JP2003213109A - Flame-retardant resin molding material and molded product therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a flame-retardant polyester resin composition which contains substantially no halogen and satisfies the V-2 level, and the V-0 level under a favorable condition, according to the UL-94 standard. <P>SOLUTION: The flame-retardant polyester resin composition comprises (A) 100 pts.wt. of a resin component (A component) containing at least 60 wt.% of an aromatic polyester resin, (B) 1-100 pts.wt. of a specific organic phosphorus compound (B-1 component) represented by formula (1-a) as a preferable example, (C) 0-50 pts.wt. of a flame-retardant modified resin (C component), and (D) 0-200 pts.wt. of a filler (D component). The molded product is produced from the composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant polyester resin composition having a high degree of flame retardancy and good physical properties and a molded article made from the same. More specifically, it relates to a substantially halogen-free flame-retardant polyester resin composition containing a specific organic phosphorus compound as a flame retardant, and a molded article made from the same.

[0002]

2. Description of the Related Art Polybutylene terephthalate (hereinafter referred to as PB
Thermoplastic aromatic polyester resins such as T) have excellent mechanical properties, heat resistance, chemical resistance, etc., and are therefore molded products for use in the electrical / electronic field, machine component field, automobile field, etc. Widely used as.

Of these, there are many applications in which flame retardancy is required, and conventionally, mainly halogen-containing compounds and antimony compounds have been used as flame retardants and flame retardant aids, respectively.
A resin provided with flame retardancy is provided.

However, the halogen-containing flame retardant may cause a decomposition product to corrode a metal in an electric product, and in recent years, some halogen-containing flame retardants have been problematic in that they affect the environment. Products are becoming non-halogenated mainly in Europe. Therefore, the demand for non-halogen flame retardants has increased, and development of non-halogen flame retardants for each resin has been actively pursued. Various non-halogen flame-retardant techniques have been reported for polyester resins, but due to various problems, they have not been put to practical use.

Phosphorus-containing compounds are often used as the non-halogen flame retardant, and phosphoric acid 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 a relatively high processing temperature, and it is pointed out that phosphine gas, which is highly toxic with red phosphorus, is generated. Also, when red phosphorus is used, the composition becomes a brown color peculiar to red phosphorus. There is also a problem that is limited. On the other hand, low-molecular weight TPP has a problem of bleed-out, and since aromatic phosphates represented by TPP generally have a plasticizing effect, there is a problem that the heat resistance of the composition is significantly lowered.

[0006] Next, literatures known to improve the flame-retardant resin composition using a phosphorus-containing compound as a flame retardant will be introduced. For example, a polyester resin, an epoxy compound having two or more epoxy groups in the molecule and a phosphorus, nitrogen or boron compound having a functional group capable of reacting with a phenol resin and / or an epoxy group are disclosed in JP-A-7-126498. A non-halogen flame retardant for a polyester resin, which is obtained by melt reaction, is disclosed. JP-A-7-27
Japanese Patent No. 8267 discloses a flame-retardant polyester resin composition obtained by adding 5 to 50 parts by weight of the non-halogen flame retardant to 100 parts by weight of a polyester resin. However, such a resin composition has not only insufficient flame retardancy, but also has poor fluidity and is disadvantageous in terms of cost.

Japanese Unexamined Patent Publication (Kokai) No. 8-208884 discloses that a thermoplastic resin such as polystyrene or polyester has a phosphorus-containing compound (specifically triphenyl phosphate) such as a phosphoric acid ester or a phosphorous acid ester and an ortho position or a para position. A flame-retardant resin composition obtained by adding substituted phenol resins together is disclosed. This resin composition has not only the problems of bleed-out and deterioration of heat resistance, but also the drawback that sufficient flame retardancy cannot be obtained.

In Japanese Patent Publication No. 2-37370, 99-34 parts by weight of a thermoplastic polyester resin having a softening point of 150 ° C. or higher, such as polyethylene terephthalate,
1 to 25 parts by weight of red phosphorus coated with a thermosetting resin,
A flame-retardant polyester resin composition comprising 10 to 55 parts by weight of a reinforcing filler is disclosed. However,
As described above, this resin composition has problems regarding coloring and generation of phosphine gas during molding.

Further, JP-A-50-58319 discloses a flame-retardant polyester fiber comprising a fiber-forming linear polyester, an aryl spirophosphate, and a halogen-containing flame retardant containing at least 40% chlorine atom or bromine atom. Compositions are disclosed. This publication specifically discloses the flame retardancy of fibers obtained by using polyethylene terephthalate in combination with aryl spiro phosphate and a halogen-containing compound as flame-retardant components.

Further, JP-A-52-12329 (German Patent No. 2630693 and British Patent No. 15152).
No. 23) discloses that flame retardancy is exhibited by blending a polyester fiber with a specific organic phosphorus-containing compound. Specifically, there is described an example in which polyethylene terephthalate and a specific organic phosphorus compound are mixed to obtain a fiber, and the fiber is used as a woven fabric, and its flame retardancy (for example, oxygen index) is slightly improved. The technique described in this publication only teaches flame retarding polyethylene terephthalate fibers.

US Pat. No. 3,866,405 discloses a flame-retardant fiber composition comprising a specific polyester resin and halogen-containing spiro diphosphate. In this publication, specifically, a polyethylene naphthalate resin is blended with a spiro diphosphate containing a halogen element, and the flame retardancy of the obtained fiber is shown. However, this US patent relates to fibers, and although the flame retardancy of polyester fibers is improved, halogen-containing flame retardants are used, and as described above, the environmental impact is a problem.

US Pat. No. 4,257,931 discloses a flame-retardant resin composition comprising a polyester resin, melamine pyrophosphate and an organic cyclic phosphorus compound. In this publication, a high flame retardant effect is obtained by using the above two flame retardants together. This flame retardant effect is largely due to melamine pyrophosphate, but when this melamine pyrophosphate is used, there is a problem in that the appearance of the molded product is poor and it is difficult to put it into practical use.

[0013]

A first object of the present invention is to provide a polyester resin composition having a high degree of flame retardancy and having a balance of industrially useful heat resistance and mechanical properties and the like. It is to provide molded articles from it.

A second object of the present invention is to achieve a high level of flame retardancy above the V-2 level of UL94 standard, and below the V-0 level under suitable conditions without containing halogen substantially. It is intended to provide a polyester resin composition capable of being produced and a molded article made from the same.

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, machine structural parts, automobile parts and the like, and molded articles made from the same. is there.

Still another object of the present invention is to provide a flame retardant resin composition having excellent transparency.

[0017]

According to the studies by the present inventors, the object of the present invention is to provide a resin component (A component) containing at least 60% by weight of (A) an aromatic polyester resin.
100 parts by weight, (B) 1 to 100 parts by weight of an organophosphorus compound (B-1 component) represented by the following general formula (1), (C) 0 to 50 parts by weight of a flame retardant improvement resin (C component), and , (D)
This is achieved by a flame-retardant resin composition comprising 0 to 200 parts by weight of a filler (component D) and a molded product made from the same.

[0018]

[Chemical 5]

(In the formula, R ¹ and R ⁴ may be the same or different and each is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. R ³ and R ⁶ are the same or different. It may be an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
R ² and R ⁵ may be the same or different and each is a phenyl group, a naphthyl group or an anthryl group, and may have a substituent on its aromatic ring. According to the present invention, a flame-retardant polyester resin composition having excellent mechanical properties and having a flame retardancy level of at least V-2 and, under suitable conditions, V-0 can be obtained.

The flame-retardant resin composition of the present invention will be described in more detail below.

In the present invention, as the resin component, the aromatic polyester resin may occupy the main component in the constituent resin component (A component), preferably the aromatic polyester resin (A-1).
The component) may be at least 60% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight. Less than 40% by weight, preferably less than 30% by weight, and particularly preferably less than 20% by weight in the component A may be another resin (component A-2). The other resins will be described later in detail.

The aromatic polyester resin (A-1 component) in the constituent resin component (A component) of the present invention contains 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. And polyester. Preferably, 80 mol% or more, more preferably 90 mol% or more of the dicarboxylic acid component is composed of the aromatic dicarboxylic acid component. On the other hand, the glycol component is preferably 8
0 mol% or more, more preferably 90 mol% or more, is composed 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, methylterephthalic acid, methylisophthalic acid and 2,6-naphthalenedicarboxylic acid. These can use 1 type (s) or 2 or more types. Examples of secondary dicarboxylic acids other than aromatic dicarboxylic acids include adipic acid, sebacic acid, decane dicarboxylic acid, azelaic acid, dodecane dicarboxylic acid, aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, and alicyclic dicarboxylic acids. it can.

