JPH01215843A - Resin composition and its molding - Google Patents

Abstract

PURPOSE:To obtain a resin composition improved in heat resistance, impact resistance and moldability, free from delamination between resin layers and prevented from surface roughening and cracking, by mixing a specified imidated copolymer with a polyamide resin and an elastomeric copolymer. CONSTITUTION:A copolymer obtained by copolymerizing an aromatic vinyl monomer (e.g., styrene) with an unsaturated dicarboxylic acid anhydride (e.g., maleic anhydride) and ammonia and/or a prim. amine are subjected to an imidation reaction at 80-350 deg.C to obtain an imidated copolymer (A) containing 45-80wt.% residues of the aromatic vinyl monomer, 20-55wt.% total of residues of the unsaturated dicarboxylic acid imide derivative and residues of the unsaturated dicarboxylic acid anhydride and at most 10wt.% (excluding 0), based on the total of the three components, residues of the unsaturated dicarboxylic acid. 10-65pts.wt. component A is mixed with 30-85pts.wt. polyamide resin (B) and 5-30pts.wt. elastomeric copolymer (C) comprising an ethylene/alpha-olefin of a number-average MW of 10,000-100,000, containing at most 7wt.% (excluding 0) unsaturated dicarboxylic acid (anhydride) and having an ethylene content of 50-85mol.%.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention has excellent heat resistance, impact resistance, and moldability, and can be used as parts for automobiles, home appliances, OA equipment, and other industrial products. The present invention relates to a resin composition that can be used as a resin composition and a molded article thereof.

(Prior Art) In general, plastics tend to have specific properties such as mechanical properties and thermal properties, and the range in which they can be used as molded products tends to be limited. For example, polyacecool, polycarbonate, polyamide, I, which are known as plastics with heat resistance exceeding 100°C
)1] ○, PBT, imidized resin, and other heat-resistant engineering plastics, but if the temperature is further limited, the plastics that can be used will also be limited. On the other hand, plastics with poor heat resistance generally have the disadvantage of poor impact resistance due to their rigidity.In order to improve this impact resistance, the development of compositions or copolymers with various elastomer polymers has been considered. ing. However, in the case of compositions, problems such as delamination, surface roughness, and cracking occur in molded products due to compatibility issues, and even in the case of copolymers, the utility value decreases due to increased product costs due to constraints on manufacturing conditions. It suffers from drawbacks such as deterioration.

(Problems to be Solved by the Invention) The present invention was developed to solve these drawbacks, and after examining the impact resistance of imidized resins in particular, we found that the impact resistance of imidized resins and compositions with specific resins and elastomers. By doing so, we have completed a resin composition and a molded product thereof that exhibits no deterioration in heat resistance and impact resistance, does not cause delamination between resins as a molded product, and can prevent surface roughness and cracking.

(Means for Solving the Problems) That is, the present invention comprises: (A) 45 to 80% by weight of aromatic vinyl monomer residues, unsaturated dicarboxylic acid imide derivative residues, and unsaturated dicarboxylic acid anhydride residues; Imidized copolymers 10 to 10 with a total amount of 20 to 55% by weight and containing 10% by weight or less of unsaturated dicarboxylic acid anhydride residues (excluding O) based on the total amount of the above three components. 65 parts by weight (B) 30 to 85 parts by weight of polyamide resin and (C)
A resin characterized by containing 5 to 30 parts by weight of an elastomer copolymer made of ethylene-α-olefin containing 7% by weight or less (but not including 0) of an unsaturated dicarboxylic acid and/or its anhydride. This is a molded article formed by molding a composition and this resin composition.

