JPS59204653A - Flame-retardant polyester resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition giving a thin-walled molded article having remarkably improved flame retardance, by compounding a base polyester resin with a halogen-containing flame retardant in combination with a reaction product of melamine, etc. with a benzenensulfonic acid compound and an antimony-containing compound. CONSTITUTION:(A) 100pts.wt. of a thermoplastic polyester resin is compounded with (B) 5-40pts.wt. of a halogen-containing flame retardant such as the compound of formula I (X is O, S, SO2, or alkylene; X1 and X2 are Cl or Br; R1 and R2 are H, OH or alkyl; m and n are 1-5; x and y are 0-4; m+x is 5; n+y is 5), (C) 2-30pts.wt. of the compound obtained by the reaction of a compound selected from dicyandiamide, melamine, etc. with the benzene-sulfonic acid compound of formula II (R1-5 are H, SO3H, NH2, NO2, etc.) and (D) an antimony- containing compound. The weight ratio of (D) to (B) is 0-3.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel flame-retardant polyester resin composition.

Thermoplastic raw polyesters, such as polyethylene terephthalate, have excellent mechanical properties, electrical properties, and heat resistance.

With excellent chemical resistance, polybutylene terephthalate and polyethylene terephthalate are often used as TA fibers and films, and in recent years polybutylene terephthalate and polyethylene terephthalate reinforced with glass fiber have been used in large quantities as engineering plastics in the field of industrial parts such as electrical parts, automobile parts, and mechanical parts. Therefore, it is essential to make the resin flame retardant, especially when using it as an electrical component.

Traditionally, halogen compounds have been used to make resin flame retardant.

Organic phosphorus compounds, halogen-containing phosphorus compounds, etc. have been used, and the purpose has been achieved to a large extent, and for thermoplastic polyester resins, organic halogen compounds or the combination of organic halogen compounds and antimony-containing compounds are said to be effective. There is.

Particularly in recent years, the wall thickness of plastic molded products such as electrical and mechanical parts has become thinner in order to reduce weight and cost, but in general, the thinner the molded product, the more likely it is to burn. Therefore, there are cases where conventional flame-retardant resin compositions cannot respond.

The reality is that improvements are strongly desired.

The inventors of the present invention have conducted extensive research to develop a &Ii flame-retardant resin composition that is even better than conventional flame-retardant polyester resin compositions. It was discovered that the flame retardance was generally improved, and the present invention was achieved.

That is, in the present invention, (a) 5 to 40 parts by weight of a halogen flame retardant (
Q dicyandiamide, dicyancyamicin.

2 to 30 parts by weight of a reaction product of one kind of compound selected from diguanide, guanidine, melamine, or their derivatives (hereinafter referred to as dicyandiamide, etc.) and a benzenesulfonic acid compound represented by the general formula CI), where R + "Rs is H, SO+ lj, NHx, C
0OH, OH.

CN, NO2 or alkyl groups, which may be the same or different.

(c) This invention relates to a flame-retardant polyester resin composition containing an organic or inorganic antimony-containing compound in a weight ratio of 0 to 3 times that of a halogen flame retardant.

The thermoplastic polyester resin used in the present invention is, for example, polyethylene terephthalate.

Polyalkylene terephthalate such as polybutylene terephthalate (or a copolymerized polyester whose main component is the alkylene terephthalate unit, and various acid components and glycol components can be used as copolymerization components. For example, acid component Examples include isophthalic acid, naphthalene dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylmethane dicarboxylic acid, diphenylsulfone dicarboxylic acid, and p-(2-hydroxyethoxy)benzoic acid.

5-Sodium sulfoisophthalic acid, adipic acid.

Examples include acid derivatives such as azelaic acid, sebacic acid, decane-1,10-dicarboxylic acid, tetradecane-1,14-dicarboxylic acid, octadecane-1,18-dicarboxylic acid, and esters thereof. The glycol component is propylene glycol.

Examples include diethylene glycol, pentyl glycol, neopentyl glycol, hexamethylene glycol, polyethylene glycol, polytetramethylene glycol, and the like.

Furthermore, as thermoplastic polyesters, in addition to the above, terephthalic acid, isophthalic acid, 2. Specific examples include aromatic polyesters synthesized from 'L-'s(p-hydroxyphenyl)propane.

The halogen-based flame retardant used in the present invention is not particularly limited as long as it contains a halogen, but examples of halogen-based flame retardants suitable for thermoplastic polyester include general formula (n) or ]II) can be mentioned.

(Xa7(xJ shoulder) However, -X- is 10-, -3-, -5Oa- or an alkylene group, , R2, are the same or different groups and are hydrogen, hydroxyl group, or alkyl group. m and n are integers of 1 to 5 + x+ y are integers of 0 to 4, m+ x = 5, n, + y =
It is an integer that satisfies 5.

