JP2002212403A - Flame-retardant resin composition and molded article therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition which can achieve flame resistance of not less than V-0 level of UL94 standard and is excellent in heat resistance. SOLUTION: (A) 100 parts by weight of a resin component (A component) containing at least 60% by weight of a polyester resin and (B) a specific cyclic organic phosphorus compound (B component) 1 to 7
A flame-retardant resin composition comprising 0 parts by weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-halogen flame-retardant polyester resin composition having high flame retardancy and heat resistance, and to a molded article thereof.

[0002]

2. Description of the Related Art Polybutylene terephthalate (hereinafter referred to as PB)
T) and other thermoplastic aromatic polyester resins have excellent mechanical properties, heat resistance, chemical resistance, etc., and are widely used as molded articles for applications in the fields of electric / electronics and automobiles. I have.

[0003] Among these, there are very many applications that require flame retardancy, and conventionally, resins having flame retardancy imparted mainly by using a halogen compound and an antimony compound as a flame retardant and a flame retardant auxiliary have been provided. ing.

However, decomposition products of halogen-based flame retardants may corrode metals in electrical products, and in recent years, some halogen-based flame retardants have been problematic in their influence on the environment. Non-halogenated products have become popular mainly in Europe. As a result, the demand for non-halogen flame retardants has increased, and the development of non-halogen flame retardants for each resin has become active. Various non-halogen flame retardant technologies have also been reported for polyesters,
Due to various problems, it has not been put to practical use.

As the non-halogen flame retardant, a phosphorus compound is generally used in general, and phosphoric esters such as red phosphorus and triphenyl phosphate (hereinafter abbreviated as TPP) are often used in this field. However,
Polyester resins such as PBT have relatively high processing temperatures, and it has been pointed out that red phosphorus generates highly toxic phosphine gas, and low molecular weight TPP has a problem of bleed-out. Furthermore, aromatic phosphate esters represented by TPP generally have a plasticizing effect, and thus have a problem that the heat resistance of the composition is significantly reduced. Further, when red phosphorus is used, the composition becomes brown peculiar to red phosphorus, and there is a problem that the range of use is limited.

[0006] As a known technique in this field, Japanese Patent Laid-Open No.
JP-A-126498 discloses a polyester resin, an epoxy compound having two or more epoxy groups in a molecule, and a phenol resin and / or a phosphorus, nitrogen or boron compound having a functional group capable of reacting with an epoxy group. A non-halogen flame retardant for polyester resin is disclosed.

JP-A-7-278267 discloses a flame-retardant polyester resin composition in which 5 to 50 parts by weight of the non-halogen flame retardant is added to 100 parts by weight of a polyester resin.

[0008] However, these resin compositions have problems that not only the flame retardancy is still insufficient, but also the fluidity is poor and the cost is disadvantageous.

Japanese Patent Application Laid-Open No. 8-208884 discloses that a thermoplastic resin such as polystyrene or polyester is combined with a phosphorus-based compound such as phosphoric acid ester or phosphite (specifically, triphenyl phosphate) in an ortho or para position. A flame-retardant resin composition obtained by adding a substituted phenolic resin in combination is disclosed.

[0010] This resin composition has not only the problems of bleed-out and reduction of heat resistance, but also the drawback that sufficient flame retardancy cannot be obtained.

Japanese Patent Publication No. 2-37370 discloses 99 to 34 parts by weight of a thermoplastic polyester resin having a softening point of 150 ° C. or more, such as polyethylene terephthalate, and 1 to 25 parts of red phosphorus coated with a thermosetting resin. A flame-retardant polyester-based resin composition comprising 10 parts by weight and 10 to 55 parts by weight of a reinforcing filler is disclosed.

However, this resin composition has a problem of coloring and a problem of phosphine gas generation as described above.

Further, JP-A-50-58319 discloses a flame-retardant polyester fiber composition comprising a fiber-forming linear polyester, an aryl spirophosphate and a halogen-based flame retardant containing at least 40% of chlorine or bromine. Is disclosed.