Examples of the aliphatic diol having 2 to 10 carbon atoms include aliphatic diols such as ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol and neopentyl glycol, and fats such as 1,4-cyclohexanedimethanol. Mention may be made of cyclic diols. Examples of glycols other than the aliphatic diol having 2 to 10 carbon atoms include p, p'-dihydroxyethoxybisphenol A and polyoxyethylene glycol.

As a preferred example of the aromatic polyester resin (A-1 component), the main dicarboxylic acid component is at least one dicarboxylic acid selected from terephthalic acid and 2,6-naphthalenedicarboxylic acid, and the main diol component is ethylene. Glycol, trimethylene glycol,
And a polyester having an ester unit composed of at least one diol selected from tetramethylene glycol.

Specific aromatic polyester resin (A-1
Component) is at least one selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, polycyclohexane dimethyl terephthalate resin, polytrimethylene terephthalate resin and polytrimethylene naphthalate resin. It is preferably a seed.

Particularly preferred is at least one selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin and polyethylene naphthalate resin. Polybutylene terephthalate resin is particularly preferable.

Further, as the aromatic polyester resin (A-1 component) of the present invention, a polyester elastomer having the above repeating unit as a main repeating unit of a hard segment can be used.

Examples of the soft segment of the polyester elastomer containing tetramethylene terephthalate or tetramethylene-2,6-naphthalene dicarboxylate as the main repeating unit of the hard segment include dicarboxylic acids such as terephthalic acid, isophthalic acid, sebacic acid and adipic acid. Of 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
It is possible to use a polyester or polycaprolactone having at least one diol selected from the group consisting of 5) and having a melting point of 100 ° C. or lower or amorphous.

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 80 mol% or more of all repeating units, Preferably 90
It is a repeating unit of not less than mol%.

The molecular weight of the aromatic polyester resin in the present invention has only to have an intrinsic viscosity that can be usually used as a molded article, and the intrinsic viscosity measured in orthochlorophenol at 35 ° C. is preferably 0.5 to. 1.6 dl / g,
More preferably, it is 0.6 to 1.5 dl / g.

The aromatic polyester resin preferably has a terminal carboxyl group (—COOH) amount of 1 to 60 equivalents / T (1 ton of polymer). The amount of this terminal carboxyl group can be determined by potentiometric titration with an alkaline solution of m-cresol solution, for example.

The constituent resin (component A) of the present invention may contain another thermoplastic resin (component A-2) in addition to the aromatic polyester resin (component A-1). As described above, the content of the other resin (A-2 component) is less than 40% by weight, preferably less than 30% by weight based on the A component.

The thermoplastic resin as the component A-2 is polyphenylene ether resin (PPE), polycarbonate resin (PC), polyamide resin (PA), polyolefin resin (PO), styrene resin, polyphenylene sulfide resin (PPS). And at least one selected from the group consisting of polyetherimide resin (PEI). Among these A-2 components, polyphenylene ether resin (PPE), polycarbonate resin (PC), polyamide resin (PA), polyolefin resin (PO) and styrene resin are preferable.

The thermoplastic resin as the component A-2 will be described in detail below.

As the polyphenylene ether resin as the component A-2, those generally known as PPE resins can be used. Specific examples of such PPE include (2, 6
-Dimethyl-1,4-phenylene) ether, (2,6
-Diethyl-1,4-phenylene) ether, (2,6
-Dipropyl-1,4-phenylene) ether, (2-
Methyl-6-ethyl-1,4-phenylene) ether,
Homopolymers and / or copolymers such as (2-methyl-6-propyl-1,4-phenylene) ether and (2,3,6-trimethyl-1,4-phenylene) ether are mentioned, and particularly preferred. Is poly (2,6-dimethyl-
1,4-phenylene) ether may be mentioned. Further, it may be a copolymer in which a styrene compound is graft-polymerized to these PPE. The method for producing such PPE is not particularly limited, and for example, US Pat. No. 3,306,
It can be easily produced by oxidative polymerization of 2,6-xylenol using a cuprous salt-amine complex as a catalyst according to the method described in No. 874.

The reduced viscosity ηsp / C (0.5 g / dl, toluene solution, measured at 30 ° C.), which is a measure of the molecular weight of the PPE resin, is 0.2 to 0.7 dl / g, preferably 0.3 to It is 0.6 dl / g. PPE resin with a reduced viscosity in this range has a good balance of molding processability and mechanical properties,
It is possible to easily adjust the reduced viscosity by adjusting the amount of the catalyst during PPE production.

The polycarbonate resin (PC) as the component A-2 is a resin obtained by an interfacial polymerization reaction of various dihydroxyaryl compounds and phosgene using a solvent such as methylene chloride, or a dihydroxyaryl compound and diphenyl carbonate. Those obtained by the transesterification reaction with A typical example is a polycarbonate obtained by reacting 2,2'-bis (4-hydroxyphenyl) propane with phosgene.

Examples of the dihydroxyaryl compound used as a raw material for polycarbonate include bis (4-hydroxyphenyl) methane, 1,1'-bis (4-hydroxyphenyl) ethane and 2,2'-bis (4-hydroxyphenyl) propane. , 2,2'-bis (4-hydroxyphenyl) butane, 2,2'-bis (4-hydroxyphenyl) octane, 2,2'-bis (4-hydroxy-3-)
Methylphenyl) propane, 2,2'-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2 '
-Bis (3,5-dimethyl-4-hydroxyphenyl)
Propane, 2,2'-bis (4-hydroxy-3-cyclohexylphenyl) propane, 2,2'-bis (4-
Hydroxy-3-methoxyphenyl) propane, 1,
1'-bis (4-hydroxyphenyl) cyclopentane, 1,1'-bis (4-hydroxyphenyl) cyclohexane, 1,1'-bis (4-hydroxyphenyl)
Cyclododecane, 4,4'-dihydroxyphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyl Examples include diphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, and bis (4-hydroxyphenyl) ketone. These dihydroxyaryl compounds may be used alone or in combination of two or more.

Preferred dihydroxyaryl compounds include bisphenols which form aromatic polycarbonate having high heat resistance, bis (hydroxyphenyl) alkanes such as 2,2'-bis (4-hydroxyphenyl) propane, and bis (4-hydroxy). And bis (hydroxyphenyl) cycloalkanes such as phenyl) cyclohexane, dihydroxydiphenyl sulfide, dihydroxydiphenyl sulfone, and dihydroxydiphenyl ketone. A particularly preferred dihydroxyaryl compound is 2,2'-bis (4-hydroxyphenyl) propane which forms a bisphenol A type aromatic polycarbonate.

When the bisphenol A type aromatic polycarbonate is produced, a part of bisphenol A may be replaced with another dihydroxyaryl compound as long as the heat resistance and mechanical strength are not impaired.

The molecular weight of the polycarbonate resin does not need to be particularly limited, but if it is too low, the strength will be insufficient.
If it is too high, the melt viscosity becomes high and it becomes difficult to mold. Therefore, the viscosity average molecular weight is usually 10,000 to 50,
000, preferably 15,000 to 30,000. The viscosity average molecular weight (M) here is methylene chloride 1
The specific viscosity (η _sp ) obtained from a solution prepared by dissolving 0.7 g of polycarbonate resin in 00 ml at 20 ° C. was obtained by inserting it into the following equation. η _sp /C=[η]+0.45×[η] ² C [η] = 1.23 × 10 ^-4 M ^0.83 (where [η] is the intrinsic viscosity and C is the polymer concentration is 0.7)

The basic means for producing a polycarbonate resin will be briefly described. In the interfacial polymerization method (solution polymerization method) using phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an amine compound such as pyridine is used. As the organic solvent, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. A catalyst such as a tertiary amine or a quaternary ammonium salt can be used to accelerate the reaction, and a molecular weight modifier such as a terminal terminating agent such as phenol or an alkyl-substituted phenol such as p-tert-butylphenol can be used. It is desirable to use. Reaction temperature is usually 0-40
It is preferable to keep the reaction temperature at several degrees Celsius for several minutes to 5 hours and the pH during the reaction at 10 or higher. In addition, it is not necessary that all of the resulting molecular chain ends have a structure derived from the end terminator.

In the transesterification reaction (melt polymerization method) using a carbonic acid diester as a carbonate precursor, the dihydric phenol in a predetermined proportion is stirred with the carbonic acid diester in the presence of an inert gas while stirring to produce the alcohol or phenols produced. Is distilled out. Although the reaction temperature varies depending on the boiling point of the alcohol or phenols produced, it is usually in the range of 120 to 350 ° C. From the initial stage of the reaction, the reaction is completed while reducing the pressure to distill off the produced alcohol or phenols. At the initial stage of the reaction, a terminal stopper is added at the same time as the dihydric phenol or the like or at an intermediate stage of the reaction. Further, in order to accelerate the reaction, it is possible to use a catalyst which is currently known and which is used in a transesterification reaction. Examples of the carbonic acid diester used in this transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Of these, diphenyl carbonate is particularly preferable.

