JP2869235B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition, and more particularly, to a thermoplastic resin composition having excellent toughness and flame retardancy and suitable for various electric and electronic parts, automobile parts, industrial parts and the like. The present invention relates to a plastic resin composition.

[0002]

2. Description of the Related Art Polyesters, particularly polybutylene terephthalate, have excellent heat resistance, mechanical properties and moldability, and are used in various fields. However, toughness is insufficient, and when a large amount of a flame retardant is added to impart flame retardancy, there is a problem that the toughness is significantly reduced.

[0003] As a method for improving the toughness of polybutylene terephthalate, polybutylene terephthalate disclosed in Japanese Patent Publication No. 45-22424 and the like has been added to α-olefin-polybutylene terephthalate.
Method of blending vinyl acetate copolymer, Japanese Patent Publication No. 58-
No. 47419, a method of blending an α-olefin-glycidyl methacrylate copolymer with polybutylene terephthalate, and a method disclosed in JP-A-1-204960.
And a graft copolymer obtained by grafting an alkyl (meth) acrylate to a copolymer mainly composed of an olefin unit and an epoxy group-containing unsaturated compound unit on a thermoplastic polyester represented by polybutylene terephthalate resin disclosed in A method for blending a rubber polymer is disclosed.

However, when a flame retardant is added to the resin composition obtained by these methods in order to impart flame retardancy, the toughness is significantly reduced, and the flame retardancy cannot be imparted if the amount of the flame retardant is reduced.

[0005]

SUMMARY OF THE INVENTION The present inventors have made intensive studies to solve the problems of the prior art, and as a result,
An object of the present invention, which has been completed, is to provide a thermoplastic resin composition having excellent toughness and flame retardancy.

[0006]

That is, the present invention relates to (A) 5 to 95% by weight of a polybutylene terephthalate resin having a relative viscosity of 1.7 to 3.0 and (B) a relative viscosity of 1.8 to 1.8%.
Thermoplastic copolymerized polyester resin having 3.2 to 5-9
A flame retardant is blended in an amount of 15 to 100 parts by weight with respect to 100 parts by weight of a resin mixture consisting of 5% by weight, and the thermoplastic polyester resin is terephthalic acid or an ester-forming derivative thereof and hydrogenated dimer acid or an ester thereof. It is obtained by using a forming derivative as an acid component and 1,4-butanediol as a glycol component, and in the total of the acid components constituting the resin mixture (A) + (B), of the hydrogenated dimer acid component. A thermoplastic resin composition having a ratio of 0.5 to 30 mol%.

Hereinafter, the present invention will be described in detail.

In the present invention, the polybutylene terephthalate resin used as the component (A) is an aromatic dicarboxylic acid or a diester thereof containing terephthalic acid or an ester-forming derivative thereof as a main component, and a glycol mainly comprising 1,4-butanediol. It is a polymer obtained by reacting glycol as a component by a known method.

Specifically, terephthalic acid or an ester-forming derivative thereof (eg, dimethyl terephthalate) is used as a main component, and is combined with isophthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, 4,
An aromatic dicarboxylic acid component appropriately using 4'-diphenoxyethane dicarboxylic acid, p-oxybenzoic acid, sebacic acid, adipic acid, etc., and ethylene glycol or ethylene oxide containing 1,4-butanediol as a main component , Trimethylene glycol, hexamethylene glycol, decamethylene glycol, cyclohexane dimethanol, and the like.

It is important that the polybutylene terephthalate resin used in the present invention has a relative viscosity η _rel of 1.7 to 3.0 as measured at 20 ° C. using a mixed solvent of tetrachloroethane: phenol = 2: 3. It is. η _rel is 1.
If it is less than 7, the toughness of the composition is poor, while η
_{If rel} exceeds 3.0, the rigidity becomes insufficient.

In the present invention, it is important that the blending amount of the polybutylene terephthalate resin is from 5 to 95% by weight, particularly preferably from 10 to 90% by weight. If the blending amount of the polybutylene terephthalate resin is less than 5% by weight, that is, if the proportion of the thermoplastic copolymerized polyester resin exceeds 95% by weight, the rigidity becomes insufficient. On the other hand, if the amount of the polybutylene terephthalate resin exceeds 95% by weight, that is, if the proportion of the thermoplastic copolymerized polyester resin is less than 5% by weight, the toughness becomes insufficient.

