JPS5842648A - Heat-resistant resin composition having good flow characteristics - Google Patents

Abstract

PURPOSE:To provide a compsn. which has good moldability and gives moldings having excellent heat resistance and appearance, by blending a carboxylic anhydride with a blend consisting of an arom. polyether resin and an arom. vinyl compd./unsaturated dicarboxylic anhydride copolymer. CONSTITUTION:0.05-10pts.wt. carboxylic anhydride such as succinic anhydride and, if necessary, a reinforcing filler such as glass fiber are uniformly melt- mixed with 100pts.wt. blend consisting of 5-95wt% arom. polyether resin such as poly (2,6-dimethylphenylene-1,4-ether), 95-5wt% arom. vinyl compd./alpha,beta- unsaturated carboxylic anhydride copolymer such as a styrene/maleic anhydride copolymer and, if necessary, 0-90wt% impact modifier such as rubber-reinforced polystyrene, to obtain the titled compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic molding resin composition that has excellent heat resistance, impact resistance, and molding processability, and has a good appearance of molded products. More specifically, aromatic polyether resin, a resin composition formed by blending a copolymer of a vinyl aromatic compound with an α, β-, β-dicarboxylic acid anhydride, and a carboxylic acid anhydride, and resistance thereof. The present invention relates to a resin composition containing an impact strength reinforcing agent.

°゛Aromatic polyether resins have excellent mechanical properties, electrical properties, heat resistance, and good dimensional stability, so they are attracting attention as resins suitable for a wide range of applications. There is. However, its biggest drawback is that it has poor moldability and impact resistance. As a method to compensate for these shortcomings, Japanese Patent Publication No. 43-17812 and Japanese Patent Publication No. 49
No. 98858 and the like proposes blending polystyrene or rubber-reinforced polystyrene with an aromatic polyether resin.

Polystyrene and aromatic polyether resins have very good compatibility, and resin compositions made from the polystyrene product have excellent physical properties and are industrially produced in large quantities. On the other hand, styrene copolymers such as styrene-acrylonitrile copolymer and styrene-7crylonitrile monodetadiene copolymer do not have good compatibility with aromatic tetra-ether resins, but are This resin composition has major drawbacks such as poor impact strength and delamination in molded products, and no resin composition has been obtained for practical use. It is well known that there is a large difference in compatibility between polystyrene and styrene copolymers with aromatic polyether resins.

Furthermore, in JP-A-52-128947, a composition consisting of a copolymer of a vinyl aromatic compound and an α,β-unsaturated dicarme/acid anhydride and an aromatic polyneedle resin is disclosed. It is disclosed that a higher heat deformation temperature can be provided compared to a resin composition consisting of an ether resin. However, vinyl aromatic compounds and α.

A resin composition made of a copolymer with β-unsaturated dicarboxylic acid anhydride and an aromatic polyether resin has remarkable moldability compared to a resin composition made of polystyrene and an aromatic polyether resin. In addition, the appearance of the molded product is also significantly inferior.

The present inventors have found excellent molding processability, molded product appearance, and
As a result of intensive research into molding materials that have both high heat distortion temperature and strength, we found aromatic polyether resins, vinyl aromatic compounds, α,β-unsaturated dinormenic anhydride polymers, and carzan. Compositions obtained by uniformly melt-mixing acid anhydrides impair molding processability and appearance of molded products (5) (4.

It was possible to greatly increase the heating deformation temperature without causing any damage, and also to improve the strength.

The present invention relates to a resin composition comprising an aromatic polyether resin, a copolymer of a vinyl aromatic compound, an α, β-, β-dicarboxylic acid anhydride, and a carboxylic acid anhydride, and The present invention provides a resin composition containing an impact strength reinforcing agent.

The resin composition of the present invention exhibits a much higher heating deformation temperature without impairing moldability than a resin composition made of polystyrene and aromatic polyether resin, and also exhibits a much higher heat deformation temperature than a resin composition made of polystyrene and aromatic polyether resin. Much better molding processability and molded product appearance than resin compositions that do not contain vinyl aromatic compounds, α, β-unsaturated dinormenic anhydride polymers, and aromatic polyether resins. , and the strength is further improved. This is surprising because there is no prior knowledge that blending a small amount of carboxylic acid anhydride significantly improves the moldability and appearance of the molded product as described above. As a specific example, when (6) luponic acid anhydride is blended into a composition consisting of polystyrene and aromatic polyether, no effect such as improvement in moldability is observed. The remarkable effects of molding processability and molded product appearance obtained when blending the carboxylic acid anhydride of the present invention are due to the combination of α,β-unsaturated dinormenic anhydride and aromatic polyether resin. Those found in certain combinations of compositions.