Polyamide resin (P
Examples of A) include ring-opening polymerization products of cyclic lactams, polymerization products of aminocarboxylic acids, and polycondensation products of dibasic acids and diamines. Specifically, nylon 6, nylon 66, nylon 46, Nylon 610, Nylon 61
2, aliphatic polyamides such as nylon 11, nylon 12, poly (meta-xylene adipamide), poly (hexamethylene terephthalamide), poly (nonamethylene terephthalamide), poly (hexamethylene isophthalamide), poly (tetramethylene) Examples thereof include aliphatic-aromatic polyamides such as isophthalamide), and copolymers and mixtures thereof. The polyamide that can be used in the present invention is not particularly limited.

The molecular weight of such a polyamide resin is not particularly limited, but it is preferable to use a relative viscosity of 1.7 to 4.5 measured in 98% sulfuric acid at a concentration of 1% at 25 ° C. It is possible, preferably 2.0 to 4.0, particularly preferably 2.0 to 3.5.

The polyolefin resin as the component A-2 is a homopolymer or copolymer of olefins such as ethylene, propylene and butene, or a copolymerization weight of a monomer component copolymerizable with these olefins. It is united. Specifically, polyethylene, polypropylene, ethylene-
Vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-α-olefin copolymer, ethylene-propylene copolymer, ethylene- Examples include butene copolymers. The molecular weight of these polyolefin resins is not particularly limited,
The higher the molecular weight, the better the flame retardancy.

The styrene resin as the component A-2 is
Homopolymers or copolymers of aromatic vinyl monomers such as styrene, α-methylstyrene or vinyltoluene, copolymers of these monomers with vinyl monomers such as acrylonitrile and methylmethacrylate, polybutadiene, etc. Diene rubber, ethylene / propylene rubber, acrylic rubber, etc. of styrene and / or styrene derivative,
Alternatively, it is obtained by graft-polymerizing styrene and / or a styrene derivative and another vinyl monomer. Specific examples of the styrene-based resin include, for example, polystyrene, high-impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), methylmethacrylate-butadiene-styrene. Copolymer (MBS resin), methyl methacrylate / acrylonitrile / butadiene / styrene copolymer (MABS resin), acrylonitrile / acrylic rubber / styrene copolymer (AAS resin), acrylonitrile / ethylene propylene rubber /
Examples thereof include resins such as styrene copolymer (AES resin), and mixtures thereof. From the viewpoint of impact resistance, a rubber-modified styrene-based resin is preferable, and the rubber-modified styrene-based resin means a polymer in which a rubber-like polymer is dispersed in particles in a matrix made of a vinyl aromatic polymer, Aromatic vinyl monomer in the presence of the rubbery polymer, known monomer bulk polymerization of the monomer mixture by adding vinyl monomer if necessary,
Obtained by bulk suspension polymerization, solution polymerization or emulsion polymerization.

Examples of the rubber-like polymer include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), saturated rubbers obtained by hydrogenating the above diene rubbers, isoprene rubbers,
Examples thereof include chloroprene rubber, acrylic rubber such as polybutyl acrylate, ethylene-propylene-diene monomer terpolymer (EPDM), and the like, and diene rubber is particularly preferable.

The aromatic vinyl monomer which is an essential component in the graft copolymerizable monomer mixture to be polymerized in the presence of the above rubbery polymer is, for example, styrene, α-methylstyrene, paramethylstyrene or the like. And styrene is most preferred.

Examples of vinyl monomers that can be added as required include acrylonitrile and methyl methacrylate.

The rubber-like polymer in the rubber-modified styrene resin is 1 to 50% by weight, preferably 2 to 40% by weight. The graft-polymerizable monomer mixture is 99 to 50% by weight, preferably 98 to 60% by weight.

The polyphenylene sulfide resin (PPS) as the component A-2 has a repeating unit represented by the following formula.

[0054]

[Chemical 6]

In the formula, n is an integer of 1 or more and 50 to 5
An integer of 00 is preferable, and an integer of 100 to 400 is more preferable, and it may be linear or crosslinked.

An example of the method for producing the polyphenylene sulfide resin is a method of reacting dichlorobenzene with sodium disulfide. A crosslinked product can be produced by polymerizing a low-polymerization degree polymer and then heating it in the presence of air to partially crosslink to increase the molecular weight. Can be manufactured by the method.

The polyetherimide resin (PEI) as the component A-2 has a repeating unit represented by the following formula.

[0058]

[Chemical 7]

In the formula, Ar ¹ represents an aromatic dihydroxy compound residue, and Ar ² represents an aromatic diamine residue. Examples of the aromatic dihydroxy compound include the aromatic dihydroxy compounds shown in the above description of the polycarbonate resin, and bisphenol A is particularly preferable. As aromatic diamine, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenyl, 3,4′-
Examples thereof include diaminodiphenyl, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, diaminodiphenylmethane, diaminodiphenyl sulfone and diaminodiphenyl sulfide.

In the above formula, n represents an integer of 5 to 1,000, preferably an integer of 10 to 500.

Examples of the method for producing a polyetherimide resin are US Pat. No. 3,847,867, US Pat. No. 3,847,869, US Pat. No. 3,850,885.
U.S. Pat. No. 3,852,242 and U.S. Pat. No. 3,855,178.

Of the various A-2 components described above, polyphenylene ether resin (PPE), polycarbonate resin (PC), polyamide resin (PA) or styrene resin is preferable.

In the flame-retardant resin composition of the present invention, an organic phosphorus compound (B-1 component) represented by the following general formula (1) is used as a flame retardant.

[0064]

[Chemical 8]

In the above general formula (1), R ¹ and R ⁴
Are hydrogen atoms or aliphatic hydrocarbon groups having 1 to 5 carbon atoms, which may be the same or different, and specific examples include a hydrogen atom, a methyl group, an ethyl group, a propyl (including isomers) group, A butyl (including an isomer) group can be mentioned, and a hydrogen atom, a methyl group and an ethyl group are preferable, and a hydrogen atom is particularly preferable.

R ³ and R ⁶ may be the same or different and are an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and specific examples include methyl group, ethyl group and propyl (including isomers). Group, a butyl (including isomers) group, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

R ² and R ⁵ may be the same or different and each is a phenyl group, a naphthyl group or an anthryl group which may have a substituent on its aromatic ring, and preferably a phenyl group. Such a phenyl group, naphthyl group or anthryl group may have a hydrogen atom in its aromatic ring substituted, and as the substituent, methyl, ethyl, propyl (including isomers), butyl (including isomers) or the The aromatic ring bonding group has 6 to 14 carbon atoms through an oxygen atom, a sulfur atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
The aryl group of is mentioned.

The organophosphorus compound (B-1 component) represented by the above formula (1) exhibits an extremely excellent flame retardant effect on the aromatic polyester resin. As far as the inventors of the present invention know, in the flame-retardation of aromatic polyester resins by halogen-free, it was not possible to attain the V-0 level by using a phosphorus compound alone. In order to achieve V-0 levels using phosphorus compounds, the combined use of flame retardant aids and carbonization promoters or different types of flame retardants was essential. However, according to the present invention, surprisingly, the organic phosphorus compound (B-1 component) can easily achieve flame retardancy of V-0 level of the aromatic polyester resin by itself. However, in the present invention, in addition to the B-1 component, the flame-retardant improvement resin described below, a phosphorus compound other than the B-1 component, a fluorine-containing resin, a filler or other additives,
Reduction of B-1 component usage rate, improvement of flame retardancy of molded products,
It can of course be incorporated for the purpose of improving the physical properties of the molded article, improving the chemical properties of the molded article or for other purposes. These other components will be specifically described later.

The organophosphorus compound (B-1 component) as the flame retardant in the flame-retardant resin composition of the present invention is represented by the general formula (1), and the most preferred representative compound is the following formula (1). -A) is a compound.

[0070]

[Chemical 9]

Next, a method for synthesizing the organic phosphorus compound (component B-1) in the present invention will be described. The component B-1 may be produced by a method other than the method described below.

Component B-1 is, for example, a reaction product obtained by reacting pentaerythritol with phosphorus trichloride and then oxidizing it.
It is obtained by treating with an alkali metal compound such as sodium methoxide and then reacting with an aralkyl halide.

Further, it is obtained by a method of reacting pentaerythritol with aralkylphosphonic acid dichloride, or a method of reacting a compound obtained by reacting pentaerythritol with phosphorus trichloride with aralkyl alcohol and then performing Arbuzov rearrangement at high temperature. You can also The latter reaction is described, for example, in US Pat.
No. 032 specification, JP-A-54-157156, and JP-A-53-39698.