This publication only describes the flame retardancy of the fiber obtained by blending an aryl spirophosphate and a halogen compound with polyethylene terephthalate as a flame retardant component.

US Pat. No. 3,866,405 discloses a flame retardant fiber composition comprising a specific polyester resin and a halogen-containing spirodiphosphate.

This publication merely describes the flame retardancy of a fiber obtained by blending a spirodiphosphate containing a halogen element with a polyethylene naphthalate resin.

Japanese Patent Application Laid-Open No. 11-256012 discloses a flame-retardant resin composition in which a spirodiphosphate compound, a specific inorganic salt and a fluororesin are blended in an alloy resin of a polycarbonate resin and a polyester resin. I have. This publication is directed to a resin mainly composed of a polycarbonate resin.

[0018]

SUMMARY OF THE INVENTION The first object of the present invention is to achieve UL94 which has not been achieved by conventional phosphorus-based flame retardants.
An object of the present invention is to provide a polyester resin composition which can achieve flame retardancy of a standard V-0 level or higher and has excellent heat resistance.

A second object of the present invention is to provide a flame-retardant polyester resin composition which has a small decrease in the deflection temperature under load and has low flame retardancy.

A third object of the present invention is to provide a deflection temperature under load,
It is an object of the present invention to provide a polyester resin composition which has a high level of impact resistance and flame retardancy in a well-balanced manner and does not substantially contain halogen.

Another object of the present invention is to provide a flame-retardant polyester resin composition which can be advantageously used for home electric appliance parts, electric / electronic parts, automobile parts and the like.

[0022]

According to the study of the present inventors, the object of the present invention is to provide (A) a resin component (A component) containing at least 60% by weight of a polyester resin.
This is achieved by a flame-retardant resin composition comprising 0 parts by weight and (B) 1 to 70 parts by weight of an organic phosphorus compound (component B) represented by the following general formula (1).

[0023]

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(In the formula, R ¹ and R ² may be the same or different and are a monovalent aromatic group represented by the following general formula (2).)

[0025]

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(Here, Ar represents any one group selected from a phenyl group, a naphthyl group, an anthryl group, a pyridyl group and a triazyl group, n is an integer of 0 to 5, and R ³ is each. May be the same or different, and may be bonded to any part other than the part bonded to phosphorus via an oxygen atom on Ar, and may be methyl, ethyl, propyl, butyl or The linking group represents an aryl group having 5 to 14 carbon atoms via oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.)

According to the present invention, when a phosphorus-containing compound having a specific structure having a spiro ring containing a diphosphate is blended with a polyester resin, it is surprisingly found that the conventional phosphorus-based flame retardant has not achieved the UL94 standard. V-0
It has been found that the flame retardant effect of satisfying the above level is exhibited and that the heat resistance is reduced, especially the load deflection temperature is reduced.

Hereinafter, the resin composition of the present invention will be described in more detail.

The thermoplastic aromatic polyester resin used as the component A in the present invention is a polyester containing an aromatic dicarboxylic acid as a main dicarboxylic acid component and an aliphatic diol having 2 to 10 carbon atoms as a main glycol component.
Preferably, at least 80 mol%, more preferably at least 90 mol%, of the dicarboxylic acid component comprises the aromatic dicarboxylic acid component. Also, the glycol component preferably comprises at least 80 mol%, more preferably at least 90 mol%, of an aliphatic diol component having 2 to 10 carbon atoms.

Preferred examples of the aromatic dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, methyl terephthalic acid, methyl isophthalic acid, and 2,6-naphthalenedicarboxylic acid. These can be used alone or in combination of two or more. Examples of the secondary dicarboxylic acid other than the aromatic dicarboxylic acid include adipic acid, sebacic acid, decanedicarboxylic acid, azelaic acid, dodecanedicarboxylic acid, and aliphatic or alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. .