In the present invention, the method for blending carmenic anhydride is as follows:
Method of blending when all components are uniformly mixed at the same time, method of pre-mixing with aromatic & IJ resin and processing, method of mixing with aromatic polyether resin and polymer of vinyl aromatic compound Examples include a method in which the resin is left as is, and a method in which it is added to a solution system of the aromatic polyether resin.

Examples of the carboxylic anhydride that can be used include succinic anhydride, benzoic anhydride, acetic anhydride, maleic anhydride, butyric anhydride, cinnamic anhydride, and phthalic anhydride. The amount of carboxylic anhydride added is based on 100 parts by weight of a resin consisting of an aromatic polyether resin and a copolymer of a pi-nyl aromatic compound and an α, β-, β-dicarboxylic anhydride. , 0.05 to 10 parts by weight, preferably 0.2 to 5 parts by weight.

The aromatic polyethylene resin referred to in the present invention has the following general formula: R3 and R4 are the same or different alkyl groups, 'aryl groups, halogens, hydrogen, etc. residues, and n represents the degree of polymerization. Hail Ding. ) (2,6-dimethylphenylene-1).
．． 4-ether), l'j(2゜6-diethylphenylene-1,4-ether), Isu(2,6-cyclophenylene-1,4-nifyl), -I')(2 ,6-dif
romphenylene-1,4-ether), poly(2-methyl-6-ethylphenylene-1,4-ether), &1
J (2-chloro6-methylphenylene-1,4-ether), poly(2-methyl-6-isonolopylphenylene-1,4-ether), poly(2,6-cy n-
f lovylphenylene-1,4-ether), I') <2
--f rom-6-methylphenylene-1゜4-ether), poly(2-chloro-6-bromphenylene-1,4
-ether), poly(2-chloro-6-ethylphenylene-1,4-ether), $ 17 (2-methylphenylene-1,4-ether), /IJ (2-/lorphenylene-1,4-ether) , / 17 (2-phenylphenylene-1,4-ether)1. telJ(2-
methyl-6-phenylphenylene-1,4-ether)
, poly(2-bromo-6-tzenylphenylene-1.4
-ether), poly(2,4'-methylphenylphenylene-1,4-ether), poly(2,3,6-drimethylphenylene-1,4-ether), poly(2,3-
dimethyl-6-ethylphenylene-1,4-ether)
copolymers thereof and vinyl aromatic compound graft copolymers thereof. The vinyl aromatic compound-grafted aromatic polyether resin referred to in the present invention refers to the above-mentioned aromatic polyether resin (9) as vinyl aromatic compounds such as styrene, α-methylstyrene, methylstyrene, dimethylstyrene, vinyltoluene, It is a copolymer obtained by graft polymerization of t-f tyrstyrene, chlorostyrene, etc.

Vinyl aromatic compounds used in the present invention and α, β
The copolymer with 4-unsaturated dicarboxylic acid anhydride contains non-t
rubber-reinforced copolymers and impact-resistant rubber-reinforced copolymers. Generally, the copolymer used in the present invention can be produced by conventional bulk polymerization, suspension polymerization, solution polymerization, or emulsion polymerization techniques that utilize radical polymerization. Furthermore, the copolymer used in the present invention is composed of 2 to 40 parts by volume of α,β-saturated dicarboxylic acid anhydride, 98 to 60 parts by weight of a vinyl aromatic compound, and 0 to 50 parts by weight of rubber. However, monomers copolymerizable with styrene such as methyl methacrylate, acetate, decyl acrylate, acrylonitrile, etc. can be introduced within a range that does not impede compatibility with the aromatic polyether resin. .

(10) Vinyl aromatic compounds forming the copolymer used in the present invention include styrene, orthomethylstyrene, paramethylstyrene, dimethylstyrene, metaethylstyrene,
Chlorstyrene, isopropylstyrene, terjarisotylstyrene, alpha-methylstyrene, ethylvinyltoluene, or mixtures thereof are used.

Also, α forms the copolymer used in the present invention.