A specific method for synthesizing the B-1 component will be described below. However, this synthesizing method is merely for the purpose of explanation, and the B-1 component used in the present invention is not limited to these synthesizing methods. It may be synthesized by modification and other synthetic methods. A more specific synthesis method will be described in the preparation example described later. (I) The organophosphorus compound of (1-a) in the component B-1; pentaerythritol is reacted with phosphorus trichloride, and then the reaction product obtained by oxidizing with tertiary butanol is treated with sodium methoxide to give 1 It can be obtained by reacting -bromoethylbenzene.

The acid value of the above-mentioned component B-1 is preferably 0.7 mgKOH / g or less, more preferably 0.5.
Those having a mgKOH / g or less are used. By using the component B-1 having an acid value in this range, a molded product excellent in flame retardancy and hue can be obtained, and a molded product having good thermal stability in which decomposition of the polyester resin hardly occurs.
Most preferably, the component B-1 has an acid value of 0.4 mgKOH / g or less. Here, the acid value means the sample (B-
1 component) means the amount (mg) of KOH necessary to neutralize the acid component in 1 g.

Further, as the component B-1, those having an HPLC purity of preferably at least 90%, more preferably at least 95% are used. Such high-purity ones are preferable because they are excellent in flame retardancy and hue of molded products. Where B
The HPLC purity of the -1 component can be effectively measured by using the following method.

The column is Develos manufactured by Nomura Chemical Co., Ltd.
il ODS-7 300 mm × 4 mmφ was used, and the column temperature was 40 ° C. A mixed solution of acetonitrile and water 6: 4 (volume ratio) was used as a solvent, and 5 μl thereof was injected. UV-260nm was used for the detector.

The method for removing impurities in the component B-1 is not particularly limited, but a method of repulp washing with a solvent such as water or methanol (washing with a solvent and repeating filtration several times) is used. Most effective and cost effective.

The component B-1 is the resin component (component A) 1
1 to 100 parts by weight, preferably 5 to 100 parts by weight
The amount is 90 parts by weight, more preferably 10 to 70 parts by weight. Particularly, the range of 15 to 50 parts by weight is preferable.
The suitable range of the blending ratio of the B-1 component is determined by the desired flame retardancy level, the type of the resin component (A component), the type of the filler, and the blending amount thereof. Furthermore, the blending amount of the B-1 component can be changed by using a flame retardant improving resin, another flame retardant or a fluorine-containing resin, and in many cases, the blending ratio of the B-1 component is reduced by using these. be able to.

Next, the flame-retardant improving resin (component C) that can be added to the flame-retardant resin composition of the present invention will be described. The flame retardancy can be improved by blending the C component. Phenolic resin (C-i component), epoxy resin (C-ii component) or styrene resin (C-iii) component is suitable as the flame retardant improving resin. Hereinafter, these C-i component to C-iii component will be specifically described.

The phenol resin used as the C-i component may be any polymer as long as it is a polymer having a plurality of phenolic hydroxyl groups, and examples thereof include novolac type, resol type and heat reaction type resins, or resins modified with these. Is mentioned. These may be an uncured resin without a curing agent added, a semi-cured resin, or a cured resin. Above all, a phenol novolac resin, which does not contain a curing agent and is non-reactive, is preferable in terms of flame retardancy, impact resistance, and economy. The shape is not particularly limited, and any of crushed products, granules, flakes, powders, needles and liquids can be used. The above phenolic resins can be used alone or as a mixture of two or more, if necessary.

The phenol resin is not particularly limited, and those generally commercially available can be used. For example, in the case of novolac type phenolic resin, the molar ratio of phenols to aldehydes is 1: 0.7 to 1:
Charge the reaction tank to 0.9, and then add oxalic acid,
After adding a catalyst such as hydrochloric acid, sulfuric acid or toluenesulfonic acid, heating and reflux reaction are performed. It can be obtained by vacuum dehydration or static dehydration in order to remove the produced water, and further removing remaining water and unreacted phenols. A co-condensed phenol resin can be obtained by using a plurality of raw material components, and these resins can be used in the same manner.

In the case of a resol type phenol resin,
The molar ratio of phenols and aldehydes is 1: 1 to 1: 2
It can be obtained by carrying out the same operation as in the novolac type phenol resin after charging the reaction tank so that the reaction mixture becomes, and adding a catalyst such as sodium hydroxide, aqueous ammonia and other basic substances.

Here, phenol means phenol, o
-Cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, isoeugenol, o-
Methoxyphenol, 4,4'-dihydroxyphenylpropane, isoamyl salicylate, benzyl salicylate, methyl salicylate, 2,6-di-tert-butyl-p-cresol and the like can be mentioned. These phenols may be used alone or as a mixture of two or more, if necessary. On the other hand, the aldehydes include formaldehyde, paraformaldehyde, polyoxymethylene, trioxane and the like. These aldehydes can also be used alone or as a mixture of two or more kinds, if necessary.

The molecular weight of the phenol resin is also not particularly limited, but preferably the number average molecular weight is 2
00-2,000, more preferably 400-1,50
Those in the range of 0 are preferable because they are excellent in mechanical properties, moldability and economy.

The epoxy resin used as the C-ii component is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac. Type epoxy resin, naphthalene type epoxy resin, biphenol type epoxy resin and the like, but not limited to these. These epoxy resins are not limited to one kind in use, and two or more kinds of epoxy resins may be used together or various kinds of modified epoxy resins may be used.

The styrene resin used with the C-iii component as the flame retardant improving resin is a homopolymer of an aromatic vinyl monomer such as styrene, α-methylstyrene or vinyltoluene or a copolymer thereof. In addition to the combination, a copolymer of these monomers and a vinyl monomer may be mentioned.
The styrene-based resin as the C-iii component has a content of the aromatic vinyl monomer component of 50% by weight or more, preferably 60% by weight or more, and particularly preferably 70% by weight or more.

Examples of the styrene resin as the C-iii component include polystyrene, high-impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin). , Methyl methacrylate / butadiene / styrene copolymer (MBS resin), methyl methacrylate / acrylonitrile / butadiene / styrene copolymer (MABS resin), acrylonitrile / acrylic rubber / styrene copolymer (AAS resin), acrylonitrile / ethylene propylene Examples thereof include resins such as rubber / styrene copolymer (AES resin), and mixtures thereof.

When the flame-retardant improving resin (component C) is blended, the ratio is 0.0 based on 100 parts by weight of component A.
The amount is 1 to 45 parts by weight, preferably 0.1 to 40 parts by weight, and particularly preferably 0.5 to 35 parts by weight. C component is C-ii
In the case of the i component, the mixing ratio is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the A component.
Even with a small amount of parts by weight, flame retardancy is significantly improved.

A filler (component D) can be added to the flame-retardant resin composition of the present invention. The filler may be an inorganic or organic filler as long as it is added for the purpose of improving the physical properties of the molded article, especially the mechanical properties. A fibrous filler is preferable.

Examples of the filler (D component) include glass chopped fibers, glass milled fibers, glass roving strands, glass flakes, glass beads, glass powder, and other glass-based fillers; carbon fibers, carbon milled fibers, carbon roving strands. , Carbon-based fillers such as carbon flakes; talc, mica, wollastonite, kaolin, montmorillonite, bentonite, sepiolite, xonotlite,
Examples include inorganic fillers such as clay and silica; organic fillers such as aramid fiber; inorganic pigments such as titanium oxide; and carbon black, which can be selected from these or a combination thereof. For the purpose of reinforcing the resin composition, it is preferable to add a fibrous filler, and it is preferable to add glass fiber, carbon fiber, or a mixture thereof.

For these inorganic fillers, a sizing agent or a surface treatment agent can be used if necessary. The type of the sizing agent or the surface treatment agent is not particularly limited, but generally a functional compound such as an epoxy compound, a silane compound, a titanate compound or the like can be mentioned, and it is preferable to select one suitable for the resin. An epoxy compound is preferable, and a bisphenol A type and / or novolac type epoxy resin is more preferable.

When the filler (D component) is blended, the proportion thereof is 1 to 200 parts by weight, preferably 1 to 150 parts by weight, relative to 100 parts by weight of the resin component (A component).
It is more preferably 1 to 100 parts by weight. If the amount is more than 200 parts by weight, the flame retardancy and physical properties of the resin composition may be deteriorated, and the operability and moldability may be difficult.

The flame-retardant resin composition of the present invention may contain a fluorine-containing resin (component E). The blending of the E component improves the flame retardancy of the molded product. In particular, dripping is suppressed in the combustion test of the molded product.