Examples of the aliphatic diol having 2 to 10 carbon atoms include aliphatic diols such as ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol and the like, and fatty acids such as 1,4-cyclohexane dimethanol. A cyclic diol can be mentioned. As the other glycol other than the aliphatic diol having 2 to 10 carbon atoms, for example, p, p'-
Examples thereof include dihydroxyethoxybisphenol A and polyoxyethylene glycol.

Preferred examples of the thermoplastic aromatic polyester resin (component (A)) include a main dicarboxylic acid component comprising at least one dicarboxylic acid selected from terephthalic acid and 2,6-naphthalenedicarboxylic acid, and a main diol component comprising ethylene. It is a polyester having an ester unit composed of at least one diol selected from glycol, trimethylene glycol and tetramethylene glycol.

Specifically, a polyester resin having a repeating unit of at least one selected from ethylene terephthalate, trimethylene terephthalate, tetramethylene terephthalate, and tetramethylene 2,6-naphthalenedicarboxylate is preferred. Particularly preferred is polybutylene terephthalate (PBT).

A polyester elastomer having the above repeating unit as a main repeating unit of a hard segment can also be used.

As a soft segment of a polyester elastomer having tetramethylene terephthalate or tetramethylene-2,6-naphthalenedicarboxylate as a main repeating unit of a hard segment, for example, dicarboxylic acid may be terephthalic acid, isophthalic acid, sebacic acid and adipic acid. And at least one dicarboxylic acid selected from the group consisting of a long-chain diol having 5 to 10 carbon atoms and H (OCH ₂ CH ₂ ) _i OH (i = 2 to 5).
A material composed of at least one diol selected from the group consisting of polyester and polycaprolactone having a melting point of 100 ° C. or less or amorphous can be used.

The main component is a component of 80 mol% or more, preferably 90 mol% or more of all dicarboxylic acid components or all glycol components, and the main repeating unit is at least 80 mol% of all repeating units. Preferably 90
It is a repeating unit of at least mol%.

The thermoplastic aromatic polyester resin used in the present invention has an intrinsic viscosity of preferably 0.5 to 1.4 dl / g, more preferably 0.6 to 1.2 dl / g, measured at 35 ° C. in orthochlorophenol. It is. If the intrinsic viscosity is less than 0.5, the mechanical strength of the obtained composition will be low, and if it exceeds 1.4, the fluidity of the obtained composition may be reduced.

In the flame-retardant resin composition of the present invention, when the resin component (A component) is 100% by weight, the polyester resin (A-1 component) is 60 to 1%.
00% by weight, preferably 80 to 100% by weight, more preferably 90 to 100% by weight. Examples of the resin other than impact-resistant polystyrene (A-2 component) in the resin component include at least one selected from the group consisting of polyphenylene ether resin, polycarbonate resin, ABS resin, impact-resistant polystyrene resin, and phenol resin. . The A-2 component is 100 parts of the resin component (A component).
0 to 40% by weight, preferably 0 to 20% by weight
%, Particularly preferably in the range from 0 to 10% by weight.

In the present invention, the organic phosphorus compound used as the component B is represented by the following general formula (1).

[0040]

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(In the formula, R ¹ and R ² may be the same or different and are a monovalent aromatic group represented by the following general formula (2).)

[0042]

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(Where Ar represents any one group selected from a phenyl group, a naphthyl group, an anthryl group, a pyridyl group and a triazyl group, n is an integer of 0 to 5; R ³ is May be the same or different, and may be bonded to any part other than the part bonded to phosphorus via an oxygen atom on Ar, and may be methyl, ethyl, propyl, butyl or The linking group represents an aryl group having 5 to 14 carbon atoms via oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.)

In the above general formula (1), R ¹ and R ²
May be the same or different, and the above general formula (2)
And in the general formula (2), Ar is any one group selected from a phenyl group, a naphthyl group, an anthryl group, a pyridyl group and a triazyl group, preferably a phenyl group Wherein n is an integer of 0 to 5, preferably 0 to 4, and R ³ may be the same or different, and a moiety bonded to phosphorus via an oxygen atom on Ar. And methyl, ethyl, propyl (including isomers), butyl (including isomers), or a group bonded to Ar is oxygen, sulfur, or a group having 1 to 4 carbon atoms. 5-14 carbon atoms via an aliphatic hydrocarbon group, preferably 6-carbon atoms
14 aryl groups.

In the general formula (1), preferred examples of R ¹ and R ² include phenyl, cresyl, xylyl, trimethylphenyl, 4-phenoxyphenyl, cumyl, naphthyl, Examples thereof include a benzylphenyl group, and a phenyl group is particularly preferable.

Such an organic phosphorus compound is basically prepared by reacting phosphorus oxytrichloride with an adjacent diol skeleton.
It is obtained by appropriately reacting a phenolic hydroxyl group. Such a reaction is described, for example, in JP-A-9-183786.
Or R.I. M. McC
onnell et al. Org. Chem. , 24 volumes, 6
The method described on pages 30 to 635 (1959) is employed.

Specifically, the organophosphorus compound used in the present invention is obtained by reacting pentaerythritol with phosphorus oxytrichloride and then reacting, for example, phenol, 2,5-dimethylphenol, cresol, or the like. Can be Alternatively, it is also possible to modify a part of the chlorine of phosphorus oxytrichloride in advance with these phenols and then to carry out the same reaction.

When the organic phosphorus compound of the general formula (1) is reacted, for example, by the above-mentioned method, an oligomer is mainly produced as a by-product. Generally, an operation of removing impurities by washing with a solvent such as methanol is performed.
However, in the range where the oligomer is present in a certain range, by remaining in the organic phosphorus compound of the B component, there is an advantage that when mixed with the resin, the fluidity is improved while maintaining the heat resistance of the resin composition, and There is an advantage that bleeding out becomes difficult when kneaded into resin. Thus, it is desirable that the organic phosphorus compound as the component B has an HPLC purity of preferably 85 to 98%, more preferably 90 to 96%. Here, the HPLC purity of the organic phosphorus compound can be measured effectively by using the following method.

The column is Develos manufactured by Nomura Chemical Co., Ltd.
The column temperature was 40 ° C. using il ODS-7 300 mm × 4 mmφ. A 6: 4 mixed solution of acetonitrile and water was used as a solvent, and 5 μl was injected. The detector used was UV-267 nm.

The polyester resin (component (A)) 100
The compounding amount of the organic phosphorus compound (component B) is 1 to 70 parts by weight, more preferably 2 to 50 parts by weight, and still more preferably 3 to 30 parts by weight with respect to parts by weight. If the amount is less than 1 part by weight, the obtained resin composition is inferior in flame retardancy, and if it is more than 70 parts by weight, the physical properties of the resin composition may be deteriorated, and the cost may be disadvantageous.

The resin composition of the present invention consists essentially of a resin component (component A) mainly composed of a polyester resin and the phosphorus-containing compound represented by the above formula (1). The compound can be compounded as a C component. By blending the component C, the flame retardant effect, physical strength, heat resistance, and the like can be improved, and the cost can be reduced.

Examples of the C component that can be further blended include the following phosphorus (C-1) to (C-5) or phosphorus compounds. (C-1) Red phosphorus (C-2) Triaryl phosphate represented by the following general formula (C-2)

[0053]

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(C-3) Condensed phosphate ester represented by the following general formula (C-3)

[0055]

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(C-4) Condensed phosphoric acid ester represented by the following general formula (C-4)

[0057]

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(C-5) An organic phosphorus compound represented by the following general formula (C-5)

[0059]

