JPS63165448A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition for providing a resin composition, capable of improving impact resistant by blending with a high-performance thermoplastic resin and suitable as housings, etc., for light electrical appliances, etc., by blending a specific resin having epoxy groups with a specific copolymer in a specific proportion. CONSTITUTION:A composition obtained by melt blending (A) 5-95pts.wt., preferably 50-80pts.wt. resin, e.g. ethylene-glycidyl methacrylate copolymer, etc., having one or more epoxy groups in one molecule and <=10,000kg/cm<2>, preferably 100-4,000kg/cm<2> flexural modulus of elasticity at room temperature with (B) 95-5pts.wt., preferably 50-20pts.wt. copolymer, consisting of an alpha-olefin and alpha,beta-unsaturated carboxylic acid and having >=5mol% contained carboxyl groups neutralized into alkali metal salts and <=10,000kg/cm<2>, preferably 100-4,000kg/cm<2> flexural modulus of elasticity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial 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.

[Conventional technology 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 is true for high-performance thermoplastic resins called engineering plastics.
A method of blending rubber with the thermoplastic resin for the purpose of improving impact resistance is disclosed in, for example, Japanese Patent Publication No. 47419/1982 and Japanese Patent Publication No. 28223/1989.

However, these methods have not sufficiently investigated what type of rubber should be blended to improve impact resistance, and in reality, various combinations of engineering plastics and rubber 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 engineering plastics have superior properties such as mechanical strength, heat resistance, and chemical properties. may be inhibited.

[Problems to be Solved by the Invention] Therefore, in view of the problems of the prior art as described above, the present inventors have conducted intensive research to solve these problems, and have found that thermoplastic resins, especially engineering We have created a completely new resin composition that, when blended with high-performance thermoplastic resins called plastics, improves impact resistance without reducing the mechanical strength, heat resistance, and chemical properties of the thermoplastic resin. This discovery led to the completion of the present invention.

[Means for solving problems]

That is, the present invention has one or more ω epoxy groups in one molecule, and has a flexural modulus of elasticity at chamber R of 10,000 kg/
A copolymer consisting of 5 to 95 parts by weight of a resin having a cd or less, a curved α-olefin, and an α,β-unsaturated carboxylic acid.
The present invention relates to a resin composition obtained by melt-mixing 95 to 5 parts by weight of a copolymer whose mol% or more is neutralized with an alkali metal salt and whose flexural modulus at room temperature is 10,000 kg/ci or less.

〔Example〕

The resin composition of the present invention contains 5 to 95 parts by weight of a resin containing one or more epoxy groups in one molecule and having a flexural modulus of 10,000 kg/cJ or less at room temperature (hereinafter referred to as a "component") and α- A copolymer consisting of an olefin and an α,β-unsaturated carboxylic acid, in which 5 mol% or more of the carboxyl groups contained in the copolymer have been neutralized with an alkali metal salt. Flexural modulus is lQOQOkg /
Copolymer having cJ or less (hereinafter referred to as surface component) 95~
It is obtained by melt-mixing 5 parts by weight.

Here, the flexural modulus as used herein refers to the value obtained by dividing the bending stress experienced by a material within the elastic limit by the strain generated in the material, and is expressed in the unit of kg/cI#. Materials with a large value have a small deformation under a constant load.

The ω component used in the present invention refers to a resin having an epoxy group synthesized by the reaction of a compound having an epoxy group, a glycidyl ether group, a glycidyl ester group, a glycidyl amine group, or a nitrogen-containing heterocycle with epichlorohydrin. As such resin, α- having 2 to 20 carbon atoms is used.
Examples include copolymers of olefins or (meth)acrylic acid alkyl esters having 2 to 36 carbon atoms and glycidyl compounds having 5 to 40 carbon atoms. As the glycidyl compound, any compound containing an α-olefin group and a glycidyl group can be used, but (meth)acrylic acid and (meth)acrylic acid containing a glycidyl group having 6 to 40 carbon atoms are usually used. Acrylic acid ether, (meth)acrylate, (meth)acrylate oligomer, etc. are used.

(Specific examples of the ω component include ethylene-glycidyl methacrylate copolymer, ethyl acrylate-glycidyl methacrylate copolymer, butyl acrylate-allyl glycidyl ether copolymer, ethylene-allyl glycidyl ether copolymer, ethylene- Examples include glycidyl methacrylate-vinyl acetate terpolymer, polybutadiene epoxidized at both ends, epoxidized 1,2-polybutadiene, etc. Among these, ethylene, propylene, L-butene, ■-hexene, ■-octene, etc. It is particularly preferable to use a copolymer of two or more of these with glycidyl acrylate, glycidyl methacrylate, glycidyl cyclohexene-4-carboxylate, etc. or a copolymer of two or more of these.
Other copolymerizable components may be added and copolymerized in the above range. Examples of copolymerizable components include vinyl acetate, methyl acrylate, and methyl methacrylate.

If component (a) contains one or more epoxy groups in one molecule, the impact resistance of the thermoplastic resin can be improved according to the present invention, but preferably 1 mol% of the epoxy group is present in the resin.
The above properties are good for improving impact resistance when blended with a thermoplastic resin. If it exceeds 10 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.

In addition, for the (ω component), those having a bending elastic modulus of 10,000 kg/cd or less at room temperature (23°C) are used, and those having a bending elastic modulus of IOθ to 40QO kg/c- are particularly preferably used. Flexural elastic modulus ga loooookg /
If it exceeds ci, the effect of improving impact resistance is particularly small, which is not preferable.

The above-mentioned components are used in such a manner that they are contained in an amount of 5 to 95 parts by weight, preferably 40 to 90 parts by weight, particularly preferably 50 to 80 parts by weight, per 100 parts by weight of the resin composition of the present invention. If the above (ω component) 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, impact resistance will be improved even if the resin composition of the present invention is blended with a thermoplastic resin. The effect is small.

The above component is a copolymer of α-olefin and acrylic acid, methacrylic acid, maleic acid, or other α,β-unsaturated carboxylic acid, and the preferable content of α-olefin in the component is is 50% by weight or more, and 5 mol% or more of the carboxyl groups in the component (i) is neutralized with an alkali metal salt.

The α-olefins include ethylene, propylene,
■-Butene, 1-octene, 1-hexene, etc. may be mentioned, but two or more of these α-olefins may be used in combination.

Furthermore, other copolymerizable components may be copolymerized with the above-mentioned (middle) component within a range not exceeding 10% by weight. Examples of copolymerizable components include methyl acrylate, methyl methacrylate, and butyl acrylate.

The carboxyl group contained in the +b> component is 5
When the resin composition of the present invention is neutralized with an alkali metal salt in an amount of mol % or more, preferably 30 mol % or more, particularly preferably 50 mol % or more, the resin composition of the present invention is neutralized with an alkali metal salt. It is good because it greatly improves impact resistance when blended with plastic resin. Preferred alkali metal salts include sodium salts and potassium salts. By neutralizing the carboxyl group in the above component (middle) 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 of improving the impact resistance of thermoplastic resins.

In addition, as with the (ω) component, the (middle) component is at room temperature (23°
Those with a bending elastic modulus of 10,000 kg/cm2 or less in C) are used, especially those with a bending elastic modulus of 100 to 4,000 k
g/cd is preferably used. If the flexural modulus exceeds 10,000 kg/cd, it is not preferable because the effect of improving impact resistance is particularly small.

The above-mentioned music component is contained in an amount of 95% in 100 parts by weight of the resin composition of the present invention.
It is used in an amount of up to 5 parts by weight, preferably 60 to IO parts by weight, particularly preferably 50 to 20 parts by weight. 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 will be 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 the component (a) and the surface component.

The melt mixing temperature is 150 to 280°C, preferably 17
The temperature is preferably 0 to 200°C. If the temperature is less than 150°C, the reaction will not be carried out quickly, and if it exceeds 280°C, gelation will occur, and even if the thermodynamic resin is blended with the 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 high-performance engineering plastics, 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, a carbonate bond, or an amide bond in the molecule is particularly preferable, and specific examples thereof include polyesters such as polyethylene terephthalate (PUT) and polybutylene ethylene phthalate, polyamides, Polycarbonate, polyacrylate, acrylic acid ester polymer, polystyrene, polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene copolymer (ABS), and further the composition of the present invention can be used as a methacrylate-butadiene-styrene copolymer (MBS). , methacrylate-acrylonitrile-butadiene-styrene copolymers (MABS) may be applied to these resins along with other toughening agents. 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 a blend resin 95 as described above.
It is preferable to add 5 to 50 parts by weight to 50 parts by weight. The amount of the resin composition of the present invention added is 51 iL
When the amount is less than 50 parts by weight, the effect of improving the impact resistance of the blend resin is small, and when it exceeds 50 parts by weight, it is not possible to improve the impact resistance by simply increasing the amount added.

The resin composition of the present invention may also contain additives commonly used in resin compositions, such as stabilizers, colorants, antistatic agents, flame retardants, and processability improvers. Further, reinforcing materials such as glass fibers and carbon fibers, fillers such as talc, mica, glass beads, calcium carbonate, etc. may also be incorporated into the resin composition of the present invention within a range not exceeding 80% 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.

A resin molded article containing the resin composition of the present invention has excellent impact resistance, and therefore can be suitably used for housings of light electrical equipment, automobile parts, power tool bodies, and the like.

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 1-3 Ethylene-glycidyl methacrylate copolymer (flow rate: 3.Og/10 minutes (ASTMD-12
38E), glycidyl methacrylate content: 10% by weight) (hereinafter referred to as BGMA-1) 75 parts by weight, ethylene component 87ffi amount, methacrylic acid component 8.5% by weight, and sodium methacrylate component 6.5%.
Random copolymer consisting of wt% (old: 1.Og/
10 minutes (measured according to ASTM D-1238)) (hereinafter referred to as EMAMNA) and 25 parts by weight, and heated at 205°C using a twin screw extruder (PCM-45 manufactured by Ikegu Iron Works).
Melt mixing and kneading and extrusion were performed by heating to .

The resulting resin composition was blended into a blend resin as shown in Table 1, extruded and kneaded using the twin-screw extruder, and a test piece was produced by injection molding, and its impact resistance was evaluated using the following method. . The results are shown in Table 1. When the resulting molten mixture was extracted with xylene (refluxed for 10 hours), less than 5ffiffi% of the extract from any of the molten mixtures of Examples 1 to 3 was obtained.

(Bending elastic modulus) The bending elastic modulus of the (ω component and mountain) component is ASTM D
-790.

(IZOD impact strength (with notch)) AS
Measured according to TM D-258.

(Falling weight strength) Displays the half height of failure when the load is 500 g, the tip radius is 3/8 inch, and the sample thickness is 3 inches.

Examples 4 and 5 100 parts by weight of the compositions of Examples 4 and 5 shown in the m1 table were added with 0.2 parts by weight of Nil Ganox 10100, manufactured by Ciba-Geigy Masu Co., Ltd. and product number Niji-Ganox, manufactured by Cipro Kasei #, as stabilizers. Test pieces were prepared in the same manner as in Example 2, except that 0.2 parts by weight of Knox 412S was added and the mixture was melt-mixed and dried under vacuum for 124 hours at 80'C. It was measured in the same manner. The results are shown in Table 1.

Comparative Example 1 Instead of blending the resin composition consisting of BGMA-1 and EMAMNA with PET in Example 2, ECMA-1
A test piece was prepared in the same manner as in Example 2, except that EMAMNA and EMAMNA were blended together 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 1-2 with PET in Example 4, BA-AGE and 1-2 were blended into PET.
2 and PET at the same time, and in Example 5, E-GM
A resin composition consisting of A-VA and 1-2 is PET i,
Near 'L/Instead of: E-GMA-VA
Test pieces were prepared in the same manner as in Examples 4 and 5, except that 1-2 and 1-2 were blended together 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.

From the above results, it can be seen that when only the resin composition of the present invention is added to a blend resin, it imparts excellent impact resistance to the blend resin.

〔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 performance of engineering plastics such as mechanical strength, heat resistance, and chemical properties. It has the effect of improving impact resistance.

Claims (1)

[Scope of Claims] 1 (a) 5 to 95 parts by weight of a resin having one or more epoxy groups in one molecule and having a flexural modulus of 10,000 kg/cm^2 or less at room temperature; and (b) α- A copolymer consisting of an olefin and an α,β-unsaturated carboxylic acid, in which 5 mol% or more of the carboxyl groups contained in the copolymer have been neutralized with an alkali metal salt. Flexural modulus is 10000kg/cm
A resin composition obtained by melt-mixing 95 to 5 parts by weight of a copolymer having a molecular weight of ^2 or less. 2. The resin composition according to claim 1, wherein the alkali metal salt is a sodium salt or a potassium salt.