JP2002226684A - Flame retardant thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester based resin composition which has excellent flame retardancy without using a halogen based flame retardant agent. SOLUTION: This polyester based resin composition is prepared by formulating (A) a polyester based resin, (B) at least one selected from among a phenol novolac resin, a polyphenylene ether resin, and a polyphenylene sulfide resin, (C) a phosphoric ester compound, and (D) a nitrogen based organic compound containing a phosphoric atom or a nitrogen based organic compound containing a sulfur atom, with specified mixing ratio, and further formulating (E) a styrene based compound containing a functional group, (F) a polyorganosiloxane resin, and (G) an inorganic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin composition exhibiting excellent flame retardancy without using a halogen flame retardant. The present invention also relates to a molded product obtained by molding the resin composition, and more specifically,
The present invention relates to a molded product that can be suitably used for a wide variety of applications, such as a case member such as a motor cover, a transformer member, a connector, a switch, a relay, a printed circuit board, an electric / electronic device component such as a coil bobbin, an automobile component, and a mechanical component.

[0002]

2. Description of the Related Art Conventionally, halogenated flame retardants have been used as a method for flame retarding polyester resins. However, in recent years, environmental pollution due to the generation of harmful gases during combustion or melting at high temperatures has been considered. Due to problems such as adverse effects on the human body, there is a strong demand for a transition to flame retardancy using a so-called “non-halogen flame retardant” that does not contain halogen.

In order to meet such demands, various proposals using non-halogen flame retardants have been made, but none of them has been satisfactory. For example, in the method using a phosphoric ester (Japanese Patent Publication No. 25706/1987), dripping (generally referred to as "drip") is likely to occur during combustion, resulting in insufficient flammability. It has disadvantages such as easy bleed-out due to insufficient compatibility with the ester, causing mold contamination and surface contamination of molded products.

Further, a method of using a phosphate compound and a nitrogen atom-containing organic compound in combination for the purpose of flame retardation (JP-A-9-132723, JP-A-9-2682)
No. 51) and a method of blending a resin having high flame retardancy such as polyphenylene sulfide or polyphenylene ether (Japanese Patent Application Laid-Open No. 10-182555, Japanese Patent Application Laid-Open No. 7-300562). In a vertical flammability test of Underwriters Laboratories Inc., dripping occurs during combustion, particularly in a thin molded product having a small thickness, and it is difficult to achieve a good level of so-called "V-0". As a matter of fact, a polyester resin composition having a non-halogen flame retardant composition, which exhibits flammability and sufficiently satisfies the requirements of the market, has not been found yet.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a polyester resin composition exhibiting excellent flame retardancy without using a halogen flame retardant, and a molded article thereof. Another object of the present invention is to provide a flame-retardant polyester resin composition which is excellent in the effect of suppressing dripping during combustion and has high mechanical strength.

[0006]

Means for Solving the Problems The present inventors have proposed (A) a polyester resin and (B) at least one aromatic resin selected from a novolak type phenol resin, a polyphenylene ether resin and a polyphenylene sulfide resin. By using (C) a phosphoric acid ester compound and (D) a specific phosphorus atom-containing nitrogen-containing organic compound or a sulfur atom-containing nitrogen-containing organic compound in combination as a flame retardant in a resin mixture, surprisingly, the drip inhibiting effect is obtained. Were found, and an excellent flame retardant effect was exhibited, and the present invention was reached.

That is, the present invention relates to a polyester resin as the component (A) and at least one aromatic resin selected from a novolak phenol resin, a polyphenylene ether resin and a polyphenylene sulfide resin as the component (B). , A phosphoric ester compound as a component (C) and a phosphorus atom-containing nitrogen-containing organic compound or a sulfur atom-containing nitrogen-containing organic compound as a component (D) at a specific ratio, and further, a functional group-containing compound as a component (E). An object of the present invention is to provide a resin composition comprising a styrene compound, a polyorganosiloxane resin as the component (F), and an inorganic filler as the component (G).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Component (A) used in the present invention
Polyester resin is not particularly limited,
Known per se, for example, a polyester resin obtained from a diol component (or the ester-forming derivative) and a dicarboxylic acid component (or the ester-forming derivative) can be used. Further, as the diol component and the dicarboxylic acid component, the compounds described below may be used alone or in combination of two or more. Further, a compound having a hydroxyl group and a carboxyl group in one molecule, such as lactone, may be used in combination.

The diol component is not particularly restricted but includes, for example, ethylene glycol, 1,2-
Propanediol, 1,3-propanediol, 1,4
-Butanediol, 2,3-butanediol, 1,6-
C2-C15 aliphatic diols such as hexanediol, 1,8-octanediol, neopentyl glycol, 1,10-decanediol, diethylene glycol, triethylene glycol, 2-methyl-1,3-propanediol, and the like. Can be mentioned. Among them, preferred aliphatic diols are ethylene glycol, 1,4-butanediol, 1,3-propanediol and the like.