The acid component of the thermoplastic polyester resin used in the present invention mainly comprises terephthalic acid and hydrogenated dimer acid.

The hydrogenated dimer acid is obtained after separating unsaturated fatty acids from a low polymer obtained by a clay catalyst and removing by-products such as trimer acid and monomeric acid by hydrogenation, and preferably has a purity of 99% by weight or more. It is. As a preferred specific example, PRIPOL10 manufactured by Uniqema Corporation is used.
08 (36 carbon atoms, aromatic type / alicyclic type / linear aliphatic type = 9/54/37 (mol%) dimer acid), PRIPOL1009 (36/13 carbon atoms, 13/64
/ 23 (mol%) dimer acid) and PRIPLAST 300 manufactured by Uniqema as an ester-forming derivative.
8 (dimethyl ester of PRIPOL 1008). The copolymerization composition ratio of the hydrogenated dimer acid, which is a constituent component of the thermoplastic polyester resin, is not particularly limited, but is preferably 1 to 50 mol%.

As the glycol component of the thermoplastic copolymer polyester resin of the present invention, it is essential that 1,4-butanediol be the main component (for example, 70 mol% or more) in view of compatibility with the polybutylene terephthalate resin. It is.

The method for producing the thermoplastic polyester resin in the present invention is not particularly limited, and it can be carried out according to a known method. For example, terephthalic acid or an ester-forming derivative thereof, hydrogenated dimer acid or an ester-forming derivative thereof, and 1,4-butanediol are directly or simultaneously esterified or polymerized after transesterification. A method can be adopted. Various known catalyst stabilizers, modifiers, additives, and the like may be used in the polymerization, esterification reaction, and transesterification reaction.

The thermoplastic copolymer polyester resin of the present invention has a relative viscosity η _rel of 1.8 as measured at 20 ° C. using a mixed solvent of tetrachloroethane: phenol = 2: 3.
It is important that the value be ~ 3.2. If η _rel is less than 1.8, the toughness of the composition is poor, while η _rel is less than 3.
If it exceeds 2, the rigidity becomes insufficient.

The composition of the present invention comprises the above (A) and (B)
It is important that the proportion of the hydrogenated dimer acid component is 0.5 to 30 mol%, preferably 1 to 20 mol%, based on the total of the acid components constituting the above. If the proportion of the hydrogenated dimer acid component is less than 0.5 mol%, the toughness is insufficient, and if it exceeds 30 mol%, the rigidity is poor.

As the flame retardant used in the present invention, a thermoplastic resin is usually used. Brominated flame retardants are preferred, and inorganic flame retardants may be used in combination. Examples of the brominated flame retardant include aliphatic type, aromatic type, phenol type, epoxy type, bisphenol type and biphenyl type. Examples of the inorganic flame retardant include antimony trioxide, tin oxide, molybdenum oxide, zinc borate, and the like.

In the present invention, the compounding amount of the flame retardant is
It is important that the amount is 15 to 100 parts by weight based on 100 parts by weight of the resin mixture composed of (A) and (B).
8 to 80 parts by weight are preferred. If it exceeds 100 parts by weight, the tensile elongation at break and the impact strength are significantly reduced, and the toughness becomes insufficient. On the other hand, if the amount is less than 15 parts by weight, V-0 of the UL standard is not achieved, and the flame retardancy becomes insufficient.

The composition of the present invention may contain known nucleating agents, lubricants, antioxidants, ultraviolet absorbers, warpage inhibitors, coloring agents and the like, if necessary.

It is preferable that all components of the thermoplastic resin composition of the present invention are sufficiently dispersed until a final molded article is obtained. As a method for this, for example, there is a method in which a pellet-shaped resin is produced using a different-direction rotating twin-screw kneading extruder, and is provided to a molding step.

[0022]

Industrial Applicability The thermoplastic resin composition of the present invention is excellent in toughness and flame retardancy, and is suitable for various electric and electronic parts, automobile parts, and industrial parts.

[0023]

The present invention will be specifically described below with reference to examples. In addition, physical property evaluation was performed according to the following method.

