JPS5849746A - polyester resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to polyester resin compositions.

Specifically, it relates to a polyester resin composition that is flame retardant and has excellent impact resistance.As a flame retardant polyester resin, diols, dicarboxylic acids or mineral esters, and aromatic diols containing noroparagens are used together. It is said that a 9-copolymer polyester resin obtained by polymerization (Japanese Patent Application Laid-Open No. 2002-120010) is used to obtain a halogen-containing aromatic diol component in order to obtain sufficient flame retardancy. When the amount is increased, there is a drawback that mechanical properties such as impact resistance deteriorate.

The present inventors have conducted extensive research to improve the impact resistance of the above-mentioned flame-retardant copolyester resin. The present invention was completed based on the knowledge 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. is obtained by copolymerizing its ester-forming derivative and a halogen-containing aromatic diol represented by the general formula %, and has a halogen content of 3 to /! The weight of copolymerized polyester fence fat is 100% and the weight of 11% is acrylic rubber.
j-20 parts by weight of the polyester resin composition.

The present invention will be explained in detail below.

J replacement) It is a copolymer with aromatic diol.

Terephthalic acid may also include other polybasic acids such as heptadalic acid, isophthalic acid, naphthalene dicarboxylic acid, adipic acid, cepacic acid, trimellitic acid, etc., at or below the JO molar scale. Examples of the ester-forming derivatives include dimethyl terephthalate and other acid esters.

As an alkylene glycol with a prime number of 0 to 10, ethylene glycol, l, 3-propanediol, /, I+
-butanediol, /, A-hexanediol, /, 1
These include polyhydroxy compounds such as glycerin, pentaerythritol, etc. with less than 30 molar! It's okay. Also, examples of its ester-forming derivatives include expanded ethylene oxide.

A halogen-containing aromatic diol is a metal compound represented by the general formula 1. For example, a halogenated bisphenol is reacted with an alkylene oxide such as ethylene oxide, propylene oxide, or an alkylene halohydrin such as epichlorohydrin. Manufactured by

Usually, upper F general formula [! ] in which R is -OH, -011
゜- group or 10H-OH,- group! But before bromine ■ OH.

is preferably chlorine; specifically, bis(4'
-(cohydroxyethoxy) -J, z-cyclophenyl]propane, co, -monobis[dar(-monohydroxypropoxy) -S, Z -romphenyl]propane% 'L cocoa[da(3-hydroxy propoxy)
-J, S-dichloropropane, co, -bis' (j-(
Cohydroxyp1 ethoxy)-1, 3. ! , &- Tetra Monk Lomphenir]
Examples include propane.

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 cap compound thereof, which is then reacted with the general formula [ 1] may be employed, such as adding a halogen-containing aromatic diol and carrying out a polycondensation reaction.

The type and amount of the halogen-containing aromatic diol used in the copolymerization are such that the halogen content of the resin in the copolymerized polyester obtained is J-'-/j weight, preferably 1-5-
IET weight and bottle selection.

If the halogen content of the copolymerized polyester resin is too low, the flame retardance will not be sufficient, and if you try to increase it too much, the mechanical properties will deteriorate, which is not desirable.
o Acrylic rubber is a rubber-like elastic material obtained by polymerization of acrylic ester or copolymerization mainly composed of acrylic ester.A typical example is acrylic ester such as butyl acrylate and a small amount of butyl methacrylate. A rubber-like polymer obtained by graft-polymerizing a graft-polymerizable monomer such as methyl methacrylate is added to a polymer obtained by polymerizing a crosslinkable hexamer such as methyl methacrylate.

Examples of the acrylic ester include butyl acrylate, methyl acrylate, ether acrylate, propyl acrylate, hexyl acrylate, coethylhexyl acrylate, and the like. ! In addition to butylene diacrylate, crosslinking monomers include
Esters of polyols and acrylic acid or methacrylic acid such as butylene dimethacrylate, trimethylolpropane trimethacrylate, vinyl compounds such as divinylbenzene, vinyl acrylate, vinyl methacrylate, allyl acrylate, allyl acrylate, diacrylate, diallyl fumarate, Examples include allyl compounds such as diallyl itaconate, monoallyl maleate, monoallyl heptamalate, and triallyl cyanurate.

In addition, the above-mentioned graft polymerizable mono! In addition to methyl methacrylate, examples of binders include methacrylic acid esters such as ethyl methacrylate, butyl methacrylate, hexyl methacrylate, coethylhexyl methacrylate, and 2-acrylic methacrylate, styrene, acrylonitrile, and the like.

