JPS62223257A - Flame-retardant thermoplastic polyester composition - Google Patents

Abstract

PURPOSE:To improve greatly impact resistance and to contemplate an improvement in flame retardance, by blending an arom. polyester or a blend thereof with an arom. polycarbonate with a thermoplastic non-rigid resin and a specified high-molecular halogen-contg. flame retarder. CONSTITUTION:This flame-retardant thermoplastic polyester compsn. is prepared from 45-94wt% arom. polyester or blend (A) thereof with an arom. polycarbonate, 4-30wt% thermoplastic non-rigid resin (B) and 2-25wt% high-molecular halogen-contg. flame retarder (C) having a halogen content of not lower than 40wt%, composed of an average of 15 or more repeating units. Pref. the weight ratio of B/C is 1/2-4/1. Any of thermoplastic resins exhibiting rubber elasticity can be used as the component B. Examples thereof are polyester elastomers, polyurethanes, polyamide elastomers and vinyl copolymers having a glass transition temp. of not higher than 0 deg.C.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides a flame-retardant polyester heat treatment material with significantly improved impact resistance, no flame retardant bleed, and less deterioration in mechanical strength and heat resistance. The present invention relates to a plastic resin composition.

(Prior art) Aromatic polyester has excellent properties such as solvent resistance, water resistance, oxidation resistance, abrasion resistance, and electrical properties, and is used in films and M! It is used in Oita as a double fiber. Furthermore, in recent years, it has been used for molding either reinforced with glass fiber or unreinforced.

Further, as an attempt to improve heat resistance, blend compositions with aromatic polycarbonates have been disclosed (for example, Japanese Patent Publication No. 86-14085 and Japanese Patent Publication No. 58-12587). However, both aromatic polyesters and blend compositions of aromatic polyesters and aromatic polycarbonates have low impact resistance, which limits their use, and like many resins, they are flammable.

Attempts to improve impact resistance include compositions containing so-called elastomer components (for example, Japanese Patent Publication No. 46-6227, Japanese Patent Publication No. 51-25251, Japanese Patent Publication No. 55-948).
No. 5) is disclosed. On the other hand, as a method of imparting flame retardancy, it is known to add a flame retardant containing halogen, phosphorus, or nitrogen, and among them, halogen-containing flame retardants have a high flame retardant effect. However, among halogen-containing flame retardants, those with low molecular weights significantly reduce mechanical properties and heat resistance, and are prone to bleeding. In order to improve this drawback, it has been proposed to use halogenated bisphenol-based carbonate oligomers (for example, JP-A-48-528
No. 84), although bleeding is prevented, improvements in mechanical properties (particularly impact resistance) and heat resistance are insufficient.

(Problems to be Solved by the Invention) An object of the present invention is to significantly improve the impact resistance of an aromatic polyester or a blend composition of an aromatic polyester and an aromatic polycarbonate, and to provide a thermal The present invention provides a plastic polyester composition.

(Means for Solving the Problems) The present invention provides (4) 45 to 941% by weight of an aromatic polyester or a blend composition of aromatic polyester and aromatic polycarbonate, ■) 4 to 80% by weight of a thermoplastic soft resin, (C) A flame-retardant thermoplastic polyester composition comprising 2 to 25'M% of a high molecular weight halogen-containing flame retardant having an average of 15 or more repeating units and a halogen content of 40% by weight or more. It is.

The present invention will be explained in detail below.

The aromatic polyester used in the present invention is a polyester having an aromatic ring in the chain unit of the polymer, and is mainly composed of an aromatic dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative). It is a polymer or copolymer obtained by a condensation reaction. Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid,
naphthalene-2,7-dicarboxylic acid, diphenyl-4,
4-dicarboxylic acid, diphenoxyethanedicarboxylic acid,
Examples include aromatic dicarboxylic acids such as diphenyl ether dicarboxylic acid, and ester-forming derivatives thereof. Further, the acid component may be substituted with 20 mol % or less of aliphatic dicarboxylic acid (eg, adipic acid, sebacic acid) or an ester-forming derivative thereof. In addition, as a diol component,
For example, ethylene glycol, 1,4-butanediol,
trimethylene glycol, pentamethylene glycol,
hexamethylene glycol, neopentyl glycol,
Diethylene glycol, triethylene glycol, 1.
1-Cyclohexane dimetatool, 1.4-cyclohexane dimetatool, xylylene glycol, 2.2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfone, bis(hydroxyethoxy)benzene, 2 .2-bis(4-hydroxyphenyl)propane ethylene oxide adduct, 2.2-bis(
Examples include propylene oxide adducts of 4-hydroxyphenyl)propane, and ester-forming derivatives thereof.

