JPH03277648A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To improve heat resistance, impact strength, chemical resistance, toughness, flowability, appearance without being accompanied by laminar separation, etc., by compounding a polymer having unsatd. dicarboxylic acid anhydride residues, a specific graft copolymer, and a polyamide. CONSTITUTION:An arom. vinyl monomer, an unsatd. dicarboximide deriv., an unsatd. dicarboxylic acid anhydride, and, if necessary, another vinyl monomer copolymerizable with these monomers are copolymerized, if necessary, in the presence of a rubberlike polymer, to give a copolymer comprising 0-30 pts.wt. said rubberlike polymer and 70-100 pts.wt. monomer residues consisting of 30-65mol% arom. vinyl monomer residue, 30-50mol% acid imide deriv. residue, 1-10mol% acid anhydride residue, and 0-20mol% vinyl monomer residue. 0.1-10wt.% resulting copolymer, 30-65wt.% graft copolymer obtd. by copolymerizing a rubberlike polymer, an arom. vinyl monomer, a vinyl cyanide monomer, and, if necessary, another vinyl monomer copolymerizable with these monomers, and 30-65wt.% polyamide are compounded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic resin composition having excellent heat resistance, impact resistance, chemical resistance, toughness, fluidity, and appearance without delamination.

More specifically, the present invention relates to a thermoplastic resin composition containing as essential components a copolymer, a graft copolymer, and a polyamide containing unsaturated dicarboxylic acid imide derivative residues and unsaturated dicarboxylic acid anhydride residues in specific proportions.

[Prior Art] A method for producing a polymer containing an unsaturated dicarboxylic acid imide conductor residue has been known (U.S. Pat. No. 3.1).
No. 1140.499, U.S. Patent No. 3.998.9
No. 07 Specification). Furthermore, resin compositions in which impact resistance is improved by blending these polymers with ABS resin are also known (US Pat. No. 3,642,949).

U.S. Patent No. 3,652,726, JP-A-57-
98,536, JP-A-57-125,242). However, although the heat resistance and impact resistance of these resin compositions are improved, they have a drawback in that their chemical resistance is insufficient. In order to improve this drawback, a resin composition in which a polyamide is blended with a polymer containing an unsaturated dicarboxylic acid imide derivative is also known (Japanese Unexamined Patent Publication No. 58-71,
Publication No. 952). However, this resin composition has drawbacks such as insufficient compatibility between polymers, and therefore insufficient impact resistance (and a tendency for delamination on the surface of molded products to occur (poor appearance).

[Problems to be Solved by the Invention] As a result of extensive studies to solve these problems, the present inventors found that a copolymer containing an unsaturated dicarboxylic acid imide derivative contains aromatic vinyl monomers in a specific proportion. The compatibility between the polyamide and the graft copolymer is dramatically improved only when it contains polymer residues, unsaturated dicarboxylic acid imide derivative residues, unsaturated dicarboxylic acid anhydride residues, and other vinyl monomer residues. By mixing a copolymer containing an unsaturated dicarboxylic acid imide derivative, a graft copolymer, and a polyamide in a specific ratio, heat resistance, impact resistance, chemical resistance, toughness, and fluidity can be improved. This discovery was achieved by successfully obtaining a thermoplastic resin composition with excellent appearance and no delamination on the surface of molded products.

[Means for Solving the Problems] That is, the present invention comprises (A) component: 0 to 30 parts by weight of a rubbery polymer, 30 to 65 mol% of aromatic vinyl monomer residue, and an unsaturated dicarboxylic acid imide derivative. Monomer residue 7 composed of 30 to 50 mol% residue, 1 to 10 mol% unsaturated dicarboxylic anhydride monomer