The fluorine-containing resin used as the E component is not particularly limited as long as it has a fibril-forming ability, and examples thereof include tetrafluoroethylene, trifluoroethylene, vinyl fluoride, vinylidene fluoride and hexa. Examples thereof include homopolymers or copolymers of fluorine-containing monomers such as fluoropropylene.
Particularly, polytetrafluoroethylene having fibril forming ability is preferable. Polytetrafluoroethylene having fibril-forming ability is a powder obtained by coagulating and drying latex obtained by emulsion polymerization of tetrafluoroethylene (so-called polytetrafluoroethylene fine powder, which is classified as type 3 in ASTM standard). Stuff). Alternatively, an aqueous dispersion (so-called polytetrafluoroethylene dispersion) produced by adding a surfactant to the latex and concentrating and stabilizing the latex may be used.

The molecular weight of the polytetrafluoroethylene having fibril-forming ability is 1,000,000 to 10,000,000, more preferably 2,000,000 to 9,000,000 in terms of number average molecular weight determined from standard specific gravity.

Further, the polytetrafluoroethylene having the fibril forming ability has a primary particle diameter of 0.05 to
The thickness is preferably in the range of 1.0 μm, more preferably 0.1 to 0.5 μm. When using fine powder, a secondary particle size of 1 to 1,000 μm can be used, and more preferably 10 to 500 μm.
Can be used.

Such polytetrafluoroethylene is UL
Polytetrafluoroethylene, which has the ability to prevent melting and dripping during the burning test of the test piece in the standard vertical burning test, and is specifically a polytetrafluoroethylene having such fibril forming ability is, for example, manufactured by Mitsui DuPont Fluorochemical Co., Ltd. Examples include Teflon 6J and Teflon 30J, Polyflon MPA FA-500 manufactured by Daikin Chemical Co., Ltd., Polyflon F-201L and Polyflon D-1, and CD076 manufactured by Asahi IC Fluoropolymers Co., Ltd.

The polytetrafluoroethylene is preferably a fine powder which has been subjected to various treatments in order to prevent secondary agglomeration. Examples of such treatment include firing the surface of polytetrafluoroethylene. Examples of such treatment include coating the surface of polytetrafluoroethylene having a fibril forming ability with polytetrafluoroethylene having a non-fibril forming ability. More preferred in the present invention is polytetrafluoroethylene which has been subjected to the latter treatment. This is because in the former case, the desired fibril forming ability is likely to decrease. In such a case, it is preferable that the polytetrafluoroethylene having fibril forming ability is in the range of 70 to 95% by weight based on the total amount.
The fibril non-forming ability polytetrafluoroethylene has a number average molecular weight of 10,000 to 1,000,000, more preferably 10,000 to 80, in terms of the number average molecular weight determined from standard specific gravity.
In many cases.

Such polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) may be in the form of an aqueous dispersion, in addition to the solid form as described above.

Such polytetrafluoroethylene can be used in an ordinary solid form, an aqueous emulsion, and a dispersion form. However, since the dispersant component is liable to have a bad influence on the wet heat resistance, the polytetrafluoroethylene in the solid form is particularly preferable. What can be used preferably.

In order to improve the dispersibility in the resin and to obtain better appearance and mechanical properties, the polytetrafluoroethylene having the fibril forming ability is
An agglomerated mixture of an emulsion of polytetrafluoroethylene and an emulsion of vinyl polymer can also be mentioned as a preferable form.

Here, as the vinyl polymer, polypropylene, polyethylene, polystyrene, HIPS, AS
Resin, ABS resin, MBS resin, MABS resin, AAS
Resin, polymethyl (meth) acrylate, block copolymer composed of styrene and butadiene and hydrogenated copolymer thereof, block copolymer composed of styrene and isoprene, and hydrogenated copolymer thereof, acrylonitrile-butadiene copolymer, Ethylene-propylene random copolymers and block copolymers, ethylene-butene random copolymers and block copolymers, ethylene-α-olefin copolymers, ethylene-unsaturated carboxylic acids such as ethylene-butyl acrylate Copolymers with esters, acrylate-butadiene copolymers such as butyl acrylate-butadiene, rubbery polymers such as polyalkyl (meth) acrylates, composite rubbers containing polyorganosiloxane and polyalkyl (meth) acrylates, Or even That the composite rubber styrene, acrylonitrile, a vinyl monomer of polyalkyl methacrylate and the like and a copolymer obtained by grafting.

To prepare such an agglomerated mixture, an average particle size of 0.01 to 1 μm, especially 0.05 to 0.5 μm.
An aqueous emulsion of the above vinyl polymer having an average particle diameter of 0.05 to 10 μm, particularly 0.05 to 1.0 μm.
Mix with an aqueous emulsion of polytetrafluoroethylene having m. Such an emulsion of polytetrafluoroethylene can be obtained by polymerizing polytetrafluoroethylene by emulsion polymerization using a fluorine-containing surfactant. During the emulsion polymerization, it is also possible to copolymerize another copolymer component such as hexafluoropropylene in an amount of 10% by weight or less based on the whole polytetrafluoroethylene.

In order to obtain such an agglomerated mixture, a suitable polytetrafluoroethylene emulsion usually has a solid content of 40 to 70% by weight, particularly 50 to 65% by weight, and a vinyl polymer emulsion. Is used which has a solids content of 25 to 60% by weight, in particular 30 to 45% by weight. Further, the proportion of polytetrafluoroethylene in the agglomerated mixture is 1 to 80% by weight, particularly 1 to 100% by weight in total 100% by weight with the vinyl polymer used in the agglomerated mixture.
It is preferably 60% by weight. After mixing the above emulsion, stir and mix, put into hot water in which metal salts such as calcium chloride and magnesium sulfate are dissolved, salting out,
A production method of separating and collecting by solidifying can be preferably mentioned. In addition, a method of collecting the agitated mixed emulsion by a method such as spray drying or freeze drying can be used.

Further, various forms of the aggregate mixture of the polytetrafluoroethylene emulsion capable of forming fibrils and the vinyl polymer emulsion can be used. For example, a vinyl-based emulsion around polytetrafluoroethylene particles can be used. Examples thereof include a form in which a polymer is surrounded, a form in which polytetrafluoroethylene is surrounded around a vinyl polymer, and a form in which several particles are aggregated with respect to one particle.

Further, it is also possible to use one in which the same or another kind of vinyl polymer is graft-polymerized to the outer layer of the coagulated mixture. As such a vinyl-based monomer,
Styrene, α-methylstyrene, methyl methacrylate,
Cyclohexyl acrylate, dodecyl methacrylate, dodecyl acrylate, acrylonitrile, acrylic acid-2
Preference is given to ethylhexyl, which can be used alone or copolymerized.

Commercially available products of the agglomerated mixture of the polytetrafluoroethylene emulsion capable of forming fibrils and the vinyl polymer emulsion are commercially available from Mitsubishi Rayon Co., Ltd. as Metabrene “A3000” and G.
"BLENDEX from E Specialty Chemicals
"449" can be mentioned as a typical example.

When the E component is blended, the proportion thereof is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the A component. 0.01
If it is more than parts by weight, sufficient melt dripping prevention performance is easily obtained,
When the amount is 10 parts by weight or less, poor appearance and poor dispersion are less likely to occur, and it is economically advantageous, which is preferable.

Next, some of the embodiments of the flame-retardant resin composition of the present invention will be described.

One embodiment is the following (A)-
It is a flame-retardant resin composition comprising the component (E), and the composition according to this embodiment contains a fluorine-containing resin as the component E, and has an excellent anti-dripping effect in a combustion test of a molded article. (A) at least 60% by weight of aromatic polyester resin
100 parts by weight of resin component (A component) contained, (B) organophosphorus compound represented by the general formula (1) (B-1 component)
1 to 100 parts by weight, (C) flame-retardant improving resin (C component) 0
˜50 parts by weight, (D) filler (D component) 0 to 200 parts by weight, and (E) fluorine-containing resin (E component) 0.01 to
A flame-retardant resin composition consisting of 10 parts by weight.

Another embodiment is composed of the following (A) to (E) and has a thermal stability (MVR change rate) of 20% or less, preferably 15% or less, more preferably 10% or less, and particularly preferably. It is a flame-retardant resin composition of 5% or less, and the composition according to this embodiment is excellent in the purity (particularly acid value or HPLC purity) of the component B-1 due to the thermal stability of the molded article ( In particular, it has excellent mechanical strength (stability by heat). Here, the measurement of thermal stability is examined according to the method described later. (A) at least 60% by weight of aromatic polyester resin
100 parts by weight of resin component (A component) contained, (B) organophosphorus compound represented by the general formula (1) (B-1 component)
1 to 100 parts by weight, (C) flame-retardant improving resin (C component) 0
A flame-retardant resin composition comprising ˜50 parts by weight, (D) filler (D component) 0 to 200 parts by weight, and (E) fluorine-containing resin (E component) 0 to 10 parts by weight.