The imidized copolymer used in the resin composition of the present invention consists of an aromatic vinyl monomer and an unsaturated dicarboxylic acid imide derivative, and examples of the aromatic vinyl monomer include styrene, α-methylstyrene, There are styrene monomers such as vinyltoluene, t-butylstyrene, chlorostyrene, and substituted products thereof, and among these, styrene is particularly preferred. Unsaturated dicarboxylic acid imide derivatives □ can be obtained by copolymerizing unsaturated dicarboxylic acid anhydrides with aromatic vinyl and then reacting with ammonia and/or primary amines to obtain imide derivatives, or maleimide, N-methylmaleimide. , N
-ethylmaleimide, N-cyclohexylmaleimide,
A maleimide monomer such as N-phenylmaleimide or N-naphthylmaleimide may be directly copolymerized with an aromatic vinyl monomer. However, as a method for producing these copolymers, the former method, that is, a method in which an unsaturated dicarboxylic anhydride is copolymerized with an aromatic vinyl and then imidized, is more preferable in terms of copolymerizability and economy. Examples of unsaturated dicarboxylic anhydrides include anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid.
Maleic anhydride is particularly preferred. Primary amines used in the imidization reaction include alkyl amines such as methylamine, ethylamine, propylamine, and cyclohexylamine, and aromatic amines such as chloro- or bromine-substituted alkyl amines, aniline, tolylamine, naphthylamine, etc. Examples include bromine-substituted aromatic amines.

When the imidization reaction is carried out in a solution or suspension state, it is preferable to use an ordinary reaction vessel, such as an autoclave, and when it is carried out in a bulk molten state, an extruder equipped with a devolatilization device may be used. The temperature of the imidization reaction is about 80~
The temperature is 350°C, preferably 100 to 300°C.

If the temperature is lower than 80°C, the reaction rate is slow and the reaction takes a long time, which is not practical. On the other hand, if the temperature exceeds 350°C, the physical properties will deteriorate due to thermal decomposition of the polymer. Further, a catalyst may be used for the imidized resin, in which case a tertiary amine,
For example, triethylamine is preferably used.

In the aromatic vinyl monomer/unsaturated dicarboxylic acid imide copolymer used in the resin composition of the present invention, the aromatic vinyl monomer residue is 45 to 80% by weight. If the content is less than 45% by weight, the moldability and dimensional stability, which are characteristics of aromatic vinyl compounds, will be lost. The total amount of unsaturated dicarboxylic acid anhydride residues and unsaturated dicarboxylic acid imide derivative residues is 20 to 55% by weight.
Moreover, the amount of the unsaturated dicarboxylic acid anhydride residue is preferably 10% by weight or less (however, excluding O) based on the total of the three components, and when both of the residues are less than 20% by weight,
Insufficient heat resistance and chemical resistance. On the other hand, if the imide derivative residue exceeds 55% by weight, the copolymer becomes brittle;
Moldability also deteriorates significantly. Further, the unsaturated dicarphonic anhydride residue has activity and can react with other polymers and the like.

Further, the imidization rate of the imidized copolymer used in the resin composition of the present invention is 82% or more, and the imidization rate is 82%.
If it is less than that, the heat resistance decreases, and furthermore, when the composition is molded into a molded product, the surface of the molded product becomes rough.

Next, as the polyamide resin used in the resin composition of the present invention, for example, a polyamide obtained from an aliphatic, aromatic or alicyclic dicarboxylic acid and a diamine, a polyamide obtained from an aminocarboxylic acid or a cyclic lactam, etc. Specific examples include aliphatic polyamides such as nylon 6, nylon 6.6, nylon 6.10, nylon 11, nylon 12, and nylon 6.12, polyhexamethylene diamine terephthalamide, and polyamide. Examples include aromatic polyamides such as xamethylenediamine isophthalamide, and a mixture or copolymer of two or more of these can also be used.

