JPH0160488B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to polyester resin compositions. Specifically, the present invention relates to a polyester resin composition that is flame retardant and has excellent impact resistance. As flame-retardant polyester resin, diol,
Copolymerized polyester resins obtained by copolymerizing dicarboxylic acids or their esters and halogen-containing aromatic diols are known (Japanese Unexamined Patent Application Publication No. 1973-1992).
54494), this copolyester resin had the disadvantage that mechanical properties such as impact resistance deteriorated when the halogen-containing aromatic diol component was increased in order to obtain sufficient flame retardancy. As a result of intensive research aimed at improving the impact resistance of the flame-retardant copolyester resin described above, the present inventors found that when a rubber-like polymer is blended with the flame-retardant copolyester resin, completed the present invention after learning that impact resistance could be significantly improved without impairing flame retardancy. That is, the purpose of the present invention is to provide a polyester resin of great industrial value, and its gist is to provide polyester resins containing terephthalic acid or its ester-forming derivatives, alkylene glycols having 2 to 10 carbon atoms, or their Ester-forming derivatives and general formula (In the formula, R is an alkylene group having 2 to 4 carbon atoms, X is a halogen atom, l and m are numbers from 1 to 4, and p and q are numbers from 1 to 10.) To 100 parts by weight of a copolyester resin with a halogen content of 3 to 15% by weight, obtained by copolymerizing diol, methacrylic This is a polyester resin composition containing 0.5 to 20 parts by weight of a rubbery polymer obtained by graft polymerizing an acid ester. The present invention will be explained in detail below. The copolymerized polyester resin used in the present invention is
Terephthalic acid or its ester-forming derivatives,
It is a copolymer of an alkylene glycol having 2 to 10 carbon atoms or an ester-forming derivative thereof, and a halogen-containing aromatic diol. Terephthalic acid may contain up to about 30 mole percent of other polybasic acids such as phthalic acid, isophthalic acid, naphthalene dicarboxylic acid, adipic acid, sebacic acid, trimellitic acid. Examples of the ester-forming derivatives include alkyl esters of the above acids such as dimethyl terephthalate. Examples of alkylene glycols having 2 to 10 carbon atoms include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, etc. % or less of polyhydroxy compounds such as glycerin, pentaerythritol. Furthermore, examples of the ester-forming derivative include ethylene oxide. Halogen-containing aromatic diols have the general formula (In the formula, R is an alkylene group having 2 to 4 carbon atoms, X is a halogen atom, l and m are numbers from 1 to 4, and p and q are numbers from 1 to 10.) For example, it is produced by reacting halogenated bisphenol A with an alkylene oxide such as ethylene oxide or propylene oxide, or an alkylene halohydrin such as epichlorohydrin. Usually, R in the above general formula [] is -CH ₂ -
CH ₂ - group or

[Formula] A group in which X is bromine or chlorine is preferable, and specifically, 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromphenyl]propane,
2,2-bis[4-(2-hydroxyethoxy)
-3,5-dichlorophenyl]propane, 2,2
-Bis[4-(2-hydroxypropoxy)-
3,5-dibromphenyl]propane, 2,2-
Bis[4-(3-hydroxypropoxy)-3,
5-dibromphenyl]propane, 2,2-bis[4-(3-hydroxypropoxy)-3,5-
dichlorophenyl]propane, 2,2-bis[4
-(2-hydroxyethoxy)-3-bromphenyl]propane, 2,2-bis[4-(2-hydroxyethoxy)-2,3,5,6-tetrabromphenyl]propane, and the like. In order to copolymerize the above three components to produce a copolymerized polyester resin, the above three components are charged during transesterification or esterification, followed by a polycondensation reaction, in accordance with conventionally known polyester resin production methods. Alternatively, terephthalic acid or an ester-forming derivative thereof is reacted with an alkylene glycol or an ester-forming derivative thereof to produce bishydroxyalkyl terephthalate or a low polymer thereof, which is then reacted with the general formula [] A method in which a halogen-containing aromatic diol represented by the following formula is added to perform a polycondensation reaction can be adopted. The type and amount of the halogen-containing aromatic diol used in the copolymerization are such that the halogen content of the resulting copolymerized polyester resin is 3 to 15% by weight,
It is preferably selected to be 5 to 10% by weight. If the halogen content of the copolymerized polyester resin is too low, the flame retardance will not be sufficient, whereas if it is too high, the mechanical properties will be impaired, which is not preferable. A rubber-like polymer is a rubber-like elastic body obtained by polymerization of acrylic acid ester or copolymerization mainly consisting of acrylic acid ester.A typical example is an acrylic acid ester such as butyl acrylate and a small amount of butylene dicarbonate. Examples include rubber-like polymers obtained by graft polymerizing a graft polymerizable monomer such as methyl methacrylate to polymers obtained by polymerizing a crosslinkable monomer such as acrylate. Examples of the acrylic ester include butyl acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, and the like. In addition to butylene diacrylate, examples of crosslinking monomers include butylene dimethacrylate, polyols such as trimethylolpropane trimethacrylate, and esters of acrylic acid or methacrylic acid, divinylbenzene, vinyl acrylate, vinyl methacrylate, etc. The compounds include allyl compounds such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate, monoallyl maleate, monoallyl fumarate, and triallyl cyanurate. In addition, as the above graft polymerizable monomer,
In addition to methyl methacrylate, examples include methacrylic acid esters such as ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate. A part of this graft polymerizable monomer can also be copolymerized by using it when producing a polymer by polymerizing the above-mentioned acrylic ester and a crosslinking monomer. Examples of the above-mentioned rubbery polymers include Kane Ace FM manufactured by Kanebuchi Chemical Co., Ltd., Vitax V-6401 manufactured by Hitachi Chemical Co., Ltd., Metaprene W-300 and Metaprene W-530 manufactured by Mitsubishi Rayon Co., Ltd. , manufactured by Rohm and Haas, is also commercially available as Acryloid KM-323, Acryloid KM-330, etc. The amount of the rubbery polymer blended is about 0.5 to 20 parts by weight, preferably about 1 to 15 parts by weight, based on 100 parts by weight of the copolyester resin. If the amount is too small, the present invention cannot be expected to be effective. On the other hand, if the amount is too large, the flame retardance will decrease, and mechanical properties such as tensile strength and bending strength will decrease, which is not preferable. Methods for blending a rubbery polymer with a copolymerized polyester resin include a method of dry blending pellets of a copolymerized polyester resin and a rubbery polymer pellet, and a method of melt-kneading the blended product using an extruder. Various well-known methods can be applied, such as extrusion and pelletizing methods. The composition of the present invention can further improve flame retardancy by containing a flame retardant such as an aromatic halide, and furthermore, even when such a flame retardant is contained, impact resistance is improved. It won't be damaged. Examples of aromatic halides include halogenated diphenyls such as hexabromo biphenyl and decabromo diphenyl ether, tetrabromo bisphenol A, polycarbonate oligomers derived from tetrabromo bisphenol A, and tetrabromo bisphenol A type epoxy. Halogenated bisphenol A or its derivatives such as resins, condensates of halogenated phenols such as tribromophenol condensates, halogenated phthalic anhydrides such as tetrabromophthalic anhydride, halogens such as polypentabromobenzyl acrylate Examples include polymers containing acrylate. These aromatic halides contain 10 parts by weight of halogen per 100 parts by weight of the copolyester resin.
It is preferable to use about 7 parts by weight or less, usually about 7 parts by weight or less. Additionally, the composition of the present invention may include flame retardant aids such as antimony oxide, reinforcing agents such as glass fiber, carbon fiber, asbestos, silica, alumina, silica alumina, silica magnesia, calcium silicate, calcium carbonate, glass Additives such as fillers such as beads and glass flakes, higher fatty acids, lubricants such as paraffin wax, stabilizers, antistatic agents, antioxidants, dyes and pigments may be included. The composition of the present invention has excellent flame retardancy and impact resistance, and also has improved mold releasability, melt flowability, and thermal stability, and can be molded by well-known molding methods such as injection molding, extrusion molding, and compression molding. Depending on the method, molded products excellent as electrical/electronic parts, automobile parts, and other industrial materials can be made. EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to the following Examples unless the gist of the invention is exceeded. In the examples, "parts" and "%" indicate "parts by weight" and "% by weight," respectively. In addition, flame retardancy is UL (Underwiter's
Laboratories Inc.) 94 standard, vertical combustion method test, impact resistance is
This is the value of Izod impact strength (1/2", notched) measured according to ASTM D 256. Example of production of copolyester resin 100 parts of dimethyl terephthalate, 56 parts of 1,4-butanediol, 2,2- Bis[4-(2-hydroxyethoxy)-3,5-dibromphenyl]
23 parts of propane and 2 parts of a 0.6% 1,4-butanediol solution of tetrabutoxytitanium as a catalyst were charged into a reactor, and the transesterification reaction was carried out at 210°C for 2 hours while distilling methanol. 1.3 parts of a 0.6% solution of titanium in 1,4-butanediol and Irganox
5% 1,4- of 1010 (stabilizer manufactured by Ciba Gaiki)
Add 1.2 parts of butanediol slurry and lower the temperature to
The polycondensation reaction was carried out while gradually raising the temperature to 245°C and lowering the pressure from normal pressure to 0.3 mmHg. After a polycondensation time of 5 hours, a copolymerized polyester resin having a bromine content of 7% and an intrinsic viscosity [η] of 0.85 was obtained. Examples 1 to 3 and Comparative Examples 1, 2, 6 to 9 Copolymer obtained by polymerizing the copolymerized polyester resin produced in the above production example, 69.3 parts of butyl acrylate, 0.35 part of butylene diacrylate, and 0.35 part of diallyl maleate. In addition, a rubbery polymer obtained by graft polymerization of 30 parts of methyl methacrylate, glass fiber (manufactured by Asahi Fiberglass Co., Ltd.,
CS03MA486), tribromophenol condensate (Versicol, Firemaster 935),
or polypentabromobenzyl acrylate (a polymer obtained by dissolving pentabromobenzyl acrylate in propylene glycol and polymerizing it using benzoyl peroxide as a catalyst, melting point 105
~110℃, bromine content 70.8%) and antimony trioxide in the proportions shown in Table 1 below,
The mixture was melt-kneaded and extruded at 250°C using a mmφ extruder to form pellets. The pellets were molded using a 3.5-ounce injection molding machine (manufactured by Nissei Jushi Kogyo Co., Ltd., model TS-100), a combustion test piece, and a test piece mold specified by ASTM.
Resin temperature 250℃, mold temperature 80℃, injection time 20 seconds,
Injection molding was performed with a cooling time of 30 seconds. The flammability and impact resistance of the obtained molded article were as shown in Table 1 below. For comparison, a case where no rubbery polymer was used (Comparative Example 1), and polybutylene terephthalate (manufactured by Mitsubishi Chemical Industries, Ltd., trademark, Novad Wool 5008,
(intrinsic viscosity 0.85), when tribromophenol condensate was added to impart flame retardancy (Comparative Example 2), when the amount was halved (Comparative Example 1'), and when no rubbery polymer was added. (Comparative Example 2'), acrylonitrile-butadiene-styrene resin (ABS) (manufactured by Mitsubishi Monsanto Chemical Co., Ltd.) in place of the rubbery polymer;
Product name: Toughflex, TF×410) and acrylic rubber-styrene-acrylonitrile copolymer (AAS) (manufactured by Hitachi Chemical Co., Ltd., product name: Vitax,
6100A) (Comparative Examples 6 to 9) are also shown.