Yet another embodiment is the following (A),
A flame-retardant resin composition comprising the components (B), (C) and (E) and having a total light transmittance of 80% or more, preferably 83% or more, more preferably 85% or more. . The composition according to this aspect gives a molded article of good transparency which is substantially free of filler. Since the organophosphorus compound of the B-1 component is a non-colored powder and has excellent compatibility with the resin of the A component, the molded article of this composition has excellent transparency, and when a pigment or dye is added, A transparent molded product having a bright color is obtained. (A) at least 60% by weight of aromatic polyester resin
100 parts by weight of resin component (A component) contained, (B) organophosphorus compound represented by the general formula (1) (B-1 component)
1 to 100 parts by weight, (C) flame-retardant improving resin (C component) 0
To 50 parts by weight and (E) fluorine-containing resin (E component) 0
A flame-retardant resin composition consisting of 10 parts by weight.

The above-mentioned flame-retardant resin composition of the present invention is a composition containing substantially no halogen, and it is natural that the flame retardancy is not lower than V-2 level, but in most embodiments, it is difficult to reach V-0 level. Flammability is achieved. Specifically, the resin composition of the present invention can achieve a flame retardancy level V-0 of UL-94 standard in a molded product having a thickness of 1.6 mm, and, under suitable conditions, has a thickness of 0.8 mm. V-0 can be achieved also in a molded product.

In the flame-retardant resin composition of the present invention, the A component, B component, C component, D component and E component which compose these compositions have already been described, but other components than these are also necessary. Accordingly, other components can be used as long as they do not impair the object of the present invention. Other components that can be added will be described below.

(1) Phosphorus or phosphorus compound (F component);
In the flame-retardant resin composition of the present invention, phosphorus or a phosphorus compound (F component) known per se as a flame retardant can be used in addition to the organic phosphorus compound (B component). B
By using the F component together with the component, the flame retardant effect, the physical strength or the heat resistance can be improved, and the cost can be further reduced.

As the F component, the following (F-1) to (F-
5) can be illustrated. (F-1); Red phosphorus (F-2); Triaryl phosphate represented by the following general formula (F-2)

[0118]

[Chemical 10]

(F-3); a condensed phosphoric acid ester represented by the following general formula (F-3)

[0120]

[Chemical 11]

(F-4); a condensed phosphoric acid ester represented by the following general formula (F-4)

[0122]

[Chemical 12]

(F-5); an organophosphorus compound represented by the following general formula (F-5)

[0124]

[Chemical 13]

Q ^{1 to} Q ^{4 in the} formulas (F-2) to (F-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 this 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. As the substituents,
(I) 1 to 1 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, neopentyl group and nonyl group.
An alkyl group having 12 carbon atoms, preferably an alkyl group having 1 to 9 carbon atoms, (ii) a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentoxy group, and an alkyloxy group having 1 to 12 carbon atoms, preferably 1 carbon atom ~ 9 alkyloxy group, (iii) methylthio group, ethylthio group, propylthio group, butylthio group and pentylthio group, such as alkylthio group having 1 to 12 carbon atoms, preferably 1 to 12 carbon atoms.
9 an alkylthio group and (iv) a group represented by Ar ⁶ —W ¹ — formula (wherein W ¹ is —O—, —S— or a carbon number of 1 to 1).
8, preferably an alkylene group having 1 to 4 carbon atoms, A
r ⁶ represents an aryl group having 6 to 15 carbon atoms, preferably 6 to 10 carbon atoms).

In formulas (F-3) and (F-4),
Ar ⁴ and Ar ⁵ may be the same or different when both are present (in the case of F-4), and have 6 to 1 carbon atoms.
5 shows an arylene group, preferably an arylene group having 6 to 10 carbon atoms. Specific examples include a phenylene group or a naphthylene group. This arylene group has 1 to 4
It may have one, preferably 1 to 2 substituents.
Examples of the 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 tert-butyl group, and (ii) benzyl. group, phenethyl group, phenylpropyl group, such as an aralkyl group having 7 to 20 carbon atoms in naphthylmethyl and ^{cumyl, (iii) Q 5 -W 2} - group (where W ² represented by the formula -O- or It indicates -S-, Q ⁵ is 1 to 4 carbon atoms, preferably an alkyl group or 6 to 15 carbon atoms having 1 to 3 carbon atoms, preferably an aryl group having 6 to 10) and (iv) a phenyl group Such aryl groups having 6 to 15 carbon atoms can be mentioned.

In formulas (F-3) and (F-4),
m represents an integer of 1 to 5, preferably 1 to 3 and particularly preferably 1.

In the formula (F-4), Z is Ar ⁴ and A
a single bond or a group which binds r ⁵ , and is —Ar ⁴ —Z—
Ar ⁵ − is a residue usually derived from bisphenol. Thus Z is a single bond, -O-, -CO-, -S-,
—SO ₂ — or an alkylene group having 1 to 3 carbon atoms,
Preferred is a single bond, -O-, or isopropylidene.

Even phosphorus compounds other than the phosphorus compounds (F-1) to (F-5) or phosphorus compounds can be used together with the component B.

When the phosphorus or phosphorus compound (F component) of the above (F-1) to (F-5) is added to the resin composition,
The ratio is preferably 1 to 100 parts by weight, more preferably 5 parts by weight, per 100 parts by weight of the organic phosphorus compound (component B).
A range of -80 parts by weight, particularly preferably 10-60 parts by weight is suitable. Among the phosphorus or phosphorus compounds of the above (F-1) to (F-5), preferably (F-2) to (F-
It is the phosphorus compound of 5).

(2) Biscumyl compound: The flame-retardant resin composition of the present invention may further contain a biscumyl compound represented by the following formula.

[0132]

[Chemical 14]

When the biscumyl compound is added to the resin composition, the proportion thereof is preferably in the range of 0.01 to 3 parts by weight per 100 parts by weight of the resin component (A component),
The range of 02 to 2 parts by weight is more preferable, and the range of 0.03 to 1 part by weight is particularly preferable.

(3) Flame retardant aid: The flame retardant resin composition of the present invention may further contain known flame retardant aids. Examples of the flame retardant aid include silicone oil. The silicone oil has a polydiorganosiloxane skeleton, preferably polydiphenylsiloxane, polymethylphenylsiloxane,
Polydimethylsiloxane, or any copolymer or mixture thereof, of which polydimethylsiloxane is preferably used. Its viscosity is preferably 0.
8 to 5,000 centipoise (25 ° C), more preferably 10 to 1,000 centipoise (25 ° C), further preferably 50 to 500 centipoise (25 ° C),
Those having such a viscosity range are preferable because they have excellent flame retardancy. The amount of such silicone oil blended is 1 resin component (A component).
The range of 0.5 to 10 parts by weight is preferable with respect to 00 parts by weight.

(4) Compatibilizer: A compatibilizer may be added to the flame-retardant resin composition of the present invention, if necessary. The type of the compatibilizer is not particularly limited, and when the A-1 component and the A-2 component in the A component, or the A component and the C component are used as a mixture of two or more types,
It is preferable that the polymers can be compatibilized with each other, the resin component of the component A and / or the component C, and other additives. By adding a compatibilizer, it is possible not only to improve the mechanical properties and the like of the flame-retardant resin composition of the present invention, but also to improve the flame retardancy. The amount of the compatibilizer added is not particularly limited, and the compatibilizer may be added within a range not impairing the object of the present invention.

(5) Additives: The flame-retardant resin composition of the present invention contains various additives such as antioxidants, ultraviolet absorbers, deterioration inhibitors such as light stabilizers, lubricants and antistatic agents. ,
A release agent, a plasticizer, a coloring agent (pigment), etc. may be added. The amount of the additive used can be appropriately selected according to the type and purpose of the additive as long as flame retardancy, heat resistance, impact resistance and mechanical strength are not impaired.

The flame-retardant resin composition of the present invention is prepared by adding the resin component (A component), the organic phosphorus compound (B component) and, if necessary, other components to a V-type blender, super mixer, super floater, Henschel. A method in which preliminary mixing is performed using a mixer such as a mixer, and the preliminary mixture is supplied to a kneader and melt-mixed is preferably used. As the kneader, various melt mixers such as a kneader, a single-screw or twin-screw extruder can be used, and the resin composition is 220 to 280 ° C., preferably 230 to 270 ° C., using the twin screw extruder. The method of melting at the temperature of 1, injecting a liquid component with a side feeder, extruding, and pelletizing with a pelletizer is preferably used.

The flame-retardant resin composition of the present invention contains substantially no halogen and has very high flame-retardant performance, and is used for home electric appliance parts, electric / electronic parts, automobile parts, machine / mechanical parts, It is useful as a material for molding various molded products such as cosmetic containers. Specifically, breaker parts, switch parts, motor parts, ignition coil cases, power plugs, power outlets, coil bobbins, connectors, relay cases, fuse cases, flyback transformer parts, focus block parts, distributor caps, harness connectors, etc. Can be suitably used. Furthermore, housings, casings, or chassis, which are becoming thinner, are housings of electronic and electric products (for example, home appliances such as telephones, personal computers, printers, fax machines, copiers, VCRs, audio equipments, OA equipments or parts thereof). , Useful for casing or chassis. Printer housings, fixing unit parts, which require particularly excellent heat resistance and flame retardancy,
It is also useful as a machine / mechanical component for home appliances and office automation products such as fax machines.