The aromatic polyester used in the present invention may be a mixture of two or more aromatic polyesters. Particularly preferred aromatic polyesters include polymers and copolymers obtained from terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid or ester-forming derivatives thereof, and alkylene glycol or ester-forming derivatives thereof.

The aromatic polycarbonate used in the present invention is a homo- or copolycarbonate, or a mixture thereof, and is obtained by a known polycondensation reaction of bisphenols and phosgene or carbonic acid diester. Bisphenols include, for example, hydroquinone, resorcinol, dihydroxycyphere, bis(hydroxyphenyl)alkane, bis(hydroxyphenyl)cycloalkane, bis(hydroxyphenyl)sulfide, bis(hydroxyphenyl)ether, bis(hydroxyphenyl)ketone, and bis(hydroxyphenyl)ketone. (hydroxyphenyl) sulfoxide, bis(
hydroxyphenyl) sulfone, and human t19a-bis(
Hydroxyphenyl) diimpropylbenzene. Particularly preferred aromatic polycarbonates are poly-2,
2-bis(4-hydroxyphenyl)propane carbonate and/or polybis(4-hydroxyphenyl)sulfone carbonate.

The thermoplastic soft resin (B) used in the present invention may be any thermal IfIm resin that exhibits rubber elasticity at room temperature, such as polyester elastomer, polyurethane, polyamide elastomer, and vinyl having a glass transition temperature of 0°C or lower. Polyester elastomers include aromatic polyester blocks and polyether blocks, or aromatic polyester blocks and aliphatic polyester blocks. There are block copolymers, and preferred examples include block copolymers of polybutylene terephthalate and polyoxytetramethylene and block copolymers of polybutylene terephthalate and polycaprolactone.

Polyurethanes include polylactone ester polyols, polyadipate ester polyols, polycarbonate ester polyols, or polyethers having two or more hydroxyl groups in one molecule, and thermoplastic polymers obtained by addition-polymerizing polyfunctional isocyanates in the presence of low-molecular-weight polyols. Examples include polyurethane.

Examples of polyamide elastomers include block copolymers consisting of polyamide blocks such as polycaprolactam or polylaurolactam and polyester blocks, or polyamide blocks and polyether blocks such as polyoxyethylene, polyoxypropylene, and polyoxytetramethylene.

Examples of vinyl polymers include known olefin monomers, halogenated vinyl monomers, diene monomers, aromatic vinyl monomers, acrylic or methacrylic acid derivatives (including metal salts), Examples include random, block, and graft copolymers of vinyl monomers such as vinyl ester monomers, vinyl ether monomers, and unsaturated dibasic acid salt conductors. Preferred examples include ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-propylene-butadiene copolymer, ethylene-ethyl acrylate copolymer, styrene-butadiene block copolymer,
Partially hydrogenated styrene-butadiene block copolymer, ethylene-propylene-styrene graft copolymer, ethylene-propylene-styrene-acrylonitrile graft copolymer, ethylene-propylene-butadiene-styrene graft copolymer, ethylene-propylene- Butadiene-styrene-acrylonitrile graft copolymer, acrylonitrile-butadiene-styrene graft copolymer, butadiene-styrene-methyl methacrylate graft copolymer, butadiene-acrylonitrile copolymer, butadiene-styrene-acrylonitrile-methyl methacrylate graft copolymer , butadiene-acrylonitrile-methacrylic acid copolymer, styrene-maleic anhydride copolymer, ethylene-maleic acid copolymer, styrene-ethyl acrylate-n-butyl acrylate-allyl methacrylate graft copolymer, ethylene- Examples include zinc salts of methacrylic acid copolymers and magnesium salts of ethylene-methacrylic acid copolymers.

High molecular weight halogen-containing flame retardant (C) used in the present invention
has an average repeating unit number of 15 or more and contains 40 halogens.
It may contain at least % by weight, and preferred examples include halogenated polycarbonate whose aromatic ring is halogenated, halogenated polyphenylene oxide, halogenated bisphenol-based epoxy resin, halogenated polyester, and halogenated polystyrene.

Furthermore, the average number of repeating units is more preferably 25 or more. Furthermore, in the case of a halogen-containing flame retardant having an average number of repeating units of less than 15, bleeding of the flame retardant is likely to occur, and even if a predetermined amount of the thermoplastic soft resin (I3) is blended, the impact resistance will not be sufficiently improved. On the other hand, with high molecular weight halogen-containing flame retardants with a halogen content of less than 40% by weight, a large amount of flame retardant must be added to achieve flame retardancy, resulting in a decrease in mechanical strength including km resistance. .

