JPH01315465A - Polyether-imide-containing resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition improved in impact resistance by blending a mixture of a polyimide with polyethylene terephthalate with an elastomer component consisting of ethylene-glycidyl methacrylate copolymer. CONSTITUTION:A composition obtained by blending (A) 70-95 pts.wt. mixture consisting of (A1) a polyether-imide, e.g. a polymer containing units expressed by the formula (R is 6-30C bifunctional aromatic group; R' is 6-30C bifunctional aromatic group, 2-20C alkylene group, etc.) and (A2) a copolymer of polyethylene terephthalate (homopolymer, a copolymer thereof with other monomers or blend thereof with other polymers), preferably consisting of a polymer having >=0.7 intrinsic viscosity at (9/1)-(2/8) weight ratio of the components (A1)/(A2) with (B) 5-30 pts.wt. elastomer component consisting of ethylene glycidyl methacrylate copolymer with preferably 5-20mol% glycidyl methacrylate content.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a polyetherimide-containing resin composition useful as an engineering plastic as a constituent material of electrical parts, automobile parts, etc. The present invention relates to a resin composition that effectively utilizes the characteristics of the present invention and has good impact resistance.

[Prior Art] Polyetherimide resin has excellent properties such as heat resistance, flame retardance, rigidity, and chemical resistance, and is attracting attention as an engineering plastic for use in electrical parts, automobile parts, and the like.

However, the impact resistance of polyetherimide resins is not necessarily good. Therefore, in order to enable the use of polyetherimide resins in a wide range of applications, studies have been conducted on methods for improving the impact resistance of polyetherimide resins.

For example, for the purpose of improving the impact resistance of the resin, polypropylene (Japanese Patent Publication No. 1983-501009) is added to the resin.
, ethylene-vinyl acetate copolymer (JP-A-60-12
Publication No. 7360), EPDM terpolymer (Special Publication No. 1983)
-501008 Publication), rubber-modified vinyl aromatic polymer (Japanese Patent Application Laid-Open No. 1983-501010), and ethylene-glycidyl methacrylate copolymer (Japanese Patent Application Laid-open No. 188-1982).
It is known to blend other polymers, such as No. 847, with the resin.

[Problems to be Solved by the Invention] However, the current situation is that conventional methods for improving impact resistance, including the above-mentioned methods, do not provide sufficient effects.

For example, by blending ethylene-vinyl acetate copolymer, EPDM terpolymer, rubber-modified vinyl aromatic polymer, etc. with polyetherimide resin, the impact resistance of the resulting resin composition is improved, but it is not sufficient for practical use. I can't say that.

This is because the heat resistance of ethylene-vinyl acetate copolymer itself is not necessarily good, and EPDM terpolymer,
Rubber-modified vinyl aromatic polymers and the like contain butadiene, which is easily degraded by heat. ), it is thought that thermal deterioration of these components occurs and a sufficient effect of improving the impact resistance of the molded product cannot be obtained.

In view of the problems in the prior art described above, the present inventors conducted intensive studies in order to effectively utilize the characteristics of polyetherimide resin and to obtain a resin composition having sufficient impact resistance. As a result, by blending ethylene-glycidyl methacrylate copolymer, which is a type of olefin elastomer, into a mixture of polyetherimide and polyethylene terephthalate, the excellent properties of polyetherimide resin can be maintained while impact resistance Improved sex,
In addition, the present invention was completed based on the new finding that it is possible to obtain a resin composition that is less susceptible to deterioration of properties due to heat during molding.

That is, an object of the present invention is to provide a polyetherimide-containing resin composition that can effectively utilize the excellent properties of polyetherimide resin such as heat resistance, flame retardance, and rigidity, and has improved impact resistance. There is a particular thing.

[Means for Solving the Problems] The polyetherimide resin-containing composition of the present invention (hereinafter abbreviated as resin composition) comprises at least a component (A) consisting of a mixture of polyetherimide and polyethylene terephthalate, and ethylene. - an elastomer component (B) consisting of a glycidyl methacrylate copolymer.

Examples of the polyetherimide that can be used in the resin composition of the present invention include a polymer containing a unit having an ether bond represented by the following general formula (I).

(In the above formula, R is a divalent aromatic residue having 6 to 30 carbon atoms; R' is a divalent aromatic residue having 6 to 30 carbon atoms; 2 to 20 carbon atoms; a divalent organic selected from the group consisting of an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 2 to 20 carbon atoms, and a polydiorganosiloxane group chain-terminated with an alkylene group having 2 to 8 carbon atoms. In addition, examples of the above R include aromatic residues shown in the following formula.

The polyimide resin used in the present invention may be one synthesized by a known method or, for example, rUL resin from General Electric Company of the United States containing the structural unit shown in the following formula (II).
Polymers sold under the trademark TEMJ can be used.

The polyethylene terephthalate contained in the resin composition of the present invention can be blended into the resin composition of the present invention in the following form.

a) Homopolymer b) Copolymer with other monomers C) Polymer blend with other polymers In addition, above b)
When used in form C), the types and amounts of other components contained in these should be appropriately selected so that the desired properties of the resulting resin composition are not impaired by the other components contained in these. There is a need to.

As the polyethylene terephthalate (homopolymer), one obtained by polycondensing terephthalic acid and ethylene glycol through transesterification and/or esterification reaction or a commercially available one can be used.

When using polyethylene terephthalate (homopolymer), in order to obtain good impact resistance,
It is desirable that the intrinsic viscosity [η] is 0.7 or more.

In addition, in order to obtain polyethylene terephthalate having an intrinsic viscosity of 0.7 or more, a polymer with a relatively low intrinsic viscosity is prepared, and the degree of polymerization of the polymer is further increased by a normal solid phase polymerization method to increase the intrinsic viscosity. A method of increasing the amount can also be used.

As the above copolymer b), those obtained by copolymerizing ethylene terephthalate units with other units selected from known monomers used, for example, in the synthesis of polyesters can be used.

Components that can be used to constitute other units contained in the copolymer include (1) phthalic acid, isophthalic acid, adipic acid, sebacic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-
2,6-dicarboxylic acid and diphenyl ether-4,4
Carboxylic acids such as '-dicarboxylic acid, (2) propylene glycol, butylene glycol, neopentyl glycol, cyclohexane dimetatool,
2. A component consisting of glycols such as 2'-bis(4-hydroxyphenyl)propane, and (3) p-oxybenzoic acid, p-hydroxybenzoic acid,
Examples include oxyacid components such as p-hydroxyethoxybenzoic acid. These other components may be introduced into the reaction system at an appropriate stage during the copolymerization of ethylene terephthalate units and copolymerized. For the formation of the copolymer 14, methods commonly used for polyester synthesis can be applied. Therefore, these other components may be used in the form of esters.

Furthermore, even when used in the forms b) and c) above, it is desirable that the intrinsic viscosity is 0.7 or more, similar to the homopolymer described above.

Elastomer component (B) blended into the resin composition of the present invention
As the ethylene-glycidyl methacrylate copolymer, a copolymer obtained by copolymerizing ethylene and glycidyl methacrylate according to a conventional method, a commercially available ethylene-glycidyl methacrylate copolymer, etc. can be used.

The copolymer has compatibility and adhesion with the resin constituting the matrix of the resin composition of the present invention (resin constituting the mixture component (A)), and low-temperature impact resistance of the resulting resin composition. In consideration of expressibility under the conditions, those containing 5 to 20 mol% of glycidyl methacrylate are preferred. Examples of such copolymers include BOND FAST E and BOND FAST 2C [both manufactured by Sumitomo Chemical Co., Ltd.
Commercially available products, such as those manufactured by Co., Ltd.], and ethylene-glycidyl methacrylate copolymers synthesized by conventional methods so as to contain glycidyl methacrylate in the above mole % can be used.

The blending ratio of each of the above-mentioned components in the resin of the present invention is as follows.

These mixing ratios in component (A) consisting of a mixture of polyetherimide and polyethylene terephthalate (
The weight ratio of polyetherimide/polyethylene terephthalate is preferably in the range of 9/1 to 2/8.

In other words, if the blending amount of polyetherimide is larger than the above range, the resulting resin composition will not have sufficient impact resistance, and if it is smaller than the above range, the resin composition will not have sufficient heat resistance. will not be obtained.

The amount of the elastomer component (B) to be added to the mixture component (A) is 100 parts by weight of the total amount (A+8) of the mixture component (A) and the elastomer component (B). The content is set to be 70 to 95 parts by weight, and the elastomer component (B) is set to be 5 to 30 parts by weight.

That is, if the amount of the elastomer component (B) is less than the above range, the resulting resin composition will not have sufficient impact resistance, and if it is contained in an amount exceeding the above range, the resulting resin composition will not have sufficient impact resistance. This will impair the heat resistance of the resin composition.

The resin composition of the present invention can be obtained by blending the above-mentioned components, and the method of blending each component is not particularly limited, and may be appropriately selected from common mixing methods.

For example, by feeding each component separately into a melt mixer and melt-mixing, or by feeding two or more of each component into a mortar,
The resin composition of the present invention can be obtained by premixing using a Henschel mixer, ball mill, ribbon blender, etc., and then feeding the mixture into a melt mixer and mixing with the remaining components.

The resin composition of the present invention may contain antioxidants, ultraviolet absorbers,
It can contain one or more of various additives such as lubricants, mold release agents, colorants such as dyes and pigments.