However, LX+, X2, and Xs are the same or different groups, and cJ! or 13r, R1, R2, and R3 are the same or different groups and are hydrogen or an alkyl group, and R4 is hydrogen, an alkyl group, or an aromatic residue. Yu is an integer from 1 to 5, m and n are integers from 1 to 4, and X is an integer from 1 to 4.
The integer of 4 +y+z is an integer of 0 to 3, and +yc+1
=5. y+m=4. It is an integer that satisfies z+n=4.

p is an integer of 1 or more.

In the present invention, the benzenesulfonic acid compound used by reacting with dicyandiamide etc. can be represented by the general formula (IJ).

However, R+”Rs is H, SOa II, NHz,
COOH, Oll.

CN, NOa or alkyl groups, which may be the same or different.

Specific examples of benzenesulfonic acid compounds represented by the general formula (2) include benzenesulfonic acid, o
-, m-+ to p-aminobenzenesulfonic acid,'
O-, +n- to p-sulfobenzoic acid, O-, m- to p-phenolsulfonic acid, 2,4-phenoldisulfonic acid, 1,3.5-benzenetrisulfonic acid, p-henzenedisulfonic acid 1 m -benzenedisulfonic acid, 0. Examples include m- to p-nitrobenzenesulfonic acid, but the compound is not limited to these as long as it has at least one 5O3H group.

Furthermore, the reaction between dicyandiamide, etc. and a benzenesulfonic acid compound can be carried out by various methods.2 Usually, dicyandiamide, etc. and one or more types of hensensulfonic acid compound are melted in a suitable solvent and heated. The simplest method is to react using The amount of dicyandiamide used is usually 0.5 to 3 times the molar ratio of 2 to the benzenesulfonic acid compound, but it is most preferable to use 9 equivalent moles.

Various organic or inorganic antimony-containing compounds can be used as necessary in the present invention, and specific examples include antimony trioxide, antimony phosphate, and triphenylantimony. I can do it.

Antimony trioxide is particularly preferred.

Regarding the blending amount of each component in the present invention, if the amount of the halogenated flame retardant, which is component (a), is less than 5 parts by weight per 100 parts by weight of the thermoplastic polyester resin, it will be insufficient in terms of imparting flammability. On the other hand, even if more than 40 parts by weight is added, the effect of imparting flame retardancy is not necessarily proportional to the amount, but it is not preferable because the physical properties may deteriorate.

Therefore, the blending amount of the halogen-based Iif fuel is preferably in the range of 5 to 40 parts by weight based on 10Q parts by weight of the thermoplastic polyester resin.

Next, regarding the amount of the reaction product of dicyandiamide etc. and the benzenesulfonic acid compound represented by the general formula (I), 2 parts by weight per 100 parts by weight of the thermoplastic polynister resin.
If it is less than 30 parts by weight, it will not be sufficient to further improve the effect of the halogen flame retardant as an H flame agent, and conversely, if it is added in more than 30 parts by weight, mechanical properties and thermal properties may deteriorate. Undesirable.

Therefore, the blending amount of the reactant is 1 part thermoplastic polyester resin.
00 parts by weight, preferably 2 to 30 parts by weight, more preferably 2 to 15 parts by weight.

(Regarding the blending amount of the organic or inorganic antimony-containing compound in the Han component, even if it is blended in an amount more than three times the amount of the halogen flame retardant in component (a), the effect of the halogen flame retardant as an auxiliary agent will not change. Usually, it is preferably 0 to 3 times as much as the halogen flame retardant, and preferably 0.1 to 1 times as much as the halogen flame retardant.

Regarding the total amount of component (4) < T: I) (/\), the greater the total amount, the better the flame retardancy, but if more than a certain amount is added, the mechanical properties , as performance such as thermal properties may deteriorate.

The total blending amount is preferably 7 to 50 parts by weight, more preferably 10 to 4 parts by weight, based on 100 parts by weight of the thermoplastic polyester resin.
A range of 0 parts by weight, more preferably 15 to 30 parts by weight, is preferred.

Further, the flame-retardant polyester resin composition of the present invention may contain fibrous reinforcing materials such as glass fibers, carbon fibers, aromatic polyamide fibers, silicon carbide fibers, and titanate fibers, if necessary.

By blending such fibrous reinforcing materials, mechanical properties and thermal properties such as heat distortion temperature can be improved, and an excellent molding material can be provided.

Furthermore, the composition of the present invention may be blended with various inorganic or organic compounds such as antioxidants, ultraviolet absorbers, coloring agents, mold release agents, and fillers to produce various molded products.