Flexural modulus: ASTM D790 Tensile elongation at break: ASTM D638 Test speed 50 mm
/ Min Izod impact strength (notched, 1/4 inch): AS
TM D256 relative viscosity η _rel : solvent tetrachloroethane: phenol = 2: 3 (weight ratio), measurement temperature 20 ° C, concentration 1.000
g / dl Flammability: UL94 vertical burn test

(Production Example of Polybutylene Terephthalate Resin) Polybutylene terephthalate having relative viscosities of 1.6 and 3.1 used as a comparative example was produced as follows. 100 mol of dimethyl terephthalate, 140 mol of 1,4-butanediol, 0.03 mol of tetra-n-butyl titanate as a catalyst for transesterification and polymerization were charged into a transesterification tank, and methanol produced by heating to 210 ° C. was removed from the system. And transesterified. After the methanol was almost completely distilled off, the reaction product was transferred to a polymerization tank, and the temperature was 250 ° C. and the degree of vacuum was 0.5 mmHg over 1 hour.
And then polycondensation was carried out. The relative viscosity η _rel of the obtained polybutylene terephthalate resin was 1.6 (sample name A ′). Similarly, the relative viscosity η
A polybutylene terephthalate resin having _rel 3.1 (sample name B ') was also prepared.

(Production Example of Thermoplastic Copolyester Resin) Dimethyl terephthalate, hydrogenated dimer acid (PRIPLAST 3008, manufactured by Unichema), 1,4-butanediol, and tetra-n-butyl titanate as a transesterification and polymerization catalyst. Added with the composition shown in Table 1,
Methanol produced by heating to 10 ° C is distilled out of the system,
A transesterification reaction was performed. After the methanol distillation was almost completed, the reaction product was transferred to a polymerization vessel, brought to a temperature of 250 ° C. and a degree of vacuum of 0.5 mmHg over 1 hour, and then subjected to polycondensation. Table 2 shows the sample names and the relative viscosities η _rel of the obtained thermoplastic copolymerized polyester resins.

[0027]

[Table 1]

(Examples 1 to 3 and Comparative Examples 1 to 4) 25 parts by weight of a thermoplastic copolymer polyester resin obtained by the above method, polybutylene terephthalate resin (samples A 'and B obtained by the above method) Or PBT1 manufactured by Kanebo Co., Ltd.
19 (η _rel 1.9), PBT124 (η _rel 2.
4)) 75 parts by weight, 0.1 part by weight of an antioxidant (Irganox 1330 manufactured by Ciba-Geigy), 0.1 part by weight of nucleating agent (Hoechst wax NAW manufactured by Hoechst Japan),
And flame retardant (brominated epoxy oligomer (EBR107 manufactured by Manac) / antimony trioxide (A manufactured by Nippon Seimitsu Co., Ltd.)
(TOX-B) = 2/1 (weight ratio) mixture) 30 parts by weight were preliminarily mixed, and then melt-mixed with a 30 mm-diameter counter-rotating twin-screw extruder to obtain pellets.

After the obtained pellets were dried under reduced pressure, they were subjected to injection molding to obtain test pieces, which were subjected to physical property tests. The results are shown in Table 2.

[0030]

[Table 2]

(Examples 4 to 5, Comparative Examples 5 to 6) The thermoplastic copolymer polyester resin (sample name C) and the polybutylene terephthalate resin (PBT124 manufactured by Kanebo Co., Ltd.) obtained by the above method are shown in Table 3. And 0.1 part by weight of an antioxidant (Irganox B-225 manufactured by Ciba-Geigy) and 0.1 part by weight of a nucleating agent (Hoechst Wax OP manufactured by Hoechst Japan) with respect to 100 parts by weight of this mixture.
1 part by weight, and 40 parts by weight of a flame retardant (brominated polystyrene (Pyrocheck 68PB manufactured by Nissan Ferro) / antimony trioxide (ATOX-S manufactured by Nippon Seikosho) = 2/1 (weight ratio)) After pre-mixing, the mixture was melt-mixed with a 30 mm diameter different direction rotating twin screw extruder to obtain pellets.

After the obtained pellets were dried under reduced pressure, they were subjected to injection molding to obtain test pieces, which were subjected to physical property tests. The results are shown in Table 3.

[0033]

[Table 3]

(Examples 6 and 7, Comparative Examples 7 and 8) A thermoplastic polyester resin and a polybutylene terephthalate resin (PBT124 manufactured by Kanebo Co., Ltd.) were blended in the composition shown in Table 4, and 100 parts by weight of this mixture was used. 0.1 parts by weight of an antioxidant (Irganox 1330 manufactured by Ciba-Geigy) and a nucleating agent (Hoechst wax E manufactured by Hoechst Japan)
And a flame retardant (degabromodiphenyl ether (DE-83R manufactured by GLC) / antimony trioxide (N manufactured by Sangoku Seirensha)
o. 5) = 2/1 (weight ratio) 50 parts by weight of a mixture were added, and after preliminarily mixing, the mixture was melt-mixed with a 30 mm diameter different direction rotating twin screw extruder to obtain pellets.

After the obtained pellets were dried under reduced pressure, they were subjected to injection molding to obtain test pieces, which were subjected to physical property tests. The results are shown in Table 4.

[0036]

[Table 4]

(Example 8, Comparative Examples 9 to 11) Polybutylene terephthalate resin (PBT124 manufactured by Kanebo KK) 8
5 parts by weight, 15 parts by weight of the impact modifier shown in Table 5 or 15 parts by weight of the thermoplastic copolymer polyester resin (sample C) obtained by the above method were added, and an antioxidant (Irganox 1330 manufactured by Ciba Geigy) was added. 0.1 part by weight, a nucleating agent (Hoechst Wax NAW manufactured by Hoechst Japan) 0.1 part by weight, and a flame retardant (polypentabromobenzyl acrylate (PBB-PA manufactured by Dead Sea Bromin) / antimony trioxide (Nippon Seimitsu) ATOX-B) = 2/1
(Weight ratio) mixture) 40 parts by weight were blended, and after premixing,
The resulting mixture was melt-mixed with a 30 mm-diameter counter-rotating twin-screw extruder to obtain pellets.

After the obtained pellets were dried under reduced pressure, they were subjected to injection molding to obtain test pieces, which were subjected to physical property tests. The results are shown in Table 5.

[0039]

[Table 5]

(Example 9) 52 parts by weight of a thermoplastic copolymerized polyester resin (sample C), 48 parts by weight of a polybutylene terephthalate resin, and a flame retardant (brominated epoxy oligomer (EBR107 manufactured by Manac) / antimony trioxide (Nippon Seimitsu) ATOX-B manufactured by Minesho) = 3/1 (weight ratio)
After 30 parts by weight of the mixture were preliminarily mixed, they were melt-mixed with a 30 mm-diameter counter-rotating twin-screw extruder to obtain pellets.

After the obtained pellets were dried under reduced pressure, they were subjected to injection molding to obtain test pieces, which were subjected to physical property tests. Table 6 shows the results.

Comparative Example 12 30 parts by weight of the flame retardant used in Example 9 were blended with 100 parts by weight of a thermoplastic copolymerized polyester resin (Sample G), and pellets were obtained in the same manner. A test piece was obtained in the same manner as in Example 9 and subjected to a physical property test. The results are also shown in Table 6.

[0043]

[Table 6]

(Examples 10 to 11, Comparative Examples 13 to 14)
25 parts by weight of the thermoplastic copolymerized polyester resin (sample C) obtained by the above method, 75 parts by weight of a polybutylene terephthalate resin (PBT124 manufactured by Kanebo Co., Ltd.) and an antioxidant (Irganox 1330 manufactured by Ciba Geigy) 0.
1 part by weight, a nucleating agent (Hoechst Wax NAW manufactured by Hoechst Japan) 0.1 part by weight, a flame retardant (brominated epoxy oligomer (EBR107 manufactured by Manac) / antimony trioxide (ATOX-B manufactured by Nippon Seikosho) = 2/1 (weight ratio) mixture) with the composition shown in Table 7, and 3
The mixture was melt-mixed with a 0 mm diameter different direction rotating twin screw extruder to obtain pellets.

After the obtained pellets were dried under reduced pressure, they were subjected to injection molding to obtain test pieces, which were subjected to physical property tests. The results are shown in Table 7 together with Example 2.

[0046]

[Table 7]

Claims (1)

(57) [Claims] (1) 5-95% by weight of a polybutylene terephthalate resin having a relative viscosity of 1.7 to 3.0 and (B) a thermoplastic copolymer polyester resin 5 having a relative viscosity of 1.8 to 3.2. Resin mixture 1 consisting of .about.95% by weight
With respect to 00 parts by weight, a flame retardant is blended in an amount of 15 to 100 parts by weight. , 1,
4-butanediol is obtained as a glycol component, and the proportion of the hydrogenated dimer acid component in the total of the acid components constituting the resin mixture (A) + (B) is 0.5 to 30 mol%. A thermoplastic resin composition comprising: