrotalcite, boric acid, calcium borate, calcium borate hydrate, zinc borate, zinc borate hydrate. Substances, zinc hydroxide, zinc hydroxide hydrate, zinc tin hydroxide, zinc tin hydroxide hydrate, red phosphorus,
Examples include heat-expandable graphite and dawsonite, and a thermosetting resin such as a thermosetting melamine resin, a thermosetting phenol resin, or a thermosetting epoxy resin may be mixed or coated on the surface. 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, as long as the object of the present invention is not impaired, known flame-retardant resin compositions and molded articles of a sulfur-based antioxidant, an ultraviolet absorber, a plasticizer, and an antistatic agent may be used. A material in which one or more additives are blended can also be used.

The flame-retardant resin composition and the molded article of the present invention are usually produced by a known method. For example, (A) a polyalkylene terephthalate resin having a carboxyl terminal group amount of 40 eq / ton or less, (B) a styrene resin, (C) a phosphoric ester, and (D) a salt of a triazine compound and cyanuric acid or isocyanuric acid. And, if necessary, (E) a fiber reinforcing material, 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, an ethylene (co) polymer , (E)
Premixing inorganic fillers other than fiber reinforcement, hydrolysis resistance improver, hindered phenolic antioxidant and / or phosphite antioxidant, and if necessary, other necessary additives The mixture is supplied to an extruder or the like without or with sufficient melting and kneading to prepare a flame-retardant polybutylene terephthalate resin composition.

As an example of the above premixing, the effect of the present invention can be exerted 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. In addition, (E) a method may be used in which the fiber reinforcing material is added by installing a side feeder in the middle of the filling 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 the flame-retardant 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, and the like. A kneader-type kneader or the like can be used.

The flame-retardant resin composition thus obtained can be molded by a generally known method, for example, injection molding,
By extrusion molding, compression molding, sheet molding, film molding, etc., it is possible to make molded products of all shapes, among which injection molding is suitable, and by insert molding which integrates part of metal parts directly with molded products A molded product obtained by an injection molding method may be used.

The molded article made of the flame-retardant resin composition of the present invention is excellent in safety against electric flame inside equipment, safety against fire of the molded article itself, appearance of the molded article, mechanical properties and the like. Therefore, 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 / electronic parts incorporating metal terminals and conductors, computer-related parts, audio parts, audio parts such as laser disk (registered trademark), lighting parts, telegraph / telephone equipment-related parts, air conditioner parts, VT
Home electric parts such as R and television, copier parts, facsimile parts, optical equipment parts, automobile ignition device parts, automobile connectors, and various automobile electrical components.

In the present invention, a highly reliable flame-retardant molded product having excellent fluidity and color tone during injection molding, less bleed-out, and excellent hydrolysis resistance can be obtained. Therefore, it is particularly useful for electric / electronic parts and electric parts for automobiles.

[0096]

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) Carboxyl terminal group content was 4
0 eq / ton or less polyalkylene terephthalate resin <A-1> Carboxyl terminal group content is 37 eq / ton,
Polybutylene terephthalate resin having an intrinsic viscosity of 0.85 (25 ° C., O-chlorophenol solvent) (hereinafter PBT)
(Hereinafter abbreviated as Carbo 37eq / t).

<A-2> Carboxyl end group content is 27e
q / ton, PBT having an intrinsic viscosity of 0.83 (25 ° C., o-chlorophenol solvent) was used (hereinafter referred to as “Carbo 27”).
eq / t).

<A-3> Carboxyl terminal group content is 18e
q / ton, PBT having an intrinsic viscosity of 0.84 (25 ° C., O-chlorophenol solvent) was used (hereinafter referred to as “Carbo 18”).
eq / t).

<A-4> Carboxyl terminal group content is 8 eq.
/ Ton, PBT having an intrinsic viscosity of 0.82 (25 ° C., O-chlorophenol solvent) (hereinafter, carb 8eq)
/ T).

<A-5> Carboxyl terminal group content is 45 e
PBT having q / ton and an intrinsic viscosity of 0.85 (25 ° C., O-chlorophenol solvent) was used (hereinafter referred to as “Carbo 45”).
eq / t).