It can be used in the form of a film, sheet, ta fibrous tube, or the like.

4 Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. Note that "parts" shown in Examples and Comparative Examples indicate "parts by weight."

(1) Preparation of the reaction product of dicyandiamide and benzenesulfonic acid compound Equimolar amounts of dicyandiamide and p-aminobenzenesulfonic acid were mixed, stirred in hot water, and the resulting reaction product was filtered and dried. It was pulverized to an average particle size of 5 μm or less. [Hereinafter, the reactant 1 is abbreviated as a reactant (abbreviated as N.) Similarly, an equimolar reactant of dicyancyamidine and p-phenolsulfonic acid [abbreviated as a reactant (B)], guanidine and p-phenolsulfonic acid - equimolar reactant with nitrobenzenesulfonic acid [reactant (C)
] was adjusted.

Example 1. Comparative Example 1 100 parts of polyethylene terephthalate with an intrinsic viscosity of 0.68 (measured in phenol/tetrachloroethane-6/4 solvent, concentration 0.5%, temperature 20°C), 12 L of decabromidiphenyl ether, 4 parts of antimony dioxide, 9 reactants. (
A) 3 parts, glass fiber [manufactured by Asahi Fiber - Glass ■, 3
mm length chopped strand, product number tooth 429) 15
Blend the parts, make pellets using an extruder, and after drying, use an injection molding machine at a cylinder temperature of 240-260℃.
-270℃, mold temperature 130℃, injection holding time 10 seconds,
5 under conditions of injection pressure 300-600 kg/c+a
! NX'A! NX +A2! A test piece was molded (Example 1).

For comparison, pellets were prepared in which only the reactant (A) in Example 1 was replaced with decabromidiphenyl ether, and the amount of decabromidiphenyl ether was 15 parts. A test piece of XV2 EnxClean was molded. (Comparative Example Work) When each test piece was evaluated for flame retardancy according to the UL94 standard, the test piece of Example 1 showed v-0, but in the case of Comparative Example 1, it was evaluated as V-2. .

Examples 2-4. Comparative Examples 2 to 4 Polyethylene terephthalate 1-5 copolymerized with 10% by weight of 3 polyethylene glycol having a molecular weight of 1000 as a polyester; halogen-based H having a poly-p-phenylene oxide skeleton represented by the following general formula (IV) as a flame retardant; The N flammability of a test piece having a composition shown in Table 1 and having a thickness of 2λ was evaluated in the same manner as in Example 1 using a refueling agent.

However, the parts in the table are parts by weight based on 100 parts of polyester resin.

Table 1 Example 5 Polybutylene terephthalate 100 with intrinsic viscosity 0.66
1 part decabromodiphenol ether 12 parts 1 reactant (A
) 4 parts, antimony dioxide 5 parts, and glass fiber 30 parts composition is a! A test piece with a thickness of 1.5' thick showed flame retardancy of UL94°V-O.

Patent applicant: Unitika Co., Ltd.

Claims (1)

[Claims] (1) Based on 100 parts by weight of thermoplastic polyester resin. (In-halogen flame retardant 5 to 40 parts by weight (b) Dicyandiamide, dicyancyamicin. A compound selected from diguanide, guanidine, melamine or derivatives thereof and benzenesulfonic acid represented by the following general formula Reactants 2 to 3 with system compounds
0 parts by weight However, R+-Rs is H, Slh H, Nl2,
C0OH,011. CN, NO2 or alkyl groups, which may be the same or different. [A flame-retardant polyester resin composition containing an organic or inorganic antimony-containing compound in a weight ratio of 0 to 3 times the weight of a halogen flame retardant. 2. The flame-retardant polyester resin composition according to claim 1, wherein the halogen flame retardant is a compound represented by the following general formula (II). However, -X- is 10-, -3-, -3o2- or an alkylene group, such as XI, X2. are the same or different groups and are CI or Br, and R1, R2 are the same or different groups and are hydrogen, a hydroxyl group, or an alkyl group. mln is an integer from 1 to 5 + x+ y is an integer from O to 4, and m x = 5. n+)"" is an integer that satisfies 5. 3. The flame-retardant polyester 4-resin composition according to claim 1, wherein the halogen-based flame retardant is a compound represented by the following general formula ([, provided that XI, X2. There it is,
C line or Br, R2 and R3 are the same or different groups and are hydrogen or an alkyl group, and R4 is hydrogen, an alkyl group or an aromatic residue. No is 1-5
m, n are integers of 1 to 4, X is an integer of 0 to 4,
y and z are integers from 0 to 3, and XIJ2 = 5. y+
m=4. It is an integer that satisfies z+n=4. p is an integer of 1 or more.