These high molecular weight halogen-containing flame retardants (C) may be obtained by any known method; for example, a polymer is polymerized by a conventional method, and then dihalogen-containing flame retardant C is It can be obtained by halogenation by reacting with methane or dihalogenated ethane.Also, as another method, it can be obtained by polymerizing various halogenated monomers alone or by adding other monomers. can.

The latter method using halogenated monomers is more specifically, for example, by reacting halogenated bisphenols with carbonate esters, phosgene, dicarboxylic acids, and diglycidyl ethers to produce halogenated polycarbonates, halogenated polyesters, and halogenated polyesters, respectively. A method for obtaining a halogenated bisphenol-based epoxy resin, a method for obtaining a halogenated polyester by reacting a halogenated aromatic dicarboxylic acid with a diol, a method for obtaining a halogenated phenol, a halogenated styrene color, a halogenated polyphenylene oxide, a halogenated polystyrene, etc. There is. Further, as the halogen, chlorine and bromine are preferable.

The high molecular weight halogen-containing flame retardant (C) of the present invention may be used in combination of two or more, and may further include flame retardants containing phosphorus and/or nitrogen, and flame retardant aids such as antimony compounds, boron compounds, and molybdenum compounds. It can also be used in combination with antimony oxide, and combination use with antimony oxide is particularly preferred in terms of improving flame retardancy.

In the present invention, an aromatic polyester or a blend composition (1) of an aromatic polyester and an aromatic polycarbonate, a thermoplastic soft resin CB) and a high molecular weight compound comprising an average of 16 or more repeating units and a halogen content of 40% by weight or more The proportions of the halogen-containing flame retardant (C) are (4) 45 to 94% by weight, (B) 4 to 80% by weight (C2 to 25% by weight).

If (4) is less than 45% by weight, the excellent performance of the aromatic polyester or aromatic polyester/aromatic polycarbonate blend composition will not be exhibited, and if (4) is more than 94% by weight, the impact resistance will not be improved, resulting in difficulty. The flammability is also not satisfactory. (
If J3) is less than 4% by weight, impact resistance cannot be improved, and if it exceeds 80% by weight, mechanical strength other than #impact resistance is significantly reduced.

If (C) is less than 2M%, flame retardancy cannot be imparted, and 252! If the amount exceeds %, impact resistance and mechanical strength will be greatly reduced.

In addition, the preferred weight ratio of the thermoplastic soft resin CB) and the high molecular weight halogen-containing flame retardant (C) to sufficiently achieve both impact resistance improvement and flame retardancy is (B) / (C) = 1.
The range is from /2 to 4/1.

The blending ratio of the aromatic polyester and aromatic polycarbonate of component (4) can be set to any value as required, and as the proportion of the aromatic polycarbonate increases,
Solvent resistance and fluidity during molding decrease, but heat resistance and dimensional stability of the molded product improve.

In the present invention, an aromatic polyester or a blend composition (4) of an aromatic polyester and an aromatic polycarbonate, a thermoplastic soft resin (2), and a high-density polymer comprising an average of 15 or more repeating units and a halogen content of 40% by weight or more are used. The molecular weight halogen-containing flame retardant (Q) can be blended by melt-kneading them all at once and forming them into pellets, by molding them all at the same time, or by melt-kneading two or more components in advance to produce master pellets. Any known method can be used, such as a method of mixing with the remaining components during molding and molding.

Furthermore, the composition of the present invention may optionally contain glass fibers,
Fibrous fillers such as carbon fibers and metal fibers, inorganic fillers such as talc and mica, polyfunctional compounds such as epoxy compounds and aryl compounds, heat stabilizers, crystallization promoters, mold release agents, lubricants, and colorants. etc. can be added.

(Effects of the Invention) The flame-retardant thermoplastic polyester composition of the present invention has not only a high degree of flame retardancy but also excellent mechanical properties, especially impact resistance, compared to conventionally known compositions. There is. Taking advantage of these properties, it can be used for materials such as various interior and exterior parts and housings.

(Example) The present invention will be described in further detail using Examples below. In addition, all % in an example means weight %.