<A-6> Carboxyl terminal group content is 27e
A polyethylene terephthalate resin having q / ton and an intrinsic viscosity of 0.65 (25 ° C., O-chlorophenol solvent) was used (hereinafter abbreviated as PET carb 38 eq / t).

Reference Example 2 (B) Styrene 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 is 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).

<B-4> ABS resin ("Toyolac" type 500 manufactured by Toray Industries, Inc.) was used.

Reference Example 3 (C) Phosphate <C-1> Aromatic phosphate "PX" of the following formula (5)
-200 "(manufactured by Daihachi Chemical Co., Ltd.) was used.

[0108]

Embedded image

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

[0110]

Embedded image

Reference Example 4 (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 5 (E) Fiber Reinforcing 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 6 Fluorinated Compound <F-1> Polytetrafluoroethylene “Teflon 6”
J "(manufactured by Du Pont-Mitsui Fluorochemicals) was used (hereinafter abbreviated as Teflon).

Reference Example 7 Flame retardant aid <G-1> Polycarbonate resin "Iupilon" S30
00 (manufactured by Mitsubishi Engineering Plastics) (hereinafter abbreviated as PC resin).

<G-2> A silicone compound and silicone powder "DC4-7105" (manufactured by Dow Corning Toray Silicone Co., Ltd.) were used.

<G-3> Phenolic resin, novolak type phenol resin "Sumilite Resin" PR53195
(Sumitomo Durez) was used.

<G-4> Phosphonitrile compound <H-3> Hexachlorocyclotriphosphazene (cyclic trimer) and phenol were converted to T in the presence of triethylamine.
The reaction was performed in HF. 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 was not changed and n = 3.

Reference Example 8 Ethylene (co) copolymer <H-1> Ethylene ethyl acrylate copolymer "A-7"
09 "(manufactured by Mitsui DuPont Polychemicals).

Reference Example 9 Inorganic filler other than fiber reinforcement <I-1> Silicate talc "LMS300" (manufactured by Fuji Talc) was used.

Reference Example 10 Hindered phenolic antioxidant and / or phosphite antioxidant <J-1> pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] hindered phenolic antioxidant “IR-1010” (manufactured by Ciba Geigy Corporation) <J-2> Phosphite antioxidant “Mark PEP-3 of pentaerythritol phosphite compound
6 ″ (manufactured by Asahi Denka Co., Ltd.) Examples 1-21 and Comparative Examples 1-8 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) styrene resin,
(C) Phosphate ester, (D) MC salt, and other additives <F-1>, <G-1>, <G-2>, <G-3
>, <G-4>, <H-1>, <I-1>, <J-1
> And <J-2> were mixed in the composition shown in Tables 1 and 2, and were added from the filling portion. In addition, in the example where GF was blended, except that the side feeder was installed in the middle of the blending portion and the vent portion and (E) GF was added, the blending amount of the blending amount shown in Table 1 was blended in the same manner as above. Parts. 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 the UL94 vertical test was conducted. The flame retardancy was evaluated according to the evaluation criteria. Flame retardancy is 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 ") thickness and 1/32 inch (about 0.79
mm, hereafter abbreviated as 1/32 "). The thinner the thickness, the more severely the flame retardancy is judged. In addition, materials which are inferior in flammability and do not fall into the above-mentioned flame retardancy rank are out of the standard. (2) Tensile strength Using a Toshiba Machine's IS55EPN injection molding machine, an AS having a thickness of 3 mm 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 Similar to the above flame retardancy, a 1/16 inch (about 1.59 mm) thick flame retardant is used at a molding temperature of 270 ° C. and a mold temperature of 80 ° C. using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd. Injection molding of the test piece for property evaluation was performed, and the lower molding pressure of the lowest 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 Injection molding was performed using a Toshiba Machine's IS55EPN injection molding machine 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 drying 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 tone change of the square plate before and after the above-mentioned drying machine was measured by using a SM color computer manufactured by Suga Test Instruments Co., Ltd. in the same manner as above, and the H, H, and H color difference was measured.

The smaller the value of the Hunter color difference, the smaller the change in color tone. (5) Bleed-out test Injection molding was performed using a Toshiba Machine's IS55EPN injection molding machine 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 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 article composition is stained on the surface of the molded article.