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R ^{4 to} R ^{6 in the} above formulas (C-2) to (C-4)
May be the same or different and each is an aryl group having 6 to 15 carbon atoms, preferably an aryl group having 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group. These aryl groups may have 1 to 5, preferably 1 to 3 substituents, and (i) a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group,
an alkyl group having 1 to 12 carbon atoms (preferably an alkyl group having 1 to 9 carbon atoms) such as a c-butyl group, a t-butyl group, a neopentyl group and a nonyl group; (ii) a methoxy group, an ethoxy group, a propoxy group; (C) alkyloxy groups having 1 to 12 carbon atoms (preferably alkyloxy groups having 1 to 9 carbon atoms) such as butoxy groups and pentoxy groups, and (iii) carbon atoms such as methylthio groups, ethylthio groups, propylthio groups, butylthio groups and pentylthio groups. An alkylthio group of numbers 1 to 12 (preferably an alkylthio group of 1 to 9 carbon atoms) and (iv) a group represented by the formula Ar ³ -Y- (where Y is -O
-, -S- or 1 to 8 carbon atoms, preferably 1 to 1 carbon atoms
4 represents an alkylene group, and Ar ³ represents an aryl group having 6 to 15 carbon atoms, preferably 6 to 10 carbon atoms).

In the formulas (C-3) and (C-4), A
r ¹ and Ar ² are both present (in the case of C-4)
May be the same or different and represents an arylene group having 6 to 15 carbon atoms, preferably an arylene group having 6 to 10 carbon atoms. Specific examples include a phenylene group or a naphthylene group. The arylene group may have 1 to 4, preferably 1 to 2 substituents. Examples of such a substituent include (i) an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a t-butyl group;
(Ii) C7-C2 such as benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group and cumyl group
An aralkyl group of 0, (iii) a group represented by the formula R ⁸ -Z- (where Z represents -O- or -S-, and R ⁸ has 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms) An alkyl group or an aryl group having 6 to 15, preferably 6 to 10 carbon atoms) and (iv) an aryl group having 6 to 15 carbon atoms such as a phenyl group.

In the formulas (C-3) and (C-4), m
Represents an integer of 1 to 5, preferably an integer of 1 to 3, and particularly preferably 1.

In the formula (C-4), X represents Ar ¹ and Ar ²
-Ar ¹ -XA
r ² — is a residue usually derived from bisphenol. Thus, X is a single bond, -O-, -CO-, -S-,
-SO ₂ -or an alkylene group having 1 to 3 carbon atoms,
Preferably it is a single bond, -O- or isopropylidene.

The compound of the formula (C-5) is 6H-
Benzo [c, e] [1,2] oxaphosphorin-6-one. Each of the two benzene rings in the compound (C-5) may have 1 to 4, preferably 1 to 2 substituents. Examples of the substituent include the substituents (i) to (iv) exemplified as the substituents of the aryl group of R ^{1 to} R ^{4 in} the formulas (C-2) to (C-4).

When the above-mentioned phosphorus (C-1) to (C-5) or the phosphorus compound (component C) is blended in the resin composition of the present invention, the proportion of the phosphorus-containing compound (component B)
1 to 100 parts by weight, preferably 5 to 100 parts by weight
An appropriate range is from 80 to 80 parts by weight, particularly preferably from 10 to 60 parts by weight. Of the above-mentioned phosphorus (C-1) to (C-5) or phosphorus compound, preferably (C-2) to (C-
5) A phosphorus compound.

The resin composition of the present invention may further contain dicumyl (D component) represented by the following chemical formula.

[0067]

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This dicumyl (D component) is a resin component (A
Component) 0.01 to 3 parts by weight, preferably 0.02 to 2 parts by weight, particularly preferably 0.03 to 3 parts by weight, per 100 parts by weight.
1 part by weight is blended. It is presumed that the flame retardant effect of blending dicumyl in the above ratio is due to radical generation, and as a result, the level of flame retardancy is improved.

The resin composition of the present invention may further contain a known flame retardant aid. As flame retardant aids,
For example, silicone oil can be mentioned. Such a silicone oil has a polydiorganosiloxane skeleton, and is preferably polydiphenylsiloxane, polymethylphenylsiloxane, polydimethylsiloxane, or any copolymer or mixture thereof, and among them, polydimethylsiloxane is preferably used. . Its viscosity is preferably 0.8 to 5000 centipoise (25 ° C.), more preferably 10 to 1000 centipoise (25 ° C.), and still more preferably 50 to 500 centipoise (25 ° C.). Excellent in flammability and preferred. The amount of the silicone oil is 0.1 to 100 parts by weight of the resin component (A component).
A range of 5 to 10 parts by weight is preferred.

Further, a fluorine resin can be blended as an anti-dripping agent. Examples of such a fluorine-based resin include homo- or copolymers of fluorine-containing monomers such as tetrafluoroethylene, trifluoroethylene, vinyl fluoride, vinylidene fluoride, and hexafluoropropylene. Further, the fluorine-containing monomer and a polymerizable monomer such as ethylene, propylene, or acrylate may be copolymerized to the extent that the drip prevention performance is not impaired. Among these fluororesins, polytetrafluoroethylene is preferred. The preferred polytetrafluoroethylene is what is called type 3 according to the ASTM standard. The fluororesin is a resin component (A component) 100
0.01 to 3 parts by weight, preferably 0.1 to 1 part by weight
A suitable range is from 2 to 2 parts by weight.

The flame-retardant resin composition of the present invention may contain various additives such as antioxidants, ultraviolet absorbers, deterioration inhibitors such as light stabilizers, lubricants, antistatic agents, release agents, plasticizers. Agents, reinforcing fibers such as glass fiber and carbon fiber, fillers such as talc, mica and wollastonite, and coloring agents such as pigments may be added. The amount of the additive to be used can be appropriately selected according to the type of the additive within a range that does not impair heat resistance, impact resistance, mechanical strength, and the like.

The flame-retardant resin composition of the present invention is prepared by mixing a resin component (A component), a phosphorus compound (B component) and other components as necessary with a V-blender, a super mixer,
The mixture is preliminarily mixed using a mixer such as a super floater or a Henschel mixer, and the premix is supplied to a kneader and melt-mixed. As the kneader, various melt mixers, for example, a kneader, a single-screw or twin-screw extruder can be used, and among these, the resin composition is mixed using a twin-screw extruder or the like.
Melting at a temperature of 20 to 280 ° C., preferably 230 to 270 ° C., injecting a liquid component with a side feeder,
A method of extruding and pelletizing with a pelletizer is preferably used.

The flame-retardant resin composition of the present invention has particularly good heat resistance, and is useful as a material for molding various molded articles such as home electric appliance parts, electric / electronic parts, and automobile parts. Specifically, it can be suitably used for a switch component, a motor component, an ignition coil case, a relay case, a fuse case, and the like. The molding method is not particularly limited, such as injection molding and blow molding, but it is preferably produced by injection molding a pellet-shaped resin composition using an injection molding machine.

The molded article formed from the resin composition of the present invention has extremely excellent physical properties as compared with a conventionally known molded article containing a flame retardant as a phosphorus-containing compound.
Excellent heat resistance, especially deflection temperature under load (HDT)
Is characterized by high points. Specifically, when a polyester resin is mixed with a phosphoric ester such as triphenyl phosphate (TPP) or resorcinol bisdiphenyl phosphate (RDP), which is conventionally known as a flame retardant, the HDT inherent in the polyester resin is greatly reduced. It is known to decrease. For example, if a sufficient amount of TPP is added to the polyester resin to achieve the flame retardant effect, the retention of the deflection temperature under load (HDT) decreases to 50 to 80%.

However, when the phosphorus-containing compound (component B) of the present invention is blended with a polyester resin, the retention of HDT is maintained at least 90%, and the rate of decrease is extremely small. Under preferable conditions, the retention of the deflection temperature under load (HDT) of the molded article from the resin composition of the present invention is 95%.
It has a high retention rate as described above and sometimes shows 100% or more. When a phosphorus-based compound is blended as a flame retardant with a polyester resin in this way, the composition exhibits almost the same or higher level of deflection temperature under load (HDT) of the polyester resin itself in some cases. Things have never been known before.