Examples 1 to 8 Polyester elastomer (Kanebo Gore, MS, Velvet EFG-6) as the component, polyester elastomer (Toyobo Co., Ltd. Pelprene P-150M) as the component (B), styrene-butadiene block Copolymer (1!Kikagaku Kogyo ■Denka 5TR1602) and engineered cowshin-propylene copolymer (Japan Synthetic Rubber @4 E
POIPX), brominated polycarbonate produced by the phosgene method from tetrabromobisphenol as component (c) (average number of repeating units = 20, bromine content = 64
%), antimony trioxide (Nippon Seiko ■A) as a flame retardant aid.
TOX-B) were melt-kneaded using a single screw extruder at the ratios shown in Table 1 to produce pellets.

Next, various test pieces were injection molded under normal conditions and their physical properties were measured. The results are shown in Table-2.

Comparative Examples 1 to 7 In addition to the components used in Examples 1 to 8, brominated polycarbonate oligomers (average number of repeating units =
10, bromine content = 65%), brominated copolycarbonate made from tetrabromo bisphenol and bisphenol (average number of repeating units = 25, bromine content =
81%) and hidecaprom diphenyl ether (g-Kogyo Seiyaku ■ Pyroguard 8R-200AW) were blended and molded in the same manner as in Examples 1 to 8 in the proportions shown in Table 1, and the physical properties were investigated. The results are shown in Table-2.

Examples 4 and 6 Component (4) is a blend composition of polyethylene terephthalate (Kanebo Gosen ■ Velvet EFG-6) and aromatic polycarbonate (Mitsubishi Gas Chemical ■ Nipiro 7f3-1000), and component (B) is partially hydrogenated styrene. The same components and conditions as in Examples 1 to 8 were used, except for using -butadiene block copolymer (Shell Kagaku ■ Kraton 01652) and ethylene-vinyl acetate copolymer (Mitsui Polychemical ■ Evaflex-160). It was blended, molded, and its physical properties were measured. The composition and measurement results are shown in Table-8.

Example 6.7 Component (4) was polybutylene terephthalate (Mitsubishi Kasei ■ Tubadol 5010), component (B) was styrene-butadiene block copolymer and ethylene-vinyl acetate copolymer block copolymer, component (Q Brominated polystyrene (Pyrocheck 68FB manufactured by Nissho Ferro Organic Chemistry) and short glass fiber (Nittobo Glass Fiber 〇! 86PE manufactured by Nissho Ferro Organic Chemical Industry Co., Ltd.) are used as regular reinforced PB.
Compounding and molding were performed under the conditions of T resin, and the physical properties were investigated. The results are shown in Table 4.

Table-8 1) Mu8TM 8648 Table-4

Claims (8)

[Claims] (1) (A) Aromatic polyester or blend composition of aromatic polyester and aromatic polycarbonate 45
~94% by weight, (B) 4 to 30% by weight of a thermoplastic soft resin, (C) 2 to 25% by weight of a high molecular weight halogen-containing flame retardant consisting of an average of 15 or more repeating units and having a halogen content of 40% by weight or more. A flame-retardant thermoplastic polyester composition comprising: (2) The weight ratio of the thermoplastic soft resin (B) and the high molecular weight halogen-containing flame retardant (C) is (B)/(C) = 1/2 to 4/
1. The composition according to claim 1, which is (3) Claim 1, wherein the aromatic polyester is a polymer or copolymer obtained from terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, or an ester-forming derivative thereof, and alkylene glycol or an ester-forming derivative thereof. Composition of. (4) Aromatic polycarbonate is poly-2,2-bis(
4-hydroxyphenyl)propane carbonate and/or
The composition according to claim 1, which is polybis(4-hydroxyphenyl)sulfone carbonate. (5) Thermoplastic soft resin (B) is polyester elastomer, polyurethane, polyamide elastomer and 0°C
The composition according to claim 1, which is one or more vinyl copolymers selected from vinyl copolymers having the following glass transition temperatures. (6) The vinyl copolymer is an olefin monomer, a halogenated vinyl monomer, a diene monomer, an aromatic vinyl monomer,
Claim 5, which is a random, block or graft copolymer consisting of an acrylic acid or methacrylic acid derivative (including a metal salt), a vinyl ester monomer, a vinyl ether monomer, and an unsaturated dibasic acid derivative Compositions as described. (7) The composition according to claim 1, wherein the high molecular weight halogen-containing flame retardant (C) is a halogenated polycarbonate, a halogenated polyphenylene oxide, a halogenated bisphenol-based epoxy resin, a halogenated polyester, and a halogenated polystyrene. (8) The composition according to claim 1, wherein the high molecular weight halogen-containing flame retardant (C) comprises an average of 25 or more repeating units.