JPH0474377B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a resin composition. More specifically, the present invention provides a soft material that can be used to improve the impact resistance of thermoplastic resins by blending them with thermoplastic resins, particularly thermoplastic resins having ester bonds, carbonate bonds, amide bonds, etc. in their molecules. The present invention relates to a resin composition. [Prior Art and its Problems] Conventionally, a common method for improving the impact resistance of a thermoplastic resin is to blend a rubber substance into the thermoplastic resin to modify it. The same applies to high-performance thermoplastic resins called engineering plastics, and methods of blending rubber with thermoplastic resins for the purpose of improving impact resistance have been published, for example, in Japanese Patent Publication No. 58-47419 and Kimiaki
It is disclosed in Publication No. 59-28223, etc. However, in these methods, there has not been sufficient consideration as to what kind of rubber materials should be blended to improve impact resistance, and in reality, various combinations of engineering plastics and rubber materials have been used. At present, we are searching for a combination that has impact resistance. In addition, when high-performance engineering plastics are blended with a rubber material with a relatively low elastic modulus, impact resistance improves, but the superior performance of engineering plastics such as mechanical strength, heat resistance, and chemical properties is diminished. It may be inhibited. [Problems to be Solved by the Invention] In view of the problems of the prior art as described above, the inventors of the present invention have conducted extensive research to solve these problems, and have found that thermoplastic resins, especially engineering A new resin composition that, when blended with high-performance thermoplastic resins called plastics, can improve impact resistance without reducing the mechanical strength, heat resistance, and chemical properties of the thermoplastic resin. They discovered this and completed the present invention. [Means for Solving the Problems] That is, the present invention provides (a) a material having one or more epoxy groups in one molecule, and having a flexural modulus of 10,000 kg/molecular weight at room temperature.
5 to 95 parts by weight of a copolymer of an α-olefin having ² to 20 carbon atoms or a (meth)acrylic acid alkyl ester having 2 to 36 carbon atoms and a glycidyl compound having 5 to 40 carbon atoms, and ( b) A copolymer consisting of α-olefin and α, β-unsaturated carboxylic acid, in which 5 mol% or more of the carboxyl groups contained in the copolymer are neutralized with an alkali metal salt. The present invention relates to a resin composition prepared by melt-mixing 95 to 5 parts by weight of a copolymer having a flexural modulus of 10,000 Kg/cm ² or less at room temperature. [Example] The resin composition of the present invention has one or more epoxy groups in one molecule, and has a flexural modulus of 10,000 at room temperature.
Kg/cm ² or less resin (hereinafter referred to as component (a)) 5
A copolymer consisting of ~95 parts by weight and α-olefin and α,β-unsaturated carboxylic acid, 5 mol% of the carboxyl groups contained in the copolymer.
By melt-mixing 95 to 5 parts by weight of a copolymer (hereinafter referred to as component (b)) which has been neutralized with an alkali metal salt and has a flexural modulus of 10,000 Kg/cm ² or less at room temperature, It will be done. Here, the flexural modulus as used herein refers to a value obtained by dividing the bending stress that a material receives within its elastic limit by the strain generated in the material, and is expressed in units of Kg/cm ² . The larger the value of the material, the smaller the deformation under a constant load. Component (a) used in the present invention is α- having 2 to 20 carbon atoms.
Glycidyl compounds that are copolymers of olefin or (meth)acrylic acid alkyl esters having 2 to 36 carbon atoms and glycidyl compounds having 5 to 40 carbon atoms are those containing an α-olefin group and a glycidyl group. Although any material can be used, (meth)acrylic acid, (meth)acrylic acid ether, (meth)acrylate, and (meth)acrylate oligomer containing a glycidyl group having 6 to 40 carbon atoms are usually used. Specific examples of the component (a) include ethylene-glycidyl methacrylate copolymer, ethyl acrylate-glycidyl methacrylate copolymer, butyl acrylate-allyl glycidyl ether copolymer, ethylene-allyl glycidyl ether copolymer, and ethylene. Examples include -glycidyl methacrylate-vinyl acetate terpolymer, polybutadiene with epoxidized ends, and 1,2-polybutadiene with epoxidation. Among these, ethylene, propylene, 1-butene, 1-hexene, 1-octene, etc., or combinations of two or more of these with glycidyl acrylate, glycidyl methacrylate, glycidyl cyclohexene-4-carboxylate, etc., or two or more of these Particular preference is given to using copolymers. Further, other copolymerizable components may be added to the copolymer in an amount of up to 10% by weight and copolymerized. Examples of copolymerizable components include vinyl acetate, methyl acrylate, and methyl methacrylate. In the component (a), there is one epoxy group per molecule.
The impact resistance of the thermoplastic resin can be improved by the present invention if the amount is 1 mol% or more, but it is preferable that the resin contains 1 mol% or more to improve the impact resistance when blended with the thermoplastic resin. Very good. Ten
When the amount exceeds mol%, the composition of the present invention becomes hard, and even when blended with a thermoplastic resin, the improvement in impact resistance tends to be small. Further, as the component (a), those having a bending elastic modulus of 10,000 Kg/cm ² or less at room temperature (23° C.) are used, and those having a bending elastic modulus of 100 to 4,000 Kg/cm ² are particularly preferably used. If the flexural modulus exceeds 10,000 Kg/cm ² , it is not preferable because the effect of improving impact resistance is particularly small. The component (a) is used in such a manner that it is contained in 5 to 95 parts by weight, preferably 40 to 90 parts by weight, and particularly preferably 50 to 80 parts by weight in 100 parts by weight of the resin composition of the present invention. . If the component (a) is contained in the resin composition of the present invention in an amount less than 5 parts by weight or more than 95 parts by weight, the resin composition of the present invention may not have impact resistance even when blended with a thermoplastic resin. The improvement effect is small. Component (b) above refers to α-olefin, acrylic acid, methacrylic acid, maleic acid, and other α,β-
A copolymer with an unsaturated carboxylic acid, the preferable content of α-olefin in the component (b) is 50% by weight or more, and 5% by mole or more of the carboxyl groups in the component (b). It is neutralized by an alkali metal salt. Examples of the α-olefin include ethylene, propylene, 1-butene, 1-octene, and 1-hexene, and two or more of these α-olefins may be used in combination. Furthermore, other copolymerizable components may be copolymerized with the component (b) within a range not exceeding 10% by weight. Examples of copolymerizable components include methyl acrylate, methyl methacrylate, and butyl acrylate. At least 5 mol% of the carboxyl groups contained in component (b) are neutralized with an alkali metal salt, preferably at least 30 mol%, particularly preferably at least 50 mol%. If the thermoplastic resin is neutralized, the impact resistance when the resin composition of the present invention is blended with a thermoplastic resin is greatly improved. Preferred alkali metal salts include sodium salts and potassium salts. By neutralizing the carboxyl group in the component (b) with an alkali metal salt, the resin composition of the present invention can greatly improve the impact resistance of the thermoplastic resin. In particular, those in which 30 mol% or more of the carboxyl groups are neutralized with sodium have a very remarkable effect on improving the impact resistance of thermoplastic resins. In addition, the above component (b) is similar to component (a) at room temperature (23
Those with a bending elastic modulus of 10,000 Kg/cm ² or less at temperature (℃) are used, especially those with a bending elastic modulus of 100 to 4,000 Kg/cm ²
Those are preferably used. The bending modulus is
If it exceeds 10,000 Kg/cm ² , it is not preferable because the effect of improving impact resistance is particularly small. Component (b) is used in an amount of 95 to 5 parts by weight, preferably 60 to 10 parts by weight, particularly preferably 50 to 20 parts by weight, per 100 parts by weight of the resin composition of the present invention. If it is contained in the resin composition of the present invention in an amount less than 5 parts by weight or more than 95 parts by weight, the effect of improving impact resistance is small even if the resin composition of the present invention is blended with a thermoplastic resin. The resin composition of the present invention can be obtained by melt-mixing and reacting components (a) and (b). Melt mixing temperature is 150-280℃, preferably 170-200℃
℃ is better. If the temperature is less than 150°C, the reaction will not occur quickly, and if it exceeds 280°C, gelation will occur, and even if blended with a thermoplastic resin, the effect of improving impact resistance will be small. When the resin composition of the present invention is blended with a thermoplastic resin, particularly a high-performance engineering plastic, it exhibits the effect of improving the impact resistance of the thermoplastic resin (hereinafter referred to as blended resin). As such a blend resin, a resin having an ester bond, carbonate bond, or amide bond in the molecule is particularly preferable, and specific examples include polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate, polyamides, polycarbonates, and polyacrylates. , acrylic acid ester polymer, polystyrene, polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene copolymer (ABS), and the composition of the present invention, methacrylate-butadiene-styrene copolymer (MBS), methacrylate-
These resins may also be applied with other toughening agents such as acrylonitrile-butadiene-styrene copolymers (MABS). Furthermore, the resin composition of the present invention is also highly effective in improving the impact strength of plastics reinforced with glass fibers. The resin composition of the present invention is preferably used by adding 5 to 50 parts by weight to 95 to 50 parts by weight of the above-mentioned blend resin. If the amount of the resin composition of the present invention added is less than 5 parts by weight, the effect of improving the impact resistance of the blended resin is small, and if it exceeds 50 parts by weight, the impact resistance will be reduced by increasing the amount added. There is no hope for improvement. The resin composition of the present invention contains additives commonly used in resin compositions, such as stabilizers, colorants,
Antistatic materials, heat retardants, processability improvers, etc. can also be added. Further, reinforcing materials such as glass fibers and carbon fibers, fillers such as talc, mica, glass beads, carbon calcium, etc. may also be incorporated into the resin composition of the present invention within a range not exceeding 60% by weight. A resin containing the resin composition of the present invention can be produced by various known methods, such as a method using an extruder. The resin molded article containing the resin composition of the present invention is
Since it has excellent impact resistance, it can be suitably used for housings of light electrical equipment, automobile parts, power tool bodies, etc. Next, the resin composition of the present invention will be explained in more detail based on Examples, but the present invention is not limited only to these Examples. Examples 1 to 3 Ethylene-glycidyl methacrylate copolymer (flow rate: 3.0 g/10 min (ASTM D-
1238E), glycidyl methacrylate content: 10% by weight) (hereinafter referred to as EGMA-1)
A random copolymer (MI:
1.0g/10 minutes (measured according to ASTM D-1238)
(hereinafter referred to as EMAMNA) and heated to 205° C. using a twin screw extruder (PCM-45 manufactured by Ikegu Tekko Co., Ltd.) to perform melt mixing and kneading extrusion. The resulting resin composition was blended into a blend resin as shown in Table 1, extrusion kneaded using the twin screw extruder, and a test piece was produced by injection molding.
Impact resistance was evaluated by the following method. The results are shown in Table 1. In addition, when the obtained molten mixture was extruded with xylene (refluxed for 10 hours), Example 1
Less than 5% by weight of extractables were obtained from any of the molten mixtures. (Flexural modulus) The flexural modulus of component (a) and (b) is ASTM
Measured according to D-790. (IZOD impact strength (notched)) Measured according to ASTM D-256. (Falling weight strength) Load 500g, tip radius 3/8 inch, sample thickness 3mm
Displays the half-failure height in the case of . Examples 4 and 5 Compositions of Examples 4 and 5 as shown in Table 1
Ciba Geigy Co., Ltd. product, as a stabilizer to 100 parts by weight.
The procedure was the same as in Example 2, except that 0.2 parts by weight of product number: Irganox 1010 and 0.2 parts by weight of product number: Seanox 412S manufactured by Cipro Kasei Co., Ltd. were added, and the melt-mixed mixture was dried under vacuum at 80 ° C. for 24 hours. A test piece was prepared, and its impact resistance was measured in the same manner as in Examples 1 to 3. The results are shown in Table 1. Comparative Example 1 Instead of blending the resin composition consisting of EGMA-1 and EMAMNA with PET in Example 2,
A test piece was prepared in the same manner as in Example 2, except that EGMA-1 and EMAMNA were simultaneously blended with PET, and the impact resistance was measured in the same manner as in Example 2. The results are shown in Table 2. Comparative Examples 2 and 3 Instead of blending the resin composition consisting of BA-AGE and I-2 with PET in Example 4, BA-AGE
AGE and I-2 were blended simultaneously with PET, and instead of blending the resin composition consisting of E-GMA-VA and I-2 with PET in Example 5, E-
Test pieces were prepared in the same manner as in Examples 4 and 5, except that GMA-VA and I-2 were blended simultaneously with PET, and the impact resistance was measured in the same manner as in Examples 1 to 3. The results are shown in Table 2.

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〔Effect of the invention〕

By adding the resin composition of the present invention to a thermoplastic resin, the impact resistance of the added thermoplastic resin can be greatly improved. In particular, even when the resin composition of the present invention is blended with high-performance thermoplastic resins called engineering plastics, it does not inhibit the excellent mechanical strength, heat resistance, chemical properties, etc. of engineering plastics. It has the effect of improving impact resistance.

Claims (1)

[Claims] 1 (a) having one or more epoxy groups in one molecule;
Flexural modulus at room temperature is 10000Kg/ ^cm2 or less,
5 to 95 parts by weight of a copolymer of an α-olefin having 2 to 20 carbon atoms or a (meth)acrylic acid alkyl ester having 2 to 36 carbon atoms and a glycidyl compound having 5 to 40 carbon atoms, and (b) α-olefin and , α,β-unsaturated carboxylic acid, in which 5 mol% or more of the carboxyl groups contained in the copolymer are neutralized with an alkali metal salt, and the flexural elasticity at room temperature is Copolymer 95~ with a rate of 10000Kg/ ^cm2 or less
A resin composition obtained by melt-mixing 5 parts by weight. 2. The resin composition according to claim 1, wherein the alkali metal salt is a sodium salt or a potassium salt.