Also, 1,2-cyclohexanediol,
Alicyclic diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol can be used. These alicyclic diols can be used as either the cis or trans configuration isomer or as a mixture of both, and there is no particular limitation on the mixing ratio of the cis and trans isomers. Preferred alicyclic diols are 1,4-
Cyclohexanedimethanol.

Further, aromatic dihydric phenols such as resorcinol, hydroquinone, and naphthalene diol, polyethylene glycol having a molecular weight of 400 to 6000, polyglycols such as polypropylene glycol and polytetramethylene glycol, and bisphenol A such as bisphenol A
Bisphenols described in No. 203956 can also be used. In addition, the diol component,
Diesters such as diacetate and dipropionate may be used.

Representative examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, orthophthalic acid and 2,2'-
Biphenyldicarboxylic acid, 3,3′-biphenyldicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4 ′
-Diphenyl ether dicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid,
2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,2-di (4-carboxyphenyl)
Aromatic dicarboxylic acids such as ethane; aliphatic and alicyclic dicarboxylic acids such as adipic acid, succinic acid, oxalic acid, malonic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid and cyclohexanedicarboxylic acid; I can do it. The acid component may be an ester derivative, for example, an alkyl ester such as methyl and ethyl, and an aryl ester such as phenyl and cresyl.

Preferred dicarboxylic acids are terephthalic acid, naphthalenedicarboxylic acid and their ester-forming derivatives (preferably dimethyl terephthalate, dimethyl naphthalenedicarboxylate).

Examples of the lactone include caprolactone.

The polyester resin (A) used in the present invention
Can be produced by a known method. The catalyst used at that time may be any of ordinary catalysts such as an antimony compound, a titanium compound, a tin compound and a germanium compound.

The polyester resin (A) used in the present invention is preferably a polyester resin of an aromatic dicarboxylic acid and an alkylene glycol. Specifically, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, poly 1,4-cyclohexylene methylene terephthalate, poly (1,4-cyclohexylene methylene terephthalate-co-isophthalate), poly ( 1,4-butylene terephthalate-co-isophthalate) and poly (ethylene-co-1,4-cyclohexylene methylene terephthalate). One of these components (A) may be used alone.
A combination of more than one species may be used.

The acid value of the polyester resin (A) used in the present invention is not particularly limited, but is preferably 3.0 mgK from the viewpoints of hydrolysis resistance, heat stability, and suppression of coloring.
OH / g or less, more preferably 2.5 mgKOH / g or less.

The intrinsic viscosity [η] of the polyester resin (A) measured at 30 ± 0.1 ° C. in a mixed solvent of phenol / tetrachloroethylene = 50/50 by weight is as follows:
Although not particularly limited, preferably 0.6 to 1.
It is 1 dl / g.

Next, a polyphenylene ether (hereinafter abbreviated as PPE) resin which is one of the components (B) used in the present invention is known per se and represented by the formula [1].

[0020]

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(In the formula (1), R1, R2, R3 and R4 are each independently selected from a hydrogen atom, a hydrocarbon group and a substituted hydrocarbon group (eg, a halogenated hydrocarbon group)) And / or a homopolymer and / or copolymer consisting of

Specific examples of the polyphenylene ether resin (B) include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,6-diethyl-1,4-)
Phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-
6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether Ter, poly (2,6-dimethoxy-1,4-
Phenylene) ether, poly (2,6-dichloromethyl-1,4-phenylene) ether, poly (2,6-dibromomethyl-1,4-phenylene) ether, poly (2,6- Diphenyl-1,4-phenylene) ether, poly (2,6-ditolyl-1,4-phenylene) ether, poly (2,6-dichloro-1,4-phenylene) ether, poly ( 2,6-dibenzyl-1,4-phenylene) ether, poly (2,5-dimethyl-1,4)
-Phenylene) ether and the like. Among them, a particularly preferred PPE resin is poly (2,6-dimethyl-
1,4-phenylene) ether.

Specific examples of the polyphenylene ether copolymer include the above-mentioned polyphenylene ether repeating unit, that is, a polyphenylene ether copolymer obtained by copolymerizing an alkyl 3-substituted phenol in the formula [1]. Copolymers, for example, copolymers partially containing 2,3,6-trimethylphenol as copolymerized units can be exemplified.

Further, the component (B) may be a copolymer obtained by graft-polymerizing a styrene-based compound on these PPE-based resins. Examples of the styrene-based compound-grafted PPE-based resin include copolymers obtained by graft-polymerizing styrene, α-methylstyrene, vinyltoluene, chlorostyrene, or the like as a styrene-based compound to the above-mentioned polyphenylene ether.