As the molding method, injection molding, blow molding,
Although not particularly limited, such as press molding, it is preferably manufactured by injection molding a pelletized resin composition using an injection molding machine.

[0140]

The present invention will be described below with reference to examples.
The invention is not limited to these examples. The evaluation was performed by the following method. (1) Flame retardancy (UL-94 evaluation) Flame retardance is 1/16 inch (1.6 mm) and 1 / thickness.
Using a 32 inch (0.8 mm) test piece, the evaluation was performed according to the vertical combustion test defined in UL-94 of the UL standard of the United States as a flame retardancy evaluation scale. The burning of all test pieces extinguished within 10 seconds after removing the flame,
In addition, V-0 is the one in which the drop does not cause cotton ignition, V-2 is the one in which the combustion extinguishes within 30 seconds and the drop causes cotton ignition, and those below this evaluation standard are not.
It was set to V. (2) Flame retardancy (OI test) It was performed according to JIS-K-7201. The higher the value, the better the flame retardancy. (3) Acid value The measurement was carried out according to JIS-K-3504. (4) MVR (fluidity test) The measurement was performed according to ISO-1133. (5) Thermal stability (rate of change in MVR) The pellet was treated at 130 ° C for 24 hours. The MVR of the pellets before and after the treatment was measured under the conditions of 230 ° C. and a load of 3.8 kg, and the rate of change (ΔY) was calculated by the following formula. _{ΔY = (| Y 2 -Y 1} | / Y 1) × 100 (%) Y 1; pretreatment ^{MVR (cm 3 / 10min) Y} 2; after treatment MVR (cm ³ / 10min)

Next, a preparation example of the organophosphorus compound used in the examples is shown.

Preparation Example 1 of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-diα-methylbenzyl-3,9-dioxide (FR-1) 6.81 parts of pentaerythritol and 0.16 of pyridine were placed in a reaction vessel equipped with a preparation thermometer, a condenser and a dropping funnel.
Parts and 8.65 parts of toluene were charged and stirred. 13.76 parts of phosphorus trichloride was added to the reaction vessel using the dropping funnel, and after the addition was completed, the mixture was heated and stirred at 60 ° C. After the reaction, the mixture was cooled to room temperature, and the obtained reaction product was diluted with methylene chloride.
6.50 parts was added, and 7.42 parts of tertiary butanol and 1.25 parts of methylene chloride were added dropwise while cooling with ice. The obtained crystals were washed with toluene and methylene chloride and filtered. The obtained filtered material is 80 ° C., 1.33 × 1
It was dried at 0 ² Pa for 12 hours to obtain 10.76 parts of a white solid. The obtained solid was found to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-dihydro-3,9-dioxide by ³¹ PNMR and ¹ HNMR spectra. confirmed.

2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane obtained in a reaction vessel equipped with a thermometer, a condenser and a dropping funnel,
7.31 parts of 3,9-dihydro-3,9-dioxide,
47.22 parts of DMF was charged and stirred. 3.53 parts of sodium methoxide was added to the reaction vessel under ice cooling. After stirring with ice cooling for 2 hours, the mixture was stirred at room temperature for 5 hours. After further distilling off DMF, 18.89 parts of DMF was added, and 11.84 parts of (1-bromoethyl) benzene was added dropwise to the reaction mixture with ice cooling. After stirring under ice cooling for 3 hours, DMF was distilled off, washed with water and methanol and filtered. The obtained filtered material is 120 ° C., 1.33 × 10
^{It was} dried at ² Pa for 19 hours to obtain 8.5 parts of a white solid.
The obtained solid was found to be 2,4,8,10-tetraoxa- by ³¹ PNMR, ¹ HNMR spectrum and elemental analysis.
3,9-diphosphaspiro [5,5] undecane, 3,9
It was confirmed to be 9-diα-methylbenzyl-3,9-dioxide. ^{The 31} PNMR purity was 99%. The HPLC purity measured by the method described in the text was 99%. The acid value was 0.03 mgKOH / g.

¹ H-NMR (CDCl ₃ , 300 MH
z): δ7.2-7.4 (m, 10H), 4.0-4.
2 (m, 4H), 3.4-3.8 (m, 4H), 3.3
(Qd, 4H), 1.6 (ddd, 6H), ³¹ P-NM
R (CDCl ₃ , 120 MHz): δ28.7 (S),
Melting point: 190-210 ° C, elemental analysis calculated value: C, 5
7.80; H, 6.01, measured value: C, 57.83;
H, 5.96 The following components were used as the components used in Examples and Comparative Examples.

(I) Polyester resin (A-1 component) Polybutylene terephthalate (TRB-produced by Teijin Ltd.)
H) was used (hereinafter referred to as PBT-1). 230 ° C,
The MVR value measured with a load of 3.8 kg was 9.5 cm ³ /
It was 10 minutes. Polybutylene terephthalate (TRB-made by Teijin Ltd.)
J) was used (hereinafter referred to as PBT-2). 230 ° C,
The MVR value measured with a load of 3.8 kg is 12.5 cm ^3.
It was / 10 min. Polyethylene terephthalate (TR-8 manufactured by Teijin Ltd.)
580H) was used (hereinafter referred to as PET-1). 28
The MVR value measured at 0 ° C. and a load of 1.2 kg is 42.4.
was cm ³ / 10min. Polyethylene terephthalate (TR-8 manufactured by Teijin Ltd.)
550T) was used (hereinafter referred to as PET-2). 28
The MVR value measured at 0 ° C and a load of 1.2 kg is 51.5.
was cm ³ / 10min.

(II) Thermoplastic Resin (Component A-2) Polyphenylene ether (Zylon P-402 manufactured by Asahi Chemical Industry Co., Ltd.) was used (hereinafter referred to as PPE). Polycarbonate (Panlite L- manufactured by Teijin Chemicals Ltd.)
1225WP) was used (hereinafter referred to as PC). Nylon 6 (NF-8020 manufactured by Teijin Ltd.) was used (hereinafter referred to as PA).

(III) Organic Phosphorus Compound (Component B-1) 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane synthesized in Preparation Example 1,
3,9-diα-methylbenzyl-3,9-dioxide {in the general formula (1), R ¹ and R ⁴ are hydrogen atoms, R ³ and R ⁶ are methyl groups, and R ² and R ⁵ are phenyl. Group phosphorus compound (hereinafter referred to as FR-1)}

(IV) Other organic phosphorus compounds triphenyl phosphate {T manufactured by Daihachi Chemical Industry Co., Ltd.
PP (hereinafter referred to as TPP)} 1,3-phenylenebis [di (2,6-dimethylphenyl) phosphate] {Ar in the general formula (F-3)
⁴ is a phenylene group, Q ¹ , Q ² , Q ³ and Q ⁴ are 2,6-
An organic phosphate compound that is a dimethylphenyl group,
ADEKA STAB FP-500 (hereinafter F
P-500)}

(V) Flame Retardant Improvement Resin (Component C) Polystyrene GPPS (styrene polymer manufactured by Wako Pure Chemical Industries, Ltd.) was used (hereinafter referred to as C-1). Acrylonitrile-styrene copolymer (Styrac-AS783 manufactured by Asahi Kasei Co., Ltd.) was used (hereinafter C
-2). Phenolic resin (PR-5 manufactured by Sumitomo Bakelite Co., Ltd.)
3195) was used (hereinafter referred to as C-3). An epoxy resin (Epicoat 828 manufactured by Japan Epoxy Resin Co., Ltd.) was used (hereinafter referred to as C-4).

(VI) Filler (Component D) Glass milled fiber (PFE- manufactured by Nitto Boseki Co., Ltd.)
301S) was used (hereinafter referred to as D-1). A glass chopped fiber (ECS03T-187H manufactured by Nippon Electric Glass Co., Ltd.) was used (hereinafter referred to as D-2).

(VII) Fluorine-Containing Resin (Component E) Polytetrafluoroethylene (Polyflon MPAFA-500 manufactured by Daikin Chemical Industries, Ltd.) was used (hereinafter referred to as E-1). AS-coated polytetrafluoroethylene (BLENDEX 449 manufactured by GE Specialty Chemicals) was used (hereinafter referred to as E-2). In addition, BLENDEX449
Regarding, the PTFE content was 50%, the acrylonitrile component content was 10%, and the styrene component content was 40%.