The elastomer copolymer containing ethylene-α/olefin used in the resin composition of the present invention has a number average molecular weight in the range of 10,000 to 100,000 and an ethylene content of 50 to 85 mol%. preferable. Also α・
As the olefin, propylene, 1-butene, -pentene, etc. are used, with propylene and 1-butene being preferred. Furthermore, the elastomer copolymer containing ethylene-α-olefin is preferably one modified with an alkyl peroxide and an unsaturated dicarboxylic acid or its anhydride. is particularly preferred. Unsaturated dicarboxylic acid and/or
Or the amount of the anhydride added is 7% by weight or less (however, excluding 0), preferably 0.5 to 7% by weight, 7% by weight or less
If it exceeds % by weight, gelation of the composition will occur. 0 again
If the amount is less than 5% by weight, the compatibility of the composition is poor and layer peeling may occur. This elastomer copolymer containing ethylene-α/olefin can be produced by using the manufacturing method of Example 1 disclosed in Japanese Patent Publication No. 58-445.
Elastomer copolymers can be obtained.

The proportion of each component in the resin composition of the present invention is 10 to 65 parts by weight, preferably 20 to 65 parts by weight as the imidized copolymer.
50 parts by weight, 30 to 85 parts by weight as polyamide resin
Parts by weight, preferably 40 to 70 parts by weight, ethylene-α・
5 to 30 as an elastomer copolymer containing olefin
Parts by weight, preferably 7 to 25 parts by weight. If the amount of the imidized copolymer is less than 10 parts by weight, the heat resistance will decrease, and if it exceeds 65 parts by weight, the impact resistance will decrease. If the polyamide resin is less than 40 parts by weight, the impact resistance will be reduced, and if it exceeds 85 parts by weight, the impact resistance will be reduced. Furthermore, if the amount of the elastomer copolymer containing edilene-α-olefin is less than 5 parts by weight, the impact resistance will decrease, and if it exceeds 30 parts by weight, the heat resistance will decrease.

It is also desirable to improve the heat resistance and rigidity of the layer by adding glass fiber, carbon fiber, potassium titanate fiber, metal fiber, etc. as a filler to the resin composition of the present invention. Inorganic substances such as calcium carbonate, clay, talc, mica, magnesium sulfate, and titanium oxide can also be added. Furthermore, if necessary, ultraviolet absorbers, antioxidants, flame retardants, lubricants, colorants, etc. can also be used.

The resin composition of the present invention can be produced by pre-mixing the resin and elastomer components in a mixer, such as a Henschel mixer or a super mixer, and then melt-mixing in an extruder to pelletize the resin composition. be able to.

The resin composition of the present invention can be used to obtain a molded body using a general plastic molding machine, and examples of the molded body include automotive parts such as meter hoods, defroster garnishes, register bezels, clusters, instrument panels, etc. There are speaker grilles, inset ceilings, etc. In addition, parts for home appliances, OA equipment, and other industrial products include cases, radiator covers, knobs, buttons, handles, arms, exhaust ports, ventilation ports, reel stands, reel shafts, bobbins, and other heat-resistant , can be used in applications where impact resistance is desired.

(Example) The present invention will be explained in detail below with reference to Examples.

Examples 1 to 4 The imidized copolymer is shown in Example 1 of JP-A-57-5590. A copolymer with an imidization rate of 92% obtained by reacting 60% by weight of an aromatic vinyl monomer and 40% by weight of an unsaturated dicarboxylic acid anhydride according to the manufacturing method was used as a polyamide resin (Toshiku Co., Ltd.) Product name “0M101
7'' (hereinafter referred to as nylon-6) and a maleic anhydride-containing ethylene-α/olefin elastomer copolymer having a number average molecular weight of 700,000 by the manufacturing method (according to the examples) shown in JP-A-52-49289. of ethylene-
5% by weight of maleic anhydride in α-olefin copolymer
The 1 and ethylene-α/olefin copolymers obtained by grafting were mixed in the proportions shown in Table 1, mixed in a Henschel mixer and pelletized in an extruder to obtain each resin composition, and then their physical properties were measured.

The physical property measurement results are shown in Table 1.

Comparative Examples 1 to 4 The same operations as in Example 1 were performed except that the same resin as in Example 1 was used and the proportions shown in Table 1 were set.

The physical property measurement results are shown in Table 1.

Examples 5 to 11 In addition to the same components used in Example 1, Mitsubishi Chemical Industries, Ltd. product name r3010SRj was used as a polyamide resin.
(hereinafter referred to as nylon 6.6), Ube Industries Co., Ltd. product name 'r7125UJ (hereinafter referred to as nylon 6°12)
and r3024UJ (hereinafter referred to as nylon 12) manufactured by the company were used to obtain resin compositions having the proportions shown in Table 2 G, and their physical properties were measured. The physical property measurement results are shown in Table 2.

Examples 12 to 14 60% by weight of aromatic vinyl monomer and 40% by weight of unsaturated dicarboxylic acid anhydride obtained as an imidized copolymer according to the production method of Example 1 shown in JP-A-57-55901. %
A copolymer with an imidization rate of 92°95.99% was used, and the polyamide resin was nylon 6.
Using an ethylene-α/olefin elastomer copolymer containing 5% by weight of maleic anhydride, resin compositions having the proportions shown in Table 3 were obtained, and their physical properties were measured. Table 3 shows the physical property measurement results.

Examples 15 to 18 The same imidized copolymers and polyamide resins as in Example 1 were used, and the maleic anhydride content of the ethylene-α/olefin elastomer copolymers is shown in Table 3. Using the ratios shown in the table above, resin compositions having the ratios shown in the table above were obtained and their physical properties were measured. Table 3 shows the results of physical property measurements.

Example 19 Using each of the resin compositions of Examples 1 to 4 and Examples 9 to 11, injection molding was performed using Toshiba Machine Co., Ltd. injection molding m10 ounce at a temperature of 250 to 300°C and an injection pressure of 40 to 70 kg/
Under the molding conditions of self-gauge pressure and mold temperature of 50 to 100℃,
A video cassette for television was molded. When the appearance of video cassette n-10 made of each resin composition was visually inspected, all had a good appearance with no delamination, rough skin, or cracks.

Physical properties were measured using the following measurement method.

1) Heat distortion temperature ASTM D-648 load 18.6 kg/co! 2)
Izod impact strength: Compliant with ASTM D-256. Width 1/4 inch, with notch, without notch 3) Melt flow index JISK-6874 load 5 kg/cta (effects of the invention) As described above, the resin composition of the present invention has heat resistance.

Molded articles made of this resin composition have excellent impact resistance, and are effective in preventing delamination, surface roughening, cracking, warping, and the like.

Patent applicant Denki Kagaku Kogyo Co., Ltd.

Claims (1)

[Claims] 1. (A) 45 to 80% by weight of aromatic vinyl monomer residues;
The total amount of unsaturated dicarboxylic acid imide derivative residues and unsaturated dicarboxylic acid anhydride residues is 20 to 55% by weight, and the amount of unsaturated dicarboxylic acid anhydride residues is 20 to 55% by weight based on the total of the three components. 10 to 65 parts by weight of imidized copolymer containing 10% by weight or less (but not including 0) (B) 30 to 85 parts by weight of polyamide resin and (C)
A resin characterized by containing 5 to 30 parts by weight of an elastomer copolymer made of ethylene-α-olefin containing 7% by weight or less (but not including 0) of an unsaturated dicarboxylic acid and/or its anhydride. Composition. 2, (A) aromatic vinyl monomer residue 45 to 80% by weight,
The total amount of unsaturated dicarboxylic acid imide derivative residues and unsaturated dicarboxylic acid anhydride residues is 20 to 55% by weight, and the amount of unsaturated dicarboxylic acid anhydride residues is 20 to 55% by weight based on the total of the three components. 10 to 65 parts by weight of imidized copolymer containing 10% by weight or less (but not including 0) (B) 30 to 85 parts by weight of polyamide resin and (C)
A molded article of a resin composition containing 5 to 30 parts by weight of an elastomer copolymer made of ethylene-α-olefin containing 7% by weight or less (but not including 0) of an unsaturated dicarboxylic acid and/or its anhydride.