The composition may also include one or more of reinforcing materials such as glass fibers, carbon fibers, boron fibers, silicon carbide fibers, and metal fibers, and fillers such as clay, silica, graphite, glass peas, alumina, and calcium carbonate. may be blended.

[Examples] The present invention will be explained in more detail below using Examples and Comparative Examples.

In addition, the intrinsic viscosity of polyethylene terephthalate shown in the following examples is determined by using a phenol-tetrachloroethane mixture [phenol/tetrachloroethane = 50% as a solvent].
150 (weight ratio)] at a temperature of 25°C.

In addition, as an impact resistance test, ASTM D-256
A notched Izot impact test was conducted at 23°C according to the method.

Furthermore, the flexural modulus was determined according to ASTM D-790, and the heat distortion temperature (HDT) was determined according to ASTM D-648 at 4,6k.
Each measurement was carried out under a load condition of "gf/cm".

Examples 1 to 5 Polyetherimide (ULTEM 1000, manufactured by General Electric Co., Ltd.), polyethylene terephthalate with an intrinsic viscosity of 1.2 (AA-200, manufactured by Axie Co., Ltd.), and ethylene-glycidyl methacrylate copolymer (Bond First E, manufactured by Sumitomo Chemical Co., Ltd.) (manufactured by MITSUMI Co., Ltd.) were melt-mixed at 290°C using a single-screw extruder (TP-25, manufactured by Thermoplastics) at the compounding ratio shown in Table 1, and the extruded resin composition strands were cooled with water and then cut into appropriate lengths. It was cut to obtain resin composition pellets.

Next, the obtained pellet was molded using an injection molding machine (M-100, manufactured by Kakashi Seisakusho, cylinder temperature 300°C, mold temperature 80°C).
) to obtain test pieces for various evaluations.

Using the obtained test piece, an impact resistance test, flexural modulus, and heat distortion temperature were measured. The results are shown in Table 1.

Comparative Examples 1 to 4 Injection-molded resin composition test pieces were obtained in the same manner as in Example 1, except that each component was blended in the proportions shown in Table 1.

Table 1 shows the results of the impact resistance test, flexural modulus, and heat distortion temperature measurement of the obtained test piece.

As is clear from the results in Table 1, the resin compositions obtained in Examples 1 to 5 had good impact resistance, elastic modulus, and heat resistance.

On the other hand, when the blending ratio of polyetherimide is too high or the blending ratio of elastomer component (B) is too low (Comparative Examples 1 and 3), the elastic modulus and heat resistance derived from polyetherimide are Although it was possible to obtain a product, a sufficient effect of improving impact resistance was not obtained.

Furthermore, when the blending ratio of polyetherimide was too low or the blending ratio of elastomer component (B) was too high (Comparative Examples 2 and 4), the elastic modulus and heat resistance were insufficient.

Comparative Examples 5 to 7 Injection-molded resin composition test pieces were obtained in the same manner as in Example 2, except that each component shown in Table 2 was used as the elastomer component (B) instead of Bond Fast E.

Table 2 shows the results of the impact resistance test of the obtained test piece.

Comparative Example 8 Intrinsic viscosity [η] = 0 as polyethylene terephthalate
．． A resin composition test piece was obtained by injection molding in the same manner as in Example 2 except that polyethylene terephthalate No. 6 was used.

The results of the impact resistance test of the obtained test pieces are shown in Table 2. As is clear from the results of Table 2, each polymer (Comparative Examples 5 to 7) improved the impact resistance of the polyetherimide resin-containing composition. It was confirmed that the effect was not sufficient.

It was also confirmed that when polyethylene terephthalate having an intrinsic viscosity of less than 0.7 was used (Comparative Example 8), sufficient impact resistance could not be obtained.

[Effects of the Invention] The resin composition of the present invention has a composition in which an elastomer component consisting of an ethylene-glycidyl methacrylate copolymer is blended with a mixture of polyetherimide and polyethylene terephthalate, and has good heat resistance derived from polyetherimide. They share properties such as heat resistance, flame retardance, rigidity, and chemical resistance, as well as good impact resistance mainly achieved by the blending effect of the elastomer components.

Therefore, the present invention has made it possible to expand the use of resin compositions containing polyetherimide in various applications, especially those that particularly require impact resistance.

Patent applicant: Mitsubishi Rayon Co., Ltd.

Claims (1)

[Claims] 1) Component (A) consisting of a mixture of polyetherimide and polyethylene terephthalate, and an elastomer component (B) consisting of an ethylene-glycidyl methacrylate copolymer.
), and these components are added to 100 parts by weight of the total amount (A+B) of component (A) and component (B).
70 to 95 parts by weight of component (B) and 5 to 30 parts by weight of a polyetherimide resin-containing composition.