：: Bleed-out is not observed in the molded article before and after the dryer is input. Δ: Bleed-out is not observed in the molded article before the dryer is input. However, bleed-out is observed in the molded article after the dryer is input. : Bleed-out is observed in the molded product before and after the dryer is put in. (6) Hydrolysis resistance 3 mm thick AS is used at a molding temperature of 270 ° C and a mold temperature of 80 ° C using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd.
AST obtained by performing injection molding of TM1 dumbbell pieces
After treating the M1 dumbbell piece at a temperature of 121 ° C. and a humidity of 100% RH for 100 hours, the tensile strength is measured according to ASTM D648, and the measured value is a percentage of a value obtained by dividing by a tensile strength of an untreated product. It was shown in percentage (%).

[0129]

[Table 1]

[0130]

[Table 2]

[0131]

[Table 3]

From the evaluation results of Examples 1 to 9 in Table 1 and Comparative Example 1 without addition of GF, the PBT of the polyalkylene terephthalate resin having a carboxyl terminal group content of 40 eq / ton or less according to the present invention shown in Examples 1 to 4 was obtained. In addition, a composition containing a styrene-based resin, phosphate ester, and MC salt has excellent mechanical properties and fluidity during injection molding while maintaining high flame retardancy, and bleed-outs are observed on the molded product surface No longer
It can be seen that a molded article having excellent hydrolysis resistance can be obtained. Also, from Example 5, the carboxyl end group content was 40 e
In the same manner as described above, a material in which PBT and PET are blended as a polyalkylene terephthalate resin having q / ton or less has excellent mechanical properties and excellent fluidity during injection molding while maintaining high flame retardancy. It can be seen that no bleed-out was observed and that a molded article having excellent hydrolysis resistance was obtained. Also, from a comparison between Example 6 and Example 8, the material using the AS resin as the styrene-based resin was superior to the material using the ABS resin in hydrolysis resistance, color tone, and color tone change. Furthermore, from the comparison of Example 2, Example 6, Example 7, and Example 8, among the styrene resins, epoxy-modified AS resin or epoxy-modified SB
It can be seen that the material using S resin is excellent in hydrolysis resistance, color tone and color tone change, and in particular, epoxy-modified AS resin is also excellent in flame retardancy and is the most preferable styrene resin.

On the other hand, from Comparative Example 1, a polyalkylene terephthalate resin PBT having a carboxyl terminal group content of more than 40 eq / ton was added to a styrene resin, a phosphoric ester,
And the composition containing the MC salt are excellent in flame retardancy, mechanical properties, fluidity during injection molding, and bleed-out, but have large color change, poor hydrolysis resistance, and lack in quality stability. Material.

Examples 10 to 11 and Comparative Examples 2 to
From 5, by blending fibrous reinforcement GF,
The tensile strength is dramatically increased, and a high-strength PBT resin is obtained. However, as compared with Comparative Examples 2 to 5, from the comparison between Example 10 and Comparative Example 2, the amount of carboxyl terminal groups was also found in the GF-reinforced resin. A composition in which a styrene-based resin, a phosphate ester, and an MC salt are blended with PBT of a polyalkylene terephthalate resin exceeding 40 eq / ton has excellent flame retardancy, mechanical properties, fluidity during injection molding, and bleed-out property. However, the material had a large change in color tone, was poor in hydrolysis resistance, and lacked quality stability.

According to Comparative Example 3, bleed-out was observed in the molded product before and after the dryer was put in the material (B) in which the styrene resin was not blended in the present invention.

Further, from Comparative Examples 4 and 5, when either the phosphate ester or the MC salt was not blended, the composition did not show the same flame retardancy as PBT of the polyalkylene terephthalate resin. Did not improve, and a flame-retardant composition could not be obtained.

The compositions of the present invention shown in Examples 13 to 21 of Table 2 are compounds which improve the flame retardancy, tracking resistance, heat aging resistance and the like of the composition of Example 11.

In Examples 13 to 16 shown in Table 3,
By blending the C resin, the silicone compound, the phenol resin and the phosphonitrile compound, the flame retardant time was shortened while maintaining other properties, and the flame retardancy was improved.