The β-unsaturated dicarzanoic anhydride has the following formula (where R1,
R2 represents hydrogen, an alkyl group, an alkenyl group, a cycloalkyl group, a phenyl group, or an alkylene group. ) can be expressed as Examples include maleic anhydride, citraco/# anhydride, itaconic anhydride, and the like.

Preferred copolymers that can be used in the present invention are styrene-
These are maleic anhydride copolymer and rubber-containing styrene-maleic anhydride copolymer. Typical resins available on the market include Dilarc 262 manufactured by Arco Polymer Co., Ltd.
(non-rubber reinforced, contains about 10% maleic anhydride) and Dilarc 250 (about 10% rubber, about 10% maleic anhydride)
%).

As the impact strength reinforcing agent referred to in the present invention, graft copolymers obtained by graft polymerizing monomers having a vinyl aromatic compound as a main component to imimetic polymers and various thermoplastic elastomers are preferable.

The graft copolymer obtained by graft polymerizing a monomer containing a vinyl aromatic compound as a main component to an imime-like polymer as referred to in the present invention refers to a graft copolymer obtained by graft polymerizing a monomer containing a vinyl aromatic compound as a main component to a latex-like rubber-like polymer. A polymer obtained by graft polymerization, a rubber-like polymer, is dissolved in a solvent containing a vinyl aromatic compound as a main component, and the solution is subjected to bulk polymerization 1. Polymers obtained by polymerization using methods such as solution polymerization or suspension polymerization! To tell. Examples of the imimetic polymer used here include polybutadiene, styrene-butadiene copolymer, ethylene-propylene copolymer, polyacrylic acid (11) ester, and polystyrene. Examples of the vinyl aromatic compound include styrene, orthomethylstyrene, paramethylstyrene, dimethylstyrene, isozolobylstyrene, tertiary-butylstyrene, alpha-methylstyrene, ethylvinyltoluene, etc., which are used together with the vinyl aromatic compound. Monomers include acrylic esters, methacrylic esters, acrylonitrile, methacrylonitrile, methacrylic acid, acrylic acid, etc., and these monomers can be used within a range that does not impede compatibility with the aromatic polyether resin. used in

Although commercially available high-impact polystyrene can also be used as an impact strength reinforcing agent, preferred graft copolymers are those with a high content of rubbery polymers, preferably im The t content of the polymer is 10
It is more than heavy.

The particle size of the dispersed rubber in the graft copolymer ranges from small particles obtained by emulsion polymerization to large particles obtained by bulk polymerization, solution polymerization, and suspension polymerization (13) (12). Can be used.

The thermoplastic elastomer referred to in the present invention includes a styrene-butadiene block copolymer, a hydrogenated styrene-butadiene block copolymer, an ethylene-zorogylene elastomer, a styrene-grafted ethylene-propylene elastomer, a polyester elastomer, and the like. Styrene
As the butadiene block copolymer, any of the AB type, ABA type, MUCHIPER type, and radial teleblock type can be used.

Incidentally, the graft copolymer and the elastomer may be used alone or in combination as the impact reinforcing agent. The impact strength reinforcing agent can be added at either the initial stage or the final stage.

The resin components in the present invention, that is, the aromatic polyether resin, the copolymer of a vinyl aromatic compound and an α,β-unsaturated dicarboxylic acid anhydride, and the impact strength reinforcing agent may be combined with each other in any ratio. However, from the balance of the physical properties of the composition, the amount of aromatic polyether (14) resin in the resin composition is between 5 and 95%, and the vinyl aromatic compound and α.

Preferably, the copolymer with β-unsaturated dicarboxylic anhydride is contained in an amount of 5 to 95% by weight, and the impact strength reinforcing agent is contained in an amount of 0 to 90% by weight. Furthermore, a rubber-like polymer in a copolymer of a rubber-reinforced vinyl aromatic compound and an α,β-unsaturated unsaturated dinorhydride, a co9omal polymer in a styrenic compound graft copolymer, and The resin composition of the present invention contains 0 to
! Most preferably, the content is 10% by weight. If the content of the rubbery polymer is too large, the heat resistance and rigidity of the resin composition will decrease, which is not preferable.