[Examples 1-26 and Comparative Examples 1-72]
The components shown in Tables 1 to 10 were mixed in a tumbler in the amounts (parts by weight) shown in Tables 1 to 10 and pelletized with a 15 mmφ twin-screw extruder (KZW15 manufactured by Technobel). The composition containing glass chopped fiber was pelletized with a 30 mmφ single screw extruder. The obtained pellets were dried with a hot air dryer at 130 ° C. for 4 hours. The dried pellets were molded by an injection molding machine (J75Si manufactured by Japan Steel Works, Ltd.). The results of evaluation using the molded plate are shown in Tables 1 to 10.

[0153]

[Table 1]

[0154]

[Table 2]

[0155]

[Table 3]

[0156]

[Table 4]

[0157]

[Table 5]

[0158]

[Table 6]

[0159]

[Table 7]

[0160]

[Table 8]

[0161]

[Table 9]

[0162]

[Table 10]

In Table 1, for the compositions of Examples 1 to 5, the cylinder temperature is 270 ° C. for Examples 1 to 3,
Molding was performed at a mold temperature of 0 ° C., a cylinder temperature of 250 ° C. and a mold temperature of 30 ° C. for Examples 4 and 5, and 0.8 mm.
A thick transparent test piece was obtained. When the total light transmittance was measured, Example 1: 84%, Example 2:83
%, Example 3: 84%, Example 4: 90%, Example 5:
It was 92%.

Further, the pellets of Example 1 were treated at 230 ° C.
MVR measured at 3.8kg load 27.5cm ^3/1
It is 0 min, which shows that the fluidity is good and the practicality is high. Furthermore, the pellets of Example 1 were heated at 130 ° C. for 2 hours.
As a result of measuring the MVR of the sample after the treatment for 4 hours,
26.8cm ³ / 10min, and the shows that resin decomposition does not occur. The ΔY of the pellet of Example 1 was 2.5%.

[0165]

EFFECTS OF THE INVENTION The flame-retardant resin composition of the present invention and the molded article formed from the same have the following advantages over conventional flame-retardant polyester resin compositions. (I) A polyester resin composition having a high degree of flame retardancy can be obtained substantially without using a halogen-containing flame retardant. (Ii) Since the organic phosphorus compound as the flame retardant has an excellent flame retarding effect on the polyester resin, the V-2 level can be achieved even with a relatively small amount used. Further, a composition having a flame retardant effect of V-0 level can be easily obtained. That is, it is not necessary to add many components to achieve the V-0 level, and a V-0 level composition can be obtained with a relatively simple composition. (Iii) By combining an organic phosphorus compound as a flame retardant with a specific flame-retardant improving resin, a V-0 level polyester composition can be easily obtained by blending a relatively small amount of the organic phosphorus compound. (Iv) Due to the structure and characteristics of the organic phosphorus compound used as a flame retardant, a resin excellent in thermal stability that hardly causes thermal deterioration of the polyester resin during molding of the polyester resin or during use of the molded product. A composition is obtained. Therefore, a composition excellent in flame retardancy, mechanical strength and thermal stability in a well-balanced manner can be obtained. (V) Since the organic phosphorus compound as the flame retardant is colorless and compatible with the polyester resin, a molded article having excellent transparency can be obtained. Conventionally, a polyester resin molded product having a V-0 level and excellent transparency has not been commercially available.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 27/12 C08L 27/12 61/06 61/06 63/00 63/00 A 101/00 101/00 F-term (reference) 4F071 AA22 AA41 AA42 AA45 AA46 AC15 AE07 AE17 BB05 4J002 BB014 BC022 BC024 BD123 BD153 CC032 CD002 CF041 CF061 CF071 CF081 CG004 CH074 CL004 CM044 CN014 EW126 FD017 FD136

Claims (19)

[Claims] 1. An organic phosphorus compound (B-1 component) represented by the following general formula (1): (A) 100 parts by weight of a resin component (A component) containing at least 60% by weight of an aromatic polyester resin. ) 1 to 100 parts by weight, (C) flame retardant improving resin (C component) 0 to 50 parts by weight, and (D) filler (D)
Component) A flame-retardant resin composition comprising 0 to 200 parts by weight. [Chemical 1] (In the formula, R ¹ and R ⁴ may be the same or different and are a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. R ³ and R ⁶ may be the same or different. And R ² and R ^{5, which} may be the same or different, are a phenyl group, a naphthyl group or an anthryl group, and have a substituent on the aromatic ring. It may be.) 2. The aromatic polyester resin (A) is a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polyethylene naphthalate resin, a polybutylene naphthalate resin, a polycyclohexane dimethyl terephthalate resin, a polytrimethylene terephthalate resin or a polytrimethylene naphtha resin. The flame-retardant resin composition according to claim 1, which is at least one selected from the group consisting of phthalate resins. 3. The flame-retardant resin composition according to claim 1, wherein the aromatic polyester resin (A) is at least one selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin and polyethylene naphthalate resin. 4. The aromatic polyester resin (A
-1 component) 60 to 100 parts by weight and polyphenylene ether resin, polycarbonate resin, polyamide resin,
At least one thermoplastic resin (A- selected from the group consisting of a polyolefin resin, a styrene resin, a polyphenylene sulfide resin, and a polyetherimide resin).
The flame-retardant resin composition according to claim 1, which comprises 2 to 40 parts by weight. 5. (B) Organophosphorus compound (B-1 component)
The flame-retardant resin composition according to claim 1, wherein the acid value is 0.7 mgKOH / g or less. 6. (B) Organic phosphorus compound (B-1 component)
The flame-retardant resin composition according to claim 1, wherein the HPLC purity is at least 90%. 7. (B) Organic phosphorus compound (B-1 component)
The flame-retardant resin according to claim 1, wherein R ² and R ⁵ in the above formula (1) are the same or different and are phenyl groups which may have a substituent on the aromatic ring. Composition. 8. (B) Organic phosphorus compound (B-1 component)
Is a compound represented by the following formula (1-a):
The flame-retardant resin composition described. [Chemical 2] 9. The flame-retardant resin composition according to claim 1, wherein the B-1 component is contained in a proportion of 5 to 90 parts by weight with respect to 100 parts by weight of the A component. 10. The (C) flame-retardant improvement resin (component C) is
Phenolic resin (C-i component), epoxy resin (C-ii
Component) and styrene resin (C-iii component), at least one selected from the group consisting of 0.01 to 45 parts by weight per 100 parts by weight of component A. Composition. 11. The (D) filler (D component) is the A component 1
The flame-retardant resin composition according to claim 1, which is contained in an amount of 1 to 150 parts by weight per 00 parts by weight. 12. An organic phosphorus compound (B-1 component) represented by the following general formula (1): (A) 100 parts by weight of a resin component (A component) containing at least 60% by weight of an aromatic polyester resin. ) 1 to 100 parts by weight, (C) flame retardant improving resin (C component) 0 to 50 parts by weight, (D) filler (D component) 0 to 200 parts by weight, and (E) fluorine-containing resin (E component) ) A flame-retardant resin composition comprising 0.01 to 10 parts by weight. [Chemical 3] (In the formula, R ¹ and R ⁴ may be the same or different and are a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. R ³ and R ⁶ may be the same or different. And R ² and R ^{5, which} may be the same or different, are a phenyl group, a naphthyl group or an anthryl group, and have a substituent on the aromatic ring. It may be.) 13. The flame-retardant resin composition according to claim 1, which contains substantially no halogen. 14. In a molded product having a thickness of 1.6 mm, U
The flame-retardant resin composition according to claim 1 or 12, which achieves a flame-retardant level V-0 of L-94 standard. 15. In a molded product having a thickness of 0.8 mm, U
The flame-retardant resin composition according to claim 1 or 12, which achieves a flame-retardant level V-0 of L-94 standard. 16. Thermal stability (rate of change in MVR) is 20%.
The flame-retardant resin composition according to claim 1 or 12, which has: 17. (A) 100 parts by weight of a resin component (component A) containing at least 60% by weight of an aromatic polyester resin, (B) an organophosphorus compound represented by the following general formula (1) (component B-1): ) 1 to 100 parts by weight, (C) flame retardancy improving resin (C component) 0 to 50 parts by weight and (E) fluorine-containing resin (E component) 0 to 10 parts by weight, and total light transmittance is 80%. The transparent and flame-retardant resin composition as described above. [Chemical 4] (In the formula, R ¹ and R ⁴ may be the same or different and are a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. R ³ and R ⁶ may be the same or different. And R ² and R ^{5, which} may be the same or different, are a phenyl group, a naphthyl group or an anthryl group, and have a substituent on the aromatic ring. It may be.) 18. A flame retardant for an aromatic polyester resin, which is an organic phosphorus compound (B-1 component) represented by the general formula (1). 19. A molded product formed from the flame-retardant resin composition according to any one of claims 1, 12 and 17.