Further, by blending the ethylene copolymer or talc of Examples 17 to 18, the tracking resistance (IEC Publication 112) was further improved.
According to the test method specified in the standard, the breakdown voltage (V) at which the insulation of the molded product is broken, and the higher the breakdown voltage, the better. ) Is from a breakdown voltage of less than 600 V to a breakdown voltage of 600 V
It was found that a molded article having the above-mentioned improved properties and excellent electrical properties was obtained. However, the material containing the ethylene copolymer had reduced flame retardancy.

Further, the compositions containing the antioxidants of Examples 19 to 21 and the ASTM No. 1 dumbbell of Example 12 were placed in a Tabai gear oven, treated at 180 ° C. for 300 hours, and the tensile strength was measured. The retention of tensile strength of each of the compositions of Example 11 was improved by about 16% or more. Therefore, it can be seen that the addition of the antioxidant improves the heat aging resistance while maintaining other performances.

Comparative Examples 6 to 8 shown in Tables 2 and 3 show that, instead of the styrene resin of the composition of the present invention, polyphenylene which is known as a thermoplastic resin which is more excellent in flame retardancy than styrene resin or PBT resin is used. This is a composition in which an ether resin, a polyphenylene sulfide resin and a nylon resin are blended in an amount of 25 parts by weight in the same manner as the styrene resin.

Table 3 shows that polyphenylene ether resin and polyphenylene sulfide resin are excellent in flame retardancy,
It is a molded article with very poor performance in all of tensile strength, fluidity, color tone, color tone change, and hydrolysis resistance, and lacks quality stability due to large color tone change and poor hydrolysis resistance. Material.

Further, nylon 6 resin was a material which was significantly inferior in all properties including flame retardancy.

[0144]

The carboxyl end group content is 40 eq / to
n or less polyalkylene terephthalate resin, a specific amount of a styrene resin, a phosphate ester, a salt of a triazine compound and cyanuric acid or isocyanuric acid, and a fiber reinforcing material, an alkaline earth metal salt if necessary, an epoxy compound And fluorine compounds, etc.,
A non-halogen flame-retardant resin composition having excellent mechanical properties and excellent fluidity during injection molding while maintaining high flame retardancy, hardly causing bleed-out, and having excellent hydrolysis resistance; and A molded article can be obtained, which is expected to greatly contribute to market expansion of polyalkylene terephthalate resin.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 25/04 C08L 25/04 51/04 51/04 F term (Reference) 4F071 AA10X AA22 AA22X AA33X AA34X AA36X AA45 AA77 AC15 AD01 AE17 AF34 AF47 AH07 AH12 AH17 BA01 BB05 BC01 4J002 BC03X BC05X BC06X BC07X BC08X BC09X BH01X BN14X BN15X BN16X BP01X CD19X CF06W CF07W CF10W CL063 DA018 DL008 EU187 EU197010 FB FA EU FE FD 00 00

Claims (6)

[Claims] (A) a carboxyl terminal group content of 40 eq /
ton or less polyalkylene terephthalate resin 100
(B) 1 to 100 parts by weight of a styrene resin, (C) 1 to 100 parts by weight of a phosphoric ester, and (D)
A flame-retardant resin composition comprising 1 to 150 parts by weight of a salt of a triazine compound and cyanuric acid or isocyanuric acid. (A) a carboxyl terminal group content of 40 eq /
ton or less polyalkylene terephthalate resin 100
The flame-retardant resin composition according to claim 1, further comprising (E) 250 parts by weight or less of a fiber reinforcing material with respect to parts by weight. 3. The flame-retardant resin composition according to claim 1, wherein the phosphoric ester (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 represent the same or different phenyl groups or phenyl groups substituted with halogen-free organic residues. X represents the following (2) Represents one selected from formulas (4) 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 , CHPh
And Ph represents a phenyl group. In addition, n in equation (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. Embedded image Embedded image Embedded image 4. The styrene resin (B) is epoxidized with an epoxy group-containing vinyl monomer or a styrene copolymer obtained by graft polymerization or copolymerization of an unsaturated anhydride and / or an epoxidizing agent. The flame-retardant resin composition according to any one of claims 1 to 3, which is a styrene (co) polymer. 5. The flame-retardant resin composition according to claim 1, wherein (B) the styrene resin is a copolymer obtained by copolymerizing acrylonitrile, styrene and glycidyl methacrylate. 6. A molded article for a mechanical mechanism part, an electric / electronic part or an automobile part, comprising the flame-retardant resin composition according to claim 1.