The method for producing such PPE is known and is not particularly limited. For example, US Pat. No. 3,306,874
No. 3,306,875; U.S. Pat. No. 3,2
No. 57,357, U.S. Pat. No. 3,257,358, JP-B-52-17880, and JP-A-50-51197.

The intrinsic viscosity of the PPE resin (B) used in the present invention measured at 30 ° C. using chloroform as a solvent is preferably 0.15 to 0.70 dl / g, more preferably 0.25 to 0.60 dl. / G. When the intrinsic viscosity is within such a range, excellent mechanical strength and moldability can be obtained.

The polyphenylene sulfide (hereinafter abbreviated as PPS) resin, which is one of the components (B) used in the present invention, is represented by the general formula [Ar-S] (wherein Ar is at least 1
Is a polymer containing a repeating unit represented by at least 70 mol% represented by a divalent aromatic group containing two carbon 6-membered rings, and a typical substance is a structural formula [Ph-S] (where Ph is phenyl This is a polymer containing at least 70 mol% of the repeating unit represented by the formula:

The PPS resin is generally produced by the following method.
It is roughly classified into those having a substantially linear structure without a branched structure or a crosslinked structure, and those having a branched structure or a crosslinked structure. In the present invention, it is effective for both types.

The PPS resin (B) preferably used in the present invention has a general formula [Ar-S] (where Ar is a divalent aromatic group containing at least one carbon 6-membered ring) as a repeating unit. (A) is 70% by mole or more. Usually, when this repeating unit is 70 mol% or more, it becomes possible to obtain a PPS-based resin (B) having excellent properties as a crystallized polymer, such as excellent strength, toughness, and chemical resistance.

The PPS resin (B) used in the present invention may contain less than 30 mol% of other copolymer structural units. Specific examples of the copolymer structural unit include, for example, structural units represented by the following formulas [2] to [7], but the present invention is not limited thereto.

Metaphenylene sulfide unit = formula [2]

[0032]

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Diphenyl ketone sulfide unit = formula [3]

[0034]

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Diphenyl sulfone sulfide unit = formula [4]

[0036]

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Diphenyl ether sulfide unit = formula [5]

[0038]

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2,6-naphthalene sulfide unit = formula [6]

[0040]

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Trifunctional unit = Formula [7]

[0042]

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Further, another component (B) used in the present invention is a novolak type phenolic resin, which is obtained by polycondensing phenol and formaldehyde in the presence of an acid catalyst. The softening point measured in glycerin by the ball and ring method is preferably 80 ° C. or higher.
In addition, a melamine-based compound other than the above monomer may be used in a range of 50% by weight or less.

The polyester resin of the component (A) and the novolak phenol resin of the component (B) in the present invention,
At least one kind of aromatic resin selected from polyphenylene ether-based resin and polyphenylene sulfide-based resin is used in an arbitrary ratio, but the preferable mixing ratio of component (A) and component (B) is (A) / ( B) = 5-97 /
95 to 3% by weight, more preferably (A) / (B) = 15
９５95 / 85-5% by weight.

Next, the phosphate compound as the component (C) used in the present invention will be described. The component (C) phosphate compound of the present invention includes a compound represented by the formula [8], but the present invention is not limited thereto.

[0046]

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(In the formula [8], A1 and A2 represent the same or different phenyl groups or a phenyl group substituted with a halogen-free organic residue. X represents a divalent or higher valent organic group; It represents an integer of 0 or more, for example, 30 or less.)

In the formula [8], examples of the organic residue include an alkyl group, a cycloalkyl group and an aryl group which may or may not be substituted. When substituted, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, a halogen, an aryl group,
Examples thereof include an aryloxy group, an arylthio group, and a halogenated aryl group. In addition, a group obtained by combining these substituents (for example, an arylalkoxyalkyl group) or such a substituent is an oxygen atom, a sulfur atom, a nitrogen atom A group (for example, an arylsulfonylaryl group or the like) combined by bonding through the above may be used as a substituent.

The divalent or higher valent organic residue in the formula [8] means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to a carbon atom from the above organic residue. I do. For example, an alkylene group, and preferably (substituted)
Examples include phenylene groups, polynuclear phenols such as those derived from bisphenols, and the relative positions of two or more free valences are arbitrary. Particularly preferred among them are bisphenol A, hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane, dihydroxydiphenyl, p, p'-
Examples include dihydroxydiphenylsulfone and dihydroxynaphthalene.