This graft polymerizable monomer is partially polymerized with the above acrylic acid ester and a crosslinkable monomer to form a polymer t.
- It can also be used during production and copolymerized.

The above-mentioned acrylic rubbers include, for example, Kane Ace 7M manufactured by Kanebuchi Chemical Co., Ltd., Pitax V-4 manufactured by Hitachi Chemical Co., Ltd.
#0/, San-Ray Iris Wll Metaplay W-300, Same W-jJO, Q-M Ant Haas Co., Acryloid KM-, 7JJ.

It is also commercially available as KM-3JO.

The blending amount of acrylic rubber is 10 parts of copolymerized polyester resin.
0.5 to 20 parts by weight, preferably Fi
It is about t - tz parts by weight. 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, flame retardancy and mechanical properties such as tensile strength and bending strength may deteriorate, which is not preferable.

The method of blending acrylic rubber with copolymerized polyester resin includes a method of tri-blending pellets of copolymerized polyester resin and pellets of acrylic rubber, and a method of melt-kneading and extruding the blend using an extruder to form pellets. Well-known methods can be applied, such as the method of converting.

By containing a flame retardant such as an aromatic halide, the composition of the present invention can further improve the flame resistance, and even if this flame retardant is included, the impact resistance will not be impaired. It doesn't look like that. Polycarbonate oligomers derived from aromatic halides such as di-7-dyl halides such as te, hexabrom biphenyl, decabrom diphenyl ether, tetraprom bisphenol, tetrabrom bisphenol,
Halogenated bisphenol or its wire conductor such as tetrabromo-pisphenol-type epoxy resin, condensate of halogenated phenol such as trifluoromephenol condensate, halogenated heptal anhydride such as tetrazo-9m heptatalic anhydride Acids, polymers of halogen-containing acrylates such as polypentabrobenzyl acrylate, etc. can be used. It is recommended that these aromatic halides be used in an amount of 10 parts by weight or less, usually 7 parts by weight or less, as a halogen per 100 parts by weight of the copolymerized polyester resin. flame retardant aids, such as glass fiber, longitudinal fiber, asbestos,
Silica, alumina, silica arunna, silica magnesia, calcium silicate, calcium carbonate, glass peas,
Additives such as fillers such as 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 flammability and impact resistance, and
However, it has also been found to have negative properties, FAR dynamics, and thermal stability, and can be used for electrical and electronic parts, automobile parts, and other industrial applications by well-known molding methods such as injection molding, extrusion, and compression molding. The present invention will be specifically explained below with reference to examples, but the present invention is not limited to the following examples.

In the Examples, "1 part" and "O" are respectively rt parts by weight and [weight, It-O], and flammability is t.
TL (UnderwiseraLaborazMes
The impact resistance is A8? M D co! Production example of O-copolymerized polyester resin, which is the value of Izot impact strength R (%1, notched) measured according to 6. Too parts of dimethyl terephthalate, 11 parts of II-butanediol, 1. ．． Part 1 of 2-bis[tei-(cohydroxyethoxy)'-'t'-dipro^7enyl]propancoJ, and 0.6% of tetrabutoxytitanium/1 part of 41-butanediol fpItIIA as a catalyst. , put it in the reactor and distill out the methanol.
A transesterification reaction was carried out at 0° C. for 1 hour. Then, tetrabutoxytitanium? 0.64b/, dabutanediol solution 1f1/, J part, and j'is/, 4' of Irganox 1010 (Chino (Meijo 4J', manufactured by Geikie))
- Add 82s of butanediol slurry and mix with Wenken.
While gradually raising the temperature to j”o, the pressure was reduced from normal pressure to 0.
Polycondensation ash was carried out while lowering the temperature to 115F. Polycondensation time, bromine content, intrinsic viscosity [calyx] 0
．． Copolymerized polyester resin of tj was obtained 90 Examples 1 to 1 and Comparative Example 1 Copolymerized polyester resin produced in the above production example, butyl acrylate) 413 parts, butylene citacrylate 30
Acrylic rubber, glass fiber (manufactured by Asahi Fiber Gutsusu ■, (, dQ3MAlt4),
Tribromophenol condensate (manufactured by Versicol, Fire Masterp 3J) and antimony trioxide were added to the following 1! The mixtures were mixed in the proportions shown in 41O-0 and melt-kneaded at 210°C and extruded to form pellets.