[Table] Examples 4 to 6 and Comparative Examples 3, 4, 10 to 13 The same copolyester resin, rubbery polymer, tribromophenol condensate as used in Example 1, or the same copolymerized polyester resin used in Example 3 The same polypentabromobenzyl acrylate and antimony trioxide were mixed in the proportions shown in Table 2 below, pelletized in the same manner as in Example 1, and injection molded. The flame retardancy and impact resistance of the obtained molded article were as shown in Table 2 below. For comparison, a case where no rubbery polymer was used (Comparative Example 3), and the same polybutylene terephthalate used in Comparative Example 2 instead of the copolymerized polyester resin, and a tribromophenol condensate were prepared. When adding flame retardance (Comparative Example 4), when reducing the amount by half (Comparative Example 3')
and when no rubbery polymer is added (Comparative Example 4′),
The results are also shown when ABS (the same resin used in Comparative Example 6) was used instead of the rubbery polymer (Comparative Examples 10 and 11) and when no impact agent was added (Comparative Examples 12 and 13). .

【table】

[Table] Example 7 and Comparative Examples 5 and 5' The same copolyester resin and rubbery polymer as used in Example 1 were mixed in the proportions shown in Table 3 below, and the same as in Example 1 was prepared. The pellets were made into pellets and injection molded. The flame retardancy and impact resistance of the obtained molded article were as shown in Table 3 below. For comparison, the results when no acrylic rubber was blended and when polybutylene terephthalate was used are also shown.

[Table] Example 8 and Comparative Examples 14 to 21 The same copolyester resin, rubbery polymer, and glass fiber used in Example 1 were mixed in the proportions shown in Table 5 below, and the It was made into pellets in the same manner and injection molded. The flame retardancy and impact resistance of the obtained molded article were as shown in Table 5 below. For comparison, the results are also shown when no rubbery polymer was used and when the same polybutylene terephthalate used in Comparative Example 2 was used instead of the copolymerized polyester resin. In addition to rubbery polymers, acrylonitrile-
Butadiene-styrene copolymer (ABS) (manufactured by Mitsubishi Monsanto Co., Ltd., product name: Futalex,
TFX410) or ethylene-ethyl acrylate copolymer (EEA) (manufactured by Nippon Unica Co., Ltd., product name: DPDJ-9169) (Comparative Examples 17 to
21) results are shown in Table 6.

【table】

【table】

Claims (1)

[Claims] 1. Terephthalic acid or an ester-forming derivative thereof, an alkylene glycol having 2 to 10 carbon atoms or an ester-forming derivative thereof, and the general formula (In the formula, R is an alkylene group having 2 to 4 carbon atoms, X is a halogen atom, l and m are numbers from 1 to 4, and p and q are numbers from 1 to 10.) To 100 parts by weight of a copolyester resin with a halogen content of 3 to 15% by weight, obtained by copolymerizing diol, methacrylic A polyester resin composition containing 0.5 to 20 parts by weight of a rubbery polymer obtained by graft polymerization of an acid ester.