As mentioned above, aromatic polyether resin, vinyl aromatic compound and α,β-unsaturated radical? The resin composition of the present invention comprises a copolymer with carboxylic acid anhydride and carboxylic acid anhydride, and the resin composition of the present invention further contains an impact strength reinforcing agent. The balance between heat resistance, moldability, appearance of the molded product, and strength is significantly better than that of the resin composition corresponding to the above which does not contain the above resin composition.

The present invention is not limited in any way by the method of obtaining the mixed resin composition. As a method, an extruder, a roll mixer, a Banbury mixer, a melt kneading method, etc. can be used.

The resin composition of the present invention can contain a reinforcing filler. As the reinforcing filler, glass fiber, carbon fiber, asbestos, wollastonite, calcium carbonate, talc, mica, zinc oxide, titanium oxide, potassium titanate, etc. are used. The filler is preferably used in an amount of 5 to 50% by weight of the entire composition. In particular, when filled with glass fiber, a product with an excellent balance of heat resistance, moldability, and strength can be obtained.

Further, the resin composition of the present invention can also contain a flame retardant and a plasticizer. As the refueling agent or plasticizer, phosphorus compounds such as triphenyl phosphate, halodane compounds,
For example, common flame retardants and plasticizers such as decabromodiphenyloxy-P are used (15).

In addition, other additives such as plasticizers, colorants, stabilizers, etc. may be included in the resin composition, and other additives, such as other polymers,
For example, polyethylene, polyzolopyrene, boriamy,
Polyester and the like can be mixed in an amount that does not impair properties such as mechanical properties.The preferred amount of these additive resins is 20% by weight or less.

The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto. The part is the weight part.

In addition, physical properties were measured using the following test methods.

Heating deformation temperature: J engineering 13- to -6871 melt-y low 1/-): Compliant with A8TM-D-12 8 (250°C, 1oklI load) Gloss [: Reflectance at an incident angle of 60°C.

Tensile strength, elongation: J El-Ni-6871 Bending strength 2 bending modulus: ASTM-D-790 (17) (16) IdeP impact strength: J-Ni-6871 Example-1
~2 η8P10 =0.64 (0.5gr/100a
Poly<2,6-dimethylphenylene-1,4-ether) and DiLark 232 (2.6-dimethylphenylene-1,4-ether)
A styrene/~maleic anhydride copolymer containing approximately 10% maleic anhydride and benzoic anhydride (manufactured by Arp-Rimmer Co., Ltd.) were mixed in the ratios shown in Table 1, using a vented extruder. A pellet-shaped resin composition was obtained by melt-mixing. Next, test pieces were made by injection molding and physical properties were measured. The results are shown in Table 1.

Comparative Example 1 In Example 1, a resin composition to which benzoic anhydride was not added was tested in the same manner as in Example 1. The results are shown in Table 1.

It is clear from Examples 1 and 2 and Comparative Example 1 that the composition of the present invention to which carbic acid anhydride is added significantly improves melt 70-rate, gloss and tensile strength.

(18) Comparative Examples-2, 6 Bo! used in Example-2. J (2,6-dimethylphenylene y-1,4-ether)tostyron ■68.5 (
Asahi Dow Co., Ltd., polystyrene) and benzoic anhydride secondary
They were mixed at the ratio shown in the table and tested in the same manner as in Example 2. The results are shown in Table 2. Example 2 Poly(2
, 6-dimethylphenylene-1,4-ether)tostyrene-maleic anhydride copolymer does not have the same effect as when benzoic anhydride is added. Generally, there are many changes in color tone due to the addition of additives, but there is no difference in color tone between Example 2 and Comparative Example 3.
The resin composition of the present application does not cause any problems in terms of color tone.

Example 6 60 parts of poly(C2,6-dimethylphenylene-1,4-ether), 40 parts of im-reinforced polystyrene (produced by solution polymerization and containing 12% by weight of dispersed im particles) and anhydrous resin After mixing 1 part of acid, melt mixing in an extruder,
A pellet-shaped resin composition was obtained. 70 parts of the obtained pelletized resin composition, 230 parts of Dicey 2023, and 1 part of Irganox 107<S (manufactured by Ciba Geyer, phenolic antioxidant) as a stabilizer were mixed, and the mixture was melt-mixed using an extruder. A pellet-shaped resin composition was obtained.

The composition was injection molded to prepare test pieces, and the physical properties were measured. Table 3 shows the results.

Example 4 In Example 3, benzoic anhydride was added instead of succinic anhydride, and a resin composition was obtained in the same manner.The physical properties of the resin composition were measured, and the results shown in Table 6 were obtained.

Example-5 In Example-3, instead of poly(2,6-dimethylphenylene-1,4-ether), poly(2,6-
A styrene-grafted poly(2,6-dimethyl (19) A resin composition was similarly obtained. Measuring its physical properties
The results shown in the table were obtained.

Comparative Example 4 In Example 6 or 4, a resin composition without the addition of cono-lambda acid anhydride or benzoic anhydride was obtained, and the physical properties were similarly measured and the results shown in Table 3 were obtained.

Comparing Examples 6 and 4 with Comparative Example 4, it is found that the resin composition of the present invention to which carbonaceous anhydride is added has a large door opening even when it is blended with im-reinforced polystyrene.
-Glossiness and W411 properties are clearly improved. Further, Example 5 in which styrene graft poly(2,6-dimethylphenylene-1,4-ether) was blended also showed poor C.

Example 6 Using rubber (strong styrene-maleic anhydride combination), '4j1. Nine cases - 6 and (2
1) (20) A resin composition was obtained by the same mixing operation. Table 4 shows the results of measuring its physical properties.

Example 7 In Example 6, a resin composition was further added with 5 parts of Kraton G-1650 (hydrogenated styrene-butadiene block copolymer, manufactured by Shell Co., Ltd.). , 4th
The physical properties shown in the table were obtained.

Comparative Example 5 In Example 6, a resin composition without the addition of succinic anhydride was obtained, and its physical properties were similarly measured. Table 4 shows the results. - Comparison between Example 6 and Comparative Example 5 θ) Even when the im-reinforced styrene-maleic anhydride copolymer is blended, the effect of carboxylic anhydride is clear. Furthermore, as shown in Example 7, by cooling Kraton G-1650 as a thermal 0T plastic elastomer (a resin composition of the present invention with significantly improved impact resistance can be obtained).

Practical example-8, je'J (2,6-dimethylphenylene-1,4-(
22) Table 2 (25) (24) (26) Table 4 Table 5 Table 111250℃, 214-Load agent Masao Miyake and 1 other person

Claims (1)

[Claims] 1. (A) aromatic & IJ ether resin; (B)
) A thermoplastic resin composition comprising a copolymer of a vinyl aromatic compound and an α,β-unsaturated dinorhydride, and (Cl carboxylic anhydride. 2. 5 to 95% by weight of (A) and (Bl is 95~
5 weight - resin ((A) + (Bl) 100
Carnic acid anhydride'V O, 05-10 based on parts by weight
The composition according to claim 1, wherein the composition is blended in parts by weight. 6. The composition according to claim 1, wherein the aromatic polyether resin is poly(2,6-dimethylphenylene-1,4-ether). 4. The composition according to claim 1, wherein the aromatic polyether resin is a styrene compound GRA7TOBORI (2,6-dimethylphenylene-1,4-ether). 5. The composition according to claim 1, wherein (B) is a styrene-anhydrous maleic monomer. 6. The composition according to claim 1, wherein (B) is a male-reinforced styrene-maleic anhydride copolymer. Z Cal? 2. The composition according to claim 1, wherein the succinic anhydride is succinic anhydride. 8. The composition according to claim 1, wherein the carboxylic anhydride is benzoic anhydride or phthalic anhydride. 9. A thermoplastic resin composition containing composition K according to claim 1 and further containing an impact strength reinforcing agent. 10. The composition according to claim 9, wherein the impact strength reinforcing agent is im-reinforced polystyrene. 11. The composition according to claim 9, wherein the impact strength reinforcing agent is a thermoplastic nidistomer. 12. 5 to 95% by weight of (A) - 5 to 95% by weight of (B), 0 to 90% by weight of impact strength reinforcing agent, and further resin (
A+B) 0.0 part of carnic acid anhydride per 100 parts by weight
The composition according to claim 9, which contains 5 to 10 parts by weight. 16. A thermoplastic W11m resin composition further comprising a reinforcing filler added to the composite acid according to claim 1 or 9. 14. The composition according to claim 16, wherein the reinforcing filler is glass fiber. 15. The glass fiber reinforced resin composition according to claim 14, which comprises 50 to 95 weight of the resin composition according to claim 1 or 9 and 50 to 5 weight of glass fibers.