Specific examples of the phosphate compound (C) include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, and octyl. Diphenyl phosphate, diisopropylphenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropylphosphate, tris (2,3 -Dibromopropyl) phosphate, and bis (chloropropyl) monooctyl phosphate, wherein A1-O
Bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bis wherein-and -OA2 are alkoxy, for example methoxy, ethoxy and propoxy, or preferably (substituted) phenoxy, for example phenoxy, methyl (substituted) phenoxy Examples include polyphosphates such as phosphate and trioxybenzene triphosphate, and preferred are triphenyl phosphate and various polyphosphates. Further, examples of commercially available products include PX-200 and CR-7.
33S, PX-201, PX-202, CR-747,
CR-741 (manufactured by Daihachi Chemical), FP-500 (manufactured by Asahi Denka), Phosphorex 580 (manufactured by Akzo Kashima)
And the like.

The method of blending the component (C) is not particularly limited. For example, when the component (C) is in a liquid state, the component (C) can be added in the middle of an extruder by a method such as liquid injection. What is necessary is just to select the method which can be effectively contact-mixed with resin according to the property of component (C).

The above component (C) is preferably used in an amount of 5 to 9 based on the total amount of components (A) and (B) of 6 to 95% by weight.
It is used in an amount of 4% by weight, particularly preferably 10 to 30% by weight based on the total amount of the components (A) and (B) of 70 to 90% by weight.

The component (D) used in the present invention is a phosphorus-containing nitrogen-containing organic compound or a sulfur-containing nitrogen-containing organic compound.

Polyamine aminotriazine compound comprising a salt with aminotriazine represented by [9], or polyaminotriazine metametaphosphate compound, a phosphorus atom-containing nitrogen compound represented by formulas [12] and [13] and a triazine sulfate compound is there.

[0054]

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The aminotriazine polyphosphate compound used in the present invention includes melamine polyphosphate, melam polyphosphate, and melem polyphosphate represented by the formula [10].

[0056]

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(In the formula [10], n is a positive number of 1 or more, and M is a formula

A triazine compound represented by [9]. )

The sulfur atom-containing nitrogenous organic compound used in the present invention is a triazine sulfate compound represented by the formula [11].

[0059]

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(In the formula [11], M is the formula

Represents the triazine compound of [9], S represents a sulfur atom, O represents an oxygen atom, and H represents a hydrogen atom. )

Examples of preferred commercial products include Melupe
r200 / 70 (manufactured by DSM), PMP-100, PMP
-200 (manufactured by Nissan Chemical Industries), MPP-A, Apinon 9
01 (manufactured by Sanwa Chemical).

Further, in the present invention, the following phosphorus-containing nitrogen-containing organic compounds are used.

[0063]

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(In the equation [12], M is the equation

[9] represents the triazine compound, P represents a phosphorus atom, O represents an oxygen atom, and H represents a hydrogen atom. )Also,

[0065]

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(In the equation [13], M is the equation

[9] represents the triazine compound, P represents a phosphorus atom, O represents an oxygen atom, and H represents a hydrogen atom. )

Specific examples of the formula [12] include a salt of nitrilotris (methylene) phosphonic acid and melamine, a formula [1]
Examples of 3] include 1-hydroxyethylidene-1,
There are salts of 1-diphosphonic acid and melamine.

In the present invention, the components (A), (B),
(C) and (D) may be used in such a manner that the total amount of the components (A) and (B) is 50 to 95% by weight, the component (C) is a phosphoric ester compound, 5 to 40% by weight, and the component (D) is phosphorus. 1 to 1 atom-containing nitrogen-containing organic compound or sulfur atom-containing nitrogen-containing organic compound
40% by weight, more preferably component (A) +
The total amount of (B) is 60 to 90% by weight, and the component (C) is 7 to
The resin composition has 30% by weight, 5 to 30% by weight of the component (D), and 100% by weight of the components (A) + (B) + (C) + (D).

In the present invention, a functional group-containing styrenic compound (E) can be further blended for the purpose of improving the impact resistance of the composition of the present invention. More specifically, the functional group-containing styrene compound (E) is a polymer or oligomer containing styrene as a repeating unit in an amount of 50% by weight or more, an epoxy group, a cyclic imino ether group, a vinyl group, a maleic anhydride, an amino group, and the like. A random copolymer, a block copolymer, a graft copolymer and / or a mixture with a compound having a reactive group. Examples thereof include polystyrene and maleic anhydride, polystyrene and a compound containing a cyclic imino ether group, polystyrene and an unsaturated glycidyl monomer, random copolymers of polystyrene and an epoxy group-containing polyolefin, block copolymers, and graft copolymers. It is a polymer and / or a mixture, preferably a combination of polystyrene and an epoxy group-containing polyolefin and a graft copolymer and / or a mixture of polystyrene and a cyclic iminoether group-containing compound. More preferably, the cyclic imino ether group is a 2-oxazoline group, 2-alkenyl-2-
It is an oxazoline group. The content of these functional groups in the styrenic compound (E) is preferably 0.1 to 10% by weight, more preferably 1 to 8% by weight.

The amount of the functional group-containing styrenic compound (E) to be used is preferably the component (A) + (B) + (C) + (D)
The component (E) is contained in an amount of 1 to 1 based on a total amount of 90 to 99% by weight of
0% by weight, more preferably component (A) + (B) + (C)
+ (D) based on the total amount of 93 to 98% by weight of the component (E)
Is 2 to 7% by weight.

Next, the component (F) used in the present invention comprises:
A polyorganosiloxane-based resin having a crosslinked structure to the extent that molecules of the polyorganosiloxane-based resin do not have fluidity at room temperature, and have a particle size of 0.1 μm to 500 μm.
A polyorganosiloxane-based resin having an appearance of a powder in a μm state or a melt viscosity at a shear rate of 100 sec ^-1 measured at 25 ° C. with a capillary-type melt viscosity meter of 10 μm.
A polyorganosiloxane resin of 00 poise or more
At least 0.1% by weight dispersed in silica powder
It is a polyorganosiloxane-based resin in which the appearance of μm to 500 μm is in a powder state.

The component (F) polyorganosiloxane resin in the present invention is preferably a polyorganosiloxane resin having a molecular structure containing a phenyl group in the molecule. Also, epoxy group, amino group, methacryl group,
Polyorganosiloxane resins containing functional groups such as oxazoline groups, acid anhydride groups, and hydroxyl groups may be used. Examples of commercially available products of such polyorganosiloxane resins include DC4-7105, DC4-7051 (containing an epoxy group, manufactured by Dow Corning Toray), and DC4-7081.
(Containing a methacryl group, manufactured by the company) and DC19641 (containing an amino group, manufactured by the company).

The amount of the polyorganosiloxane resin (F) added is 90 to 99% by weight of the total of the components (A) + (B) + (C) + (D). 1) 1 to 10% by weight.

Next, the component (G) used in the present invention is an inorganic filler and is used as a reinforcing material, but is not particularly limited. Specific examples of the component (G) include:
Glass fiber and carbon fiber, milled glass, glass beads,
Glass flake, talc, clay, silica, mica, wollastonite, barium sulfate, calcium sulfate, calcium carbonate, potassium titanate whisker, calcium carbonate whisker, aluminum borate whisker and the like can be suitably used. In order to further enhance the reinforcing effect, using these inorganic fillers coated with various coupling agents such as silane coupling agents such as aminosilane and epoxysilane, titanate coupling agents, and aluminum coupling agents Is also good.

The amount of the inorganic filler (G) used depends on the amount of the component (A)
+ (B) + (C) + (D) total amount or component (A) +
(B) + (C) + (D) + [at least one selected from (E) and (F)] is 50 to 95% by weight, and the component (G) is 5 to 50% by weight. is there.

Further, a stabilizer may be added to the resin composition of the present invention in order to improve the heat stability at melting and discoloration. Such stabilizers include, for example, phosphites, acidic phosphates, salts of polyphosphoric acids, phosphates of metals of Groups IB or IIB of the periodic table, and oxo acids of phosphorus.

Examples of the phosphite include triphenyl phosphite, diphenyl nonyl phosphite, tris- (2,4-di-t-butylphenyl) phosphite, tris nonyl phenyl phosphite, diphenyl isooctyl phosphite, , 2'-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, diphenylisodecyl phosphite, diphenyl mono (tridecyl) phosphite, 2,2'-ethylidene bis (4,6-di-t -Butylphenol) fluorophosphite, phenyldiisodecylphosphite, phenyldi (tridecyl) phosphite, tris (2-ethylhexyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, dibutylhydrogen phosphite G, trilauryl trithiophosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite,
4,4'-isopropylidene diphenol alkyl (C
12-C15) phosphite, 4,4'-butylidenebis (3-methyl-6-t-butylphenyl) di-tridecyl phosphite, bis (2,4-t-butylphenyl) pentaerythritol diphosphite, bis (2,
6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetraphenyldi Propylene glycol diphosphite, 1,
1,3-tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane, 3,4
5,6-tetrabenzo-1,2-oxaphosphane-2
-Oxides and the like can be used. Further, partial hydrolysates of these phosphites can also be used. As the phosphite, a compound commercially available from each stabilizer manufacturer as an antioxidant or the like can be used. Specific examples of commercially available products include ADK STAB PEP-36, PEP-24, and PEP-24.
EP-4C, PEP-8 (manufactured by Asahi Denka Kogyo KK), Ir
gafos 168 (trademark: Ciba-Geigy), Sa
ndstab P-EPQ (trademark: manufactured by Sandoz),
Chelex L (trademark: manufactured by Sakai Chemical Industry Co., Ltd.), 3P2
S (trademark: manufactured by Ihara Chemical Industry Co., Ltd.), Mark 3
Phosphorus stabilizers such as 29K (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), Mark P (same as above), and Weston 618 (trade name, manufactured by Sanko Chemical Industry Co., Ltd.).

The acidic phosphate includes, for example, sodium dihydrogen phosphate, monozinc phosphate, potassium hydrogen phosphate, calcium hydrogen phosphate and the like.

Polyphosphoric acid is a condensed phosphoric acid, and the phosphoric acid
Dimer (pyrophosphoric acid), trimer (tripolyphosphoric acid) and the like. Examples of such a salt include pyrophosphates such as Na ₃ HP ₂ O ₇ , K ₂ H ₂ P ₂ O ₇ , Na ₄ P ₂ O ₇ , KNa
Like _{H 2 P 2 O 7, Na} 2 H 2 P 2 O 7 and the like. The particle size of such pyrophosphates is preferably less than 75 microns, more preferably less than 50 microns, particularly preferably less than 20 microns.

Examples of the phosphate of a metal of Group IB or Group IIB of the periodic table include zinc phosphate and copper phosphate.

The oxo acids of phosphorus include phosphorous acid, phosphoric acid, polyphosphoric acid and hypophosphorous acid.

In the resin composition of the present invention, a hindered phenol-based stabilizer may be used in addition to the above-mentioned stabilizer. Examples of such a stabilizer include triethylene glycol-bis [3- (3-t-butyl-5).
-Methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 2,2-thio-diethylenebis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-butyl-4-hydroxybenzyl) benzene, bis or tris (3-t-butyl-6-methyl-4-hydroxyphenyl) propane, N, N'-hexamethylenebis (3,5-di- t-butyl-4-hydroxy-hydrocinnamamide), N, N'-trimethylenebis (3,5-
Di-t-butyl-4-hydroxy-hydrocinnamamide) and the like. Further, specific examples of commercially available products include:
BHT (trade name: Takeda Pharmaceutical Co., Ltd.), Ionox
100 (trademark: manufactured by Shell Chemical Company), Age Rit
e Superlite (trademark: Vander bitt)
), SantonoxR (trademark: manufactured by Monsanto),
Antioxidant ZKF (trademark: manufactured by Bayer), Irganox 1076 (trademark: manufactured by Ciba-Geigy), Hyoechst VPOSSPI (trademark: manufactured by Hoechst), Irganox 1010 (trademark: Ciba.)
(Manufactured by Geigy Corporation). In addition, stabilizers such as epoxy-based, thiol-based, and metal salt-based stabilizers can also be used. Furthermore,
Cyasorb UV-5411 (trademark: AAC
), Cyasorb UV-531 (trademark: ACC)
), Tinuvin 326 (trademark: Ciba-Geigy), Tinuvin 320 (same as above), Tinuv
Ultraviolet absorbents such as benzotriazoles such as in 234 (same as above), Tinuvin 120 (same as above) and Uvinul D49 (trade name: manufactured by GAF) can be used.

Further, the composition of the present invention may be mixed with a thermoplastic resin other than the thermoplastic resin of the present invention and a thermosetting resin within a range not to impair the gist of the present invention. At that time, specific examples of the thermoplastic resin and the thermosetting resin used include polyamide, polyurethane, polyethylene, polypropylene, PTX, and polystyrene.
Thermoplastic resins such as AS, PVC, POM, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyphenylene oxide, polyethylene naphthalate, polybutylene naphthalate, PCT, liquid crystal polymer; vinyl ester Resin, unsaturated polyester resin, melamine resin, benzoguanamine resin,
Thermosetting resins such as diallyl phthalate resin, alkyd resin, phenol resin, epoxy resin and polyimide resin; ethylene / glycidyl methacrylate copolymer;
Ethylene / acrylate / glycidyl methacrylate copolymer, SBR, hydrogenated SBR, epoxy group-containing SB
R, hydrogenated SBR containing epoxy group, S containing maleic anhydride
BR, NBR, hydrogenated NBR, carboxyl group-containing NB
R, acrylic rubber other than the present invention, functional group-containing acrylic rubber, ethylene / propylene copolymer, functional group-containing ethylene / propylene copolymer, silicone rubber, fluorine-based rubber, polyester-based elastomer, polyamide-based elastomer, functional It is also possible to add an impact modifier such as a group-containing polyolefin polymer.

As the flame retardant, halogen-based flame retardants,
For example, a brominated polycarbonate, a brominated polycarbonate oligomer, a brominated epoxy, and the like can be further added.

As the anti-drip agent, polytetrafluoroethylene (Teflon (registered trademark)) or the like can be used.

Further, the resin composition of the present invention may further contain other colorants such as pigments and dyes, silicone oil, low molecular weight polyolefins, pentaerythritol tetrastearate, montanic acid esters, metal salts of montanic acid esters, and glycerin. Release agents such as alkyl esters such as monostearate, polycaprolactone, polyester,
Plasticizers such as oligomers of polycarbonate, salt compounds of sulfonic acid with alkali metals or alkyl phosphoniums, antistatic agents such as polyalkylene glycols such as polyethylene oxide and polypropylene oxide, cross-linked polyester, cross-linked polyamide, cross-linked polymethyl methacrylate, etc. Various additives such as a granulated organic particulate compound or the like and an infrared absorbing agent, an antibacterial agent, a crystal nucleating agent or the like may be used.

The resin composition of the present invention can be obtained by a known method, and the method for producing the resin composition is not particularly limited.
For example, a method of dry blending using a blender or a mixer or the like and then melt-mixing using an extruder may be mentioned. Usually, a strand is prepared by melt-mixing using a single-screw or twin-screw extruder. Extruded and pelletized. The order of mixing the components is not particularly limited, but when long fibers such as glass fiber or carbon fiber are used as the filler, the breaking of these fibers is minimized so that the reinforcing effect can be sufficiently exhibited. Naturally, it is preferable to consider the kneading method and the kneading order as described above. For example, when melt-kneading using an extruder, an extruder having at least two or more raw material supply ports is used. Then, it is preferable that only the resin component or the resin component and the non-long fiber inorganic filler are charged from the first supply port (upstream side), and the long fiber is supplied from the second supply port and thereafter (downstream side). .

The above resin composition of the present invention can be prepared by any molding method such as injection molding, extrusion molding, blow molding and the like.
It can be formed into a molded article of any shape.

As described above, in the embodiment of the present invention, as the component (A), a polyester resin, and as the component (B), at least one resin selected from a novolak phenol resin, a polyphenylene ether resin, and a polyphenylene sulfide resin. A resin composition characterized by blending a kind of aromatic resin, a phosphate compound as component (C), and a phosphorus-containing nitrogen-containing organic compound or sulfur-containing nitrogen-containing organic compound as component (D). It depends on.

Another embodiment of the present invention relates to the above resin composition, which comprises blending a functional group-containing styrene compound as the component (E).

Another embodiment of the present invention relates to each of the above resin compositions, wherein a polyorganosiloxane resin is blended as the component (F).

Another embodiment of the present invention relates to each of the above resin compositions, wherein an inorganic filler is blended as the component (G).

In another aspect of the present invention, (A)
A total amount of a mixture of a polyester resin and at least one aromatic resin selected from (B) a novolak type phenol resin, a polyphenylene ether resin, and a polyphenylene sulfide resin, 50 to 95% by weight, and (C) a phosphate compound 5 (A) + (B) +
(C) + (D) according to the above resin composition in which the content is 100% by weight.

[0094]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these. In the following, all parts and percentages are by weight unless otherwise specified.

The following compounds were used in Examples and Comparative Examples. Component (A): polybutylene terephthalate resin (intrinsic viscosity 0.75, acid value 1.3 mg KOH / g) Component (B): polyphenylene ether resin (trade name: YP)
X-100L, manufactured by Mitsubishi Chemical Corporation, having an intrinsic viscosity of 0.45 dl / g measured at 30 ° C. using chloroform as a solvent) Component (C): Condensed phosphate (trademark: PX200,
Component (D): nitrogen-containing organic compound containing phosphorus atom (melamine polyphosphate) (trade name: Meluper 200/70, DMS)
Component (E): Oxazonyl group-modified polystyrene (trademark:
RPS1005, manufactured by Nippon Shokubai Co., Ltd.) Component (F): Silica-containing polyorganosiloxane resin powder (trademark: DC4-7081, manufactured by Dow Corning Toray) Component (G): Inorganic filler (glass having a diameter of 10 microns) Fiber) (trademark: manufactured by Vetrotex)

The evaluation method used in the present invention will be described below. [Method of measuring acid value of thermoplastic polyester resin] 20
1.0-2.0 g of the thermoplastic polyester resin is precisely weighed in a 0 ml Erlenmeyer flask, 60 ml of benzyl alcohol is added, and the inside of the Erlenmeyer flask is sufficiently replaced with nitrogen gas. After sealing, the Erlenmeyer flask is immersed in a constant temperature oil bath at 160 ° C., and the resin is completely dissolved while vibrating. Confirm complete dissolution, 0.1
About 1 ml of a 1% bromothymol blue / ethanol solution was added, a stirrer was inserted, and the mixture was titrated with a 1 / 50N potassium hydroxide / benzyl alcohol solution while heating and stirring on a heating stirrer. The end point of the titration was the time when the liquid changed from yellow to yellow-green. The acid value of the thermoplastic polyester resin is calculated according to the following equation.

Acid value (mgKOH / g) = [(V−V ₀ ) × F × 1.
122] / S V (ml): titration of a 1 / 50N potassium hydroxide / benzyl alcohol solution on the sample V ₀ (ml): titration of a blank 1 / 50N potassium hydroxide / benzyl alcohol solution F: Factor of 1 / 50N potassium hydroxide / benzyl alcohol solution S (g): Weight of sample

[Evaluation Method of Bending Strength] The bending strength and the bending elastic modulus were measured by an injection molding machine using a length of 127 mm and a width of 1 mm.
A rod-shaped test piece having a thickness of 2.7 mm and a thickness of 3.01 mm was formed.
According to ASTM D-790, the load speed is 5 mm / min,
Shimadzu Autograph AG50 with 50mm distance between spans
00 was measured.

[Evaluation Method of Izod Impact Value] Using an injection molding machine, length 127 mm, width 12.7 mm, thickness 3.
A bar-shaped test piece of 01 mm was formed, and this test piece was cut in half in the longitudinal direction, and a V-notch was formed on the gate side by cutting to obtain a notched test piece. According to ASTM D-790,
Izod impact values were measured.

[Evaluation Method of Flame Retardancy Test] Underwriters Laboratories Inc. (Underw
riters Laboratories Inc. vertical flammability test (UL9
4 V-0, V-1, V-2). The test was performed with a test piece having a thickness of 0.8 mm, and the evaluation was performed using five test pieces in one test, the first average burning time, the second average burning time, the total burning time of the five test pieces, The evaluation was made based on the presence or absence of cotton ignition due to dripping.

<< Examples 1 to 5 >> and << Comparative Example 1 >>,
<< Comparative Example 2 >> The above-mentioned raw materials were blended according to Tables 1 and 2, and mixed using a tumbler. The mixture was melt-kneaded at a cylinder temperature of 250 ° C. using a single-screw extruder having a diameter of 40 mm, extruded into strands, cooled, and then cut into pellets. After the obtained pellets were dried at 130 ° C. for 3 hours, they were molded into predetermined test pieces using an injection molding machine, and evaluated according to the evaluation method described above. The obtained results are shown in Tables 1 and 2.

[0102]

[Table 1]

[0103]

[Table 2]

[0104]

The resin composition of the present invention exhibits excellent flame retardancy without using a halogen-based flame retardant and has an excellent balance of properties such as mechanical strength. It can be widely used as a molding material for molded products such as electrical and electronic equipment parts such as members, transformer members, connectors, switches, relays, printed circuit boards, coil bobbins, automobile parts, and mechanical parts.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 61/08 C08L 61/08 71/12 71/12 81/02 81/02 83/06 83/06 85 / 02 85/02 F-term (reference) 4J002 BC00Z BC02Z BC12Z BN20Z BP03Z CC04X CF00W CF03W CF04W CF05W CF06W CF07W CF08W CF09W CF10W CF16W CF18W CF19W CH07X CN01X CP025 CP035 CP055 CP095 CP125 CP135 CP0 0150 CP125 CP135 CP0 0 DJ038 DJ048 DJ058 DK008 DL008 EU187 EW046 EW127 FA018 FA048 FA088 FB088 FB098 FB168 FD018 FD13Y FD135 FD136 FD137 GM00 GN00 GQ00 GQ01

Claims (5)

[Claims] 1. A polyester resin as a component (A), at least one aromatic resin selected from a novolak type phenol resin, a polyphenylene ether resin, and a polyphenylene sulfide resin as a component (B), and a component (C) ), And a phosphorus-containing nitrogen-containing organic compound or a sulfur-containing nitrogen-containing organic compound as the component (D). 2. The resin composition according to claim 1, wherein a styrene compound having a functional group is blended as the component (E). 3. The composition according to claim 1, wherein a polyorganosiloxane resin is blended as the component (F).
3. The resin composition according to item 1. 4. The resin composition according to claim 1, wherein an inorganic filler is blended as the component (G). 5. A mixture of (A) a polyester-based resin and (B) at least one aromatic resin selected from a novolak-type phenol resin, a polyphenylene ether-based resin and a polyphenylene sulfide-based resin in a total amount of 50 to 95% by weight; (C) 5 to 40% by weight of a phosphate compound, and (D) 1 to 40% by weight of a nitrogen-containing organic compound containing a phosphorus atom or a nitrogen atom containing a sulfur atom, and
The resin composition according to claim 1, wherein the components (A) + (B) + (C) + (D) are 100% by weight.