The resin composition of the present invention has a retention of a deflection temperature under load (HDT) of 90% from the polyester resin used.
%, Preferably 95% or more. Within this range of retention, it has practically great value and means that the polyester resin retains its inherent high heat resistance. Here, the load deflection temperature retention rate is the load deflection temperature X (° C.) of the polyester resin (component A) and the load deflection temperature Y of the resin composition containing the phosphorus compound (component B).
(Y / X) × 100% in relation to (° C.). Further, when the component A is substantially a polyester resin, the resin composition of the present invention may have an ASTM-D6
The value of the deflection temperature under load measured with a 1/4 inch test piece at a load of 1.81 MPa (18.5 kgf / cm ² ) by a method according to No. 48 is preferably 60 to 150 ° C., and more preferably 70 to 140 ° C. ° C.

[0077]

EXAMPLES The present invention will be described below with reference to examples.
The scope of the present invention is not limited to these examples. The evaluation was performed by the following method. (1) Flame retardancy (UL-94 evaluation) Flame retardancy is specified in UL-94 of the United States UL standard as an evaluation scale of flame retardancy using a test piece having a thickness of 1/16 inch (1.6 mm). The evaluation was performed according to the vertical combustion test. All specimens burned 10 after the flame was removed.
A fire extinguishing within 2 seconds and the dripping material did not cause cotton ignition was V-0, and a fire extinguishing within 30 seconds and the dripping material caused cotton ignition was V-2. Those below the standard were notV. (2) Deflection temperature under load (HDT), retention rate of deflection temperature under load The deflection temperature under load was measured using a 6.35 mm (1/4 inch) test piece by a method based on ASTM-D648.
It was measured with a 8.5 kg load. Further, the load deflection temperature retention rate is the load deflection temperature X of the used polyester resin.
(° C.) and the deflection temperature under load Y of the polyester resin composition
(° C.) was measured and calculated by a calculation formula of (Y / X) × 100 (%). (3) Purity of phosphorus compound The sample was dissolved in a 6: 4 mixed solution of acetonitrile and water, and 5 µl of the solution was injected into the column. The column is Develosil ODS-7 300 mm manufactured by Nomura Chemical Co., Ltd.
× 4 mmφ, and the column temperature was 40 ° C. The detector used was UV-267 nm.

Next, preparation examples of the phosphorus-containing compound used in the examples are shown.

[Preparation Example 1] 2,4,8,10-Tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-diphenoxy-
Preparation of 3,9-dioxide (b-1) 6.81 parts of pentaerythritol and 16.0 of pyridine were placed in a reaction vessel equipped with a thermometer, a condenser, and a dropping funnel.
And 80.0 parts of dioxane were charged and stirred. 21.1 parts of phenyldichlorophosphate was added to the reaction vessel using the dropping funnel, and after the addition was completed, the mixture was heated to reflux. After the reaction, the mixture was cooled to room temperature, and the obtained crystals were washed with water and filtered. The obtained filtered material is kept at 120 ° C. and 133 Pa
For 3 hours to obtain 19.6 parts of a white solid. The obtained solid was analyzed by ³¹ P, ¹ HNMR spectrum and melting point measurement to obtain 2,4,8,10-tetraoxa-3,
9-diphosphaspiro [5,5] undecane, 3,9-
It was confirmed to be diphenoxy-3,9-dioxide. The yield was 80% and the HPLC purity was 93%.