This beret, 3. J-ounce injection molding machine (manufactured by Nichi-M Resin Kogyo, T, 8-/θθ type), combustion test piece and Ad
Using a mold for molding a test piece specified by TM, the resin temperature is controlled!
0℃, mold temperature, 10℃, injection time -0 seconds, cooling time 3
Injection molding was performed in 0 seconds.

The flammability and impact resistance of the obtained molded article were as shown in the table below.

For comparison, the results obtained when acrylic rubber was not used are also shown.

Examples 3 to 3 and Comparative Examples The same copolyester resin, acrylic rubber, tribromophenol condensate, and antimony trioxide used in Example 1 were mixed in the proportions shown in the table below.
Pelletization and injection molding were performed in the same manner as in .

The flammability and impact resistance of the obtained molded article were as shown in the table below.

For comparison, the results obtained when no acrylic rubber was blended are also shown.

Example! and Comparative Example J The same copolymerized polyester resin and acrylic rubber used in Example 1 were mixed in the proportions shown in Table 3 below, pelletized in the same manner as in Example/-pc, and injection molded. .

The flammability and impact resistance of the nine molded products obtained were 9 as shown in Table 3 below.6 For comparison, the results when no acrylic rubber was blended are also shown.

Table 3 ゛Applicant Mitsubishi Chemical Industries, Ltd. Procedural Amendment (Own #) 1930 to 2006! Uta 3rd Patent Office Commissioner Kazuo Wakasugi 1 Case Display 1981 Patent Application No. 1 Dak St
No. O 2 Name of the invention Polyester resin composition 3 Person making the amendment Applicant (5f &) Mitsubishi Chemical Industries, Ltd. 4 agents 100 (11 persons) 5 Subject of amendment Detailed description of the invention column 6 Amendment Contents of ``Example/-J and Comparative Example/~C Copolymerized polyester resin (■) produced in the above production example, butyl acrylate) A?, 7 parts, bunalenediacrylate 0.J 3 parts, and diallyl maleate 0. Acrylic rubber ■ obtained by graft polymerizing 30 parts of methyl methacrylate to a copolymer obtained by polymerizing 31s, glass fiber (
Made by Asahi fiberglass, 080JM qt4),
Tribromophenol condensate (manufactured by Versicol, Fire! Starde Jj) ■, or polypentabromobenzyl acrylate (pentabromobenzyl acrylate is dissolved in tetrapyrene glycol and polymerized using benzoyl peroxide as a catalyst) Polymer obtained by
3~//DC, bromine content (o, t%) ■, and acitemon trioxide ■ are mixed in the proportions shown in Table 1 below, and melt-kneaded and extruded at -3θC using a down-φ extruder, Pelleted.

This pellet, J! Using an injection molding machine (manufactured by Nippon Co., Ltd., Model 8-100) and a mold for molding a twisted part test piece and a test piece specified by M, the resin temperature was set at JjO.
Injection molding was performed at C1 mold temperature to C1 injection time of 10 seconds and cooling time of 30 seconds.

If not available, polybutylene terephthalate (manufactured by Mitsubishi Kasei Corporation, trademark, Nopad wool root, intrinsic viscosity 0.z s ) is used instead of the copolymerized polyester resin ■.
The results are also shown when using @ and adding a tribromophenol condensate to impart flammability.

/ /'”I(・t,;,il Ii Tabi Examples D to 4 and Comparative Example J-II Same copolyester resin as used in Example 1 ■,
Acrylic rubber ■, tribromophenol composite ■ or the one used in Example J were mixed in the proportions shown in Table 1, and Example/
It was made into peshit and injection molded in the same manner as in .

The flammability and impact resistance of the obtained molded article were as shown in Table 1 below.

For comparison, when acrylic rubber ■ was not used, and when the same polybutylene terephthalate used in Comparative Example − was used instead of copolymerized polyester resin ■,
The results when flame retardance was imparted by adding tribromophenol condensate (2) are also shown.

Example 7 and comparative example! , # were mixed in the proportions indicated, pelletized and injection molded as in Example I.

The flammability and impact resistance of the obtained molded product are as follows:
It was as shown in

For comparison, the results obtained when acrylic rubber (2) was not blended are also shown.

Table 3 ” that's all

Claims (1)

[Claims] (1) fV7 is a copolymer of its ester-forming conductor, achilene glycol or its ester-forming derivative having 1 to 10 carbon atoms, and a halogen-containing aromatic diol represented by the general formula %. 100 parts by weight of the copolymerized polyester resin with a halogen content of I-#, obtained by
A polyester tree composition containing 2 to 10 parts by weight.