JPH0241355A - Polyetherimide-containing 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 [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.

[Conventional technology]

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, etc.

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 C% Table 1.
0-127560 Publication), ff1PDll+-polymer (Japanese Patent Application Publication No. 60-501008), rubber-modified vinyl aromatic polymer (Japanese Patent Application Publication No. 60-501010), and ethylene-glycidyl methacrylate copolymer (Japanese Patent Publication No. 60-501010) It is known to blend other polymers, such as JP 59-182847, with the resin.

[Problem to be solved by the invention]

However, the current situation is that conventional methods for improving impact resistance, including the methods described above, are not sufficiently effective.

For example, by blending ethylene-vinyl acetate copolymer EPDM terpolymer, rubber-modified vinyl and aromatic polymer, etc. with polyetherimide resin, the impact resistance of the resulting resin composition is improved, but it is not sufficient for practical use. It cannot be called a thing.

This is because the heat resistance of the ethylene-vinyl acetate copolymer itself is not necessarily good, and the 8PDM terpolymer
Rubber-modified vinyl aromatic polymers are susceptible to thermal deterioration and contain butadiene, so when molding a resin composition blended with these polymers, that is, under the temperature conditions required for molding polyetherimide resin (usually 330 to 550°C). It is thought that thermal deterioration of these components occurs when the molded product is not sufficiently improved in impact resistance.

In view of the problems in the prior art described above, the present inventors conducted intensive studies to effectively utilize the properties of polyetherimide resin and to obtain a resin composition having sufficient impact resistance. As a result, polyetherimide and polyt
By blending the ethylene-glycidyl methacrylate copolymer, which is an olefin elastomer, into a mixture with a polyester whose main component is 4-bis(hydroxymethy)cyclohexane terephthalate, it is possible to create an excellent variety of polyetherimide resins. The present invention has led to the new finding that it is possible to obtain a resin composite acid product that maintains its properties and improves its impact resistance, and is less likely to deteriorate its properties due to heat during molding. It has been completed.

That is, an object of the present invention is to provide a polyate V-imide-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 K.

[Means to solve the problem]

The polyether V imide resin-containing composition (hereinafter referred to as resin composition) of the present invention contains at least polyetherimide and poly-1,4-bis(hydroquine methyl)! Component (A) consisting of a mixture with a polyester containing /chlorhexane terephthalate as a main component, and an elastomer component (B) consisting of an ethylene-glycilla methacrylate copolymer.
),! : Consists of.

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 V bond represented by the following general formula (1) (in the above formula, R is 6 to 6). 2 only aromatic residues with 30 carbon atoms; R' is a divalent aromatic residue with 6 to 30 carbon atoms, an alkylene group with 2 to 20 carbon atoms, 2 to 20 A divalent organic group selected from the group consisting of a cycloalkylene group having 2 to 8 carbon atoms, and a polydioVganosiloxane group chain-terminated with an alkylene group having 2 to 8 carbon atoms.) , Examples of the above R include aromatic residues shown in the following formula.

The polyetherimide resin used in the present invention may be one synthesized by a well-known method or, for example, one expressed by the following formula (1).
A polymer containing a structural unit represented by K and sold under the trade name 6rffL'rffiM of the U.S. Rice 2A/Elect9F2 Co., Ltd. can be used.

The polyester containing poly-1,4-bis(hydroxymethyA/)cyclohexane terephthalate as a main component 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)
and C), the types and amounts of other components contained in these should be controlled so that the desired properties of the resulting resin composition are not impaired by the other components contained in these. It is necessary to choose appropriately.

Poly-1,4-bis(hydroxymethyA/)cyclohexane terephthalate (homopolymer) is obtained by polycondensing terephthalic acid and cyclohexane dimethanol-V by transesterification and/or esterification ff reaction. You can use what you have obtained or what you can find commercially.

Poly-1,4-bis(hydroxymethyV)cyclohexane terephthalate (homopolymer) is used. In this case, in order to obtain good impact resistance, it is desirable that K has an intrinsic viscosity [η] of (17 or more).

In order to obtain the homopolymer having an intrinsic viscosity of a7 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. You can also use methods to increase .

As the above-mentioned copolymer b), those obtained by copolymerizing cyclohexane terephthalate units with other units selected from, for example, well-known hetamines used in the synthesis of polyesters, etc. can be used.

Components that can be used in the structure of other units contained in the copolymer include (1) phthalic acid, isophthalic acid, adipic acid, cepacic acid, naphthalene-1,4-cicaVboxylic acid, naphthalene-λ6 - dicarboxylic acid and diphenyl ether v -
V-boxylic acids such as 4,4'-dicarboxylic acids, (2) Glyco-Vs such as 7'' robylene glycol, butylene glycol, neopentyl glycol, and 2,2'-bis(4-hydroxyphenyl)propane. and (3) oxyacid components such as p-oxybenzoic acid, p-hydroxybenzoic acid, and p-hydroxyethoxybenzoic acid.Other components of Cholera include cyclohexane terephthalate units. may be introduced into the reaction system at an appropriate stage during polycondensation and copolymerized.For the formation of the copolymer, methods used in ordinary polyester synthesis can be applied. The components may be used in the form of esters.

Furthermore, when used in the above forms 13) C and C), it is desirable that the intrinsic viscosity is 17 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 (2)), and low-temperature impact resistance of the resulting resin composition. Considering the expressivity under the conditions, it is preferable to use a copolymer containing 5 to 20 moyql of grindyl methacrylate. Examples of such a copolymer include Bond First E and Bond First 20 [--both manufactured by Sumitomo Co., Ltd. Commercially available products such as those manufactured by Kagaku Kogyoki Co., Ltd., and ethylene-glycidyl methacrylate copolymers synthesized by conventional methods so as to contain glycidyl methacrylate F using the above-mentioned method can be used.

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

The mixing ratio (weight ratio) of these in component (A), which is a mixture of polyester V imide and polyester whose main component is poly-1,4-bis(hydroquinemethyl)cyclohexane terephthalate, is polyate V imide/the polyester. −? , 5/(L5 to 2/8). In other words, if the amount of polyetherimide added exceeds the above range, it may be difficult to obtain sufficient impact resistance in the resulting resin composition. If not, and if the amount is less than the above range, the resin composition will not have sufficient heat resistance.

The blending amount of the elastomer component ω) with respect to the mixture component (A)K is based on 100 parts by weight of the total amount (mu+B) of the mixture component (4) and the nystomer component (B). 60 to 95 parts by weight, and 5 to 40 parts by weight of the nidistomer component (B).

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, This will impair the heat resistance of the resulting 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, each component may be separately fed into a melt mixer and melt-mixed, or two or more of each component may be fed into a mortar,
The resin composition of the present invention can be obtained by pre-mixing using a Henke M mixer, ball mill, lipo 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, poron fibers, silicon carbide fibers, and metal fibers, and fillers such as clay Vric, graphite, glass peas, alumina, and calcium carbonate. may be blended.

[Example] The present invention will be described in detail below using Examples and Comparative Examples.

In addition, the intrinsic viscosity of the polyester shown in the following example is determined by using a pheno-tetrachloroethane mixture as the solvent.
It was calculated from the results measured using phenol/tetrachloroethane=5015G (weight ratio)] at a temperature of 25°C.

Further, as an impact resistance test, a notched Izo impact test according to M8TM D256 was conducted at 23°C.

Furthermore, the flexural modulus is AEITM D-790K.

Each measurement was carried out under a load condition of 4.6 kg f /cr11'' according to heat deformation temperature plate (HDT) A8'rM D-648.

Examples 1 to 5 Polyetherimide (UIJTKM 1000, manufactured by General Electric Company) and glycol-modified poly-1,4-bis(hydroxymethy 1v)cyclohexane terephthalate 1POT () 101yq with intrinsic viscosity CL75
' (trade name, manufactured by Eastman Kodak Company) and ethylene-glycidyl methacrylate copolymer (1 Bond Fast E, trade name, manufactured by Sumitomo Chemical ■) were each uniaxially extruded m (Tp) at the compounding ratio shown in Table 1. -2s, manufactured by Thermoplastics) at 29'0°C, and the extruded resin composition strands were cooled with water and then cut into appropriate lengths to obtain resin composition pellets.

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

Using the obtained test pieces, 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 when the blending ratio of the elastomer component (m) is too low (Comparative Examples 1 and 3), the elastic modulus and heat resistance derived from polyetherimide are added to the resin composition. However, a sufficient effect of improving impact resistance could not be 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.

Table *1: %Tafmer MPOI510' (trade name, manufactured by Mitsui Petrochemical Industries ■) *2: %Tafmer MA8510'
(Product name, manufactured by Mitsui Petrochemical Industries ■) *3:% Metaprene@0-223' (Product name, manufactured by Mitsubishi Rayon ■) It is clear from the results in Table 2 that each polymer (Comparative Examples 5 to 7)
It was confirmed that these were not sufficient in improving the impact resistance of polyetherimide resin-containing compositions.

Examples 6 to 7 Using poly 1,4-bis(hydroquinmethyV)cyclohexane terephthalate% Kodar POTAmu-150' (trade name, manufactured by Eastman Kodak Company) modified with the acid moiety as polynisdel ('l! Example 6), or by preparing cyclohexane dimetatool and terephthalic acid at a ratio of 1.2 to 10 and esterifying at 260°C, and then polymerizing at 290°C under reduced pressure in the presence of a catalyst of s b, o. A resin composition test piece was obtained by injection molding the obtained polyester in the same manner as in Example 2 except for Example 7.

Table 3 shows the results of the impact test and heat distortion temperature measurement of the obtained test piece.

Table 3 [Effects of the Invention] The resin composition of the present invention contains ethylene-glycidyl in a mixture of polyetherimide and polyethylene terephthalate.
It has a structure in which an elastomer component made of a methacrylate copolymer is blended, and is obtained mainly by the properties such as good heat resistance, flame retardance, rigidity, and chemical resistance derived from polyetherimide and the effect of blending the elastomer component. Share good impact resistance.

Therefore, the present invention has made it possible to expand the use of resin compositions containing shibori etherimide to various uses, particularly those requiring high impact resistance.

Patent applicant: Mitsubishi Rayon Co., Ltd. Representative Toshio Sawa, Patent Attorney

Claims (1)

[Claims] 1) Component (A) consisting of a mixture of polyester containing polyetherimide and poly-1,4-bis(hydroxymethyl)cyclohexane terephthalate as the main component, and an elastomer component containing ethylene-glycidyl methacrylate copolymer as the main component ( B), and these components are combined into 60 to 95 parts by weight of component (A) and 100 parts by weight of the total amount (A+B) of component (A) and component (B).
) in a proportion of 5 to 40 parts by weight.