Note that ¹ H-NMR (DMSO-d ₆ , 30
0 MHz): δ7.38 (m, 10H), 4.75an
d4.45 (m, 8H), ³¹ P-NMR (DMSO-d
₆ , 120 MHz): δ-13.52 (S), melting point: 1
93-195 ° C. The following components were used in Examples and Comparative Examples. (A) Polyester resin polybutylene terephthalate (TRB- manufactured by Teijin Limited)
J) was used. (B) Organic phosphorus compound 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-diphenoxy-3,9-dioxide {R ^{1 in the} above formula (1) And a cyclic phosphate compound synthesized in Preparation Example 1 in which both R ² and R ² are phenyl groups (hereinafter referred to as FR-1).
PP (hereinafter referred to as TPP) 1,3-phenylenebis [di (2,6-dimethylphenyl) phosphate] ｛In the formula (C-3), R ⁴ , R ⁵ , R ⁶ and R ⁷ are 2, Organic phosphate ester compound which is a 6-dimethylphenyl group, Adekastab FP-500 (hereinafter referred to as FP-500) manufactured by Asahi Denka Kogyo Co., Ltd. 1,3-phenylenebis [diphenylphosphate] ｛The above-mentioned general formula (C- In 3), R ⁴ , R ⁵ , R ⁶ and R ⁷
Is a phenyl group, an organic phosphate compound, CR-733S manufactured by Daihachi Chemical Co., Ltd. (hereinafter referred to as CR-733S)

[Examples 1 and 2, Comparative Examples 1 to 7] The components shown in Table 1 were blended in a tumbler in the amounts (parts by weight) shown in Table 1 and a 15 mmφ twin-screw extruder (KZW1 manufactured by Technovel)
In 5), the mixture was pelletized at a resin temperature of 250 ° C., and the obtained pellets were dried with a hot air dryer at 70 ° C. for 4 hours.
The dried pellets are injected into an injection molding machine (Nippon Steel Works, Ltd.)
J75Si) at 250 ° C. cylinder temperature.
Table 1 shows the results of evaluation using the molded plate.

[0082]

[Table 1]

[0083]

According to the present invention, there is provided a polyester resin composition having excellent flame retardancy and heat resistance. This resin composition is used for molding various parts of household electric appliance parts, electric / electronic parts, automobile parts and the like. It is suitable as a material for forming articles, and is extremely useful industrially.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA45 AC15 AE07 AH07 AH12 BA01 BB05 BC03 4J002 CF031 CF071 EW046 FD136 GN00 GQ00

Claims (8)

[Claims] (A) 100 parts by weight of a resin component (A component) containing at least 60% by weight of a polyester resin and (B) an organic phosphorus compound (B component) 1 to 1 represented by the following general formula (1): A flame-retardant resin composition comprising 70 parts by weight. Embedded image (In the formula, R ¹ and R ² may be the same or different and are a monovalent aromatic group represented by the following general formula (2).) (Here, Ar represents any one group selected from a phenyl group, a naphthyl group, an anthryl group, a pyridyl group, and a triazyl group, and n is an integer of 0 to 5. R ³ is the same.) Or may be different, and may be bonded to any portion other than the portion bonded to phosphorus via an oxygen atom on Ar, and methyl, ethyl, propyl, butyl or a bonding group to Ar is , Oxygen, sulfur or an aryl group having 5 to 14 carbon atoms via an aliphatic hydrocarbon group having 1 to 4 carbon atoms.) 2. The flame-retardant resin composition according to claim 1, wherein the polyester resin as the component A is a polybutylene terephthalate resin. 3. The method according to claim 1, wherein the composition is substantially free of halogen.
The flame-retardant resin composition according to the above. 4. The resin composition according to claim 1, wherein the deflection temperature under load (M) represented by the following formula can achieve at least 90%. M (%) = (Y / X) × 100 where X indicates the deflection temperature under load (° C.) of the molded article from the resin component (A component) itself, and Y indicates the resin component (A component) and the organic phosphorus compound (B Component) shows the deflection temperature under load (° C.) of a molded article from the resin composition comprising 5. The flame-retardant resin composition according to claim 1, which can at least achieve a flame-retardant level V-0 of UL-94 standard. 6. The flame-retardant resin composition according to claim 1, wherein the HPLC purity of the component B organic phosphorus compound is 85 to 98%. 7. A molded article formed from the flame-retardant resin composition according to claim 1. 8. An injection-molded article formed from the flame-retardant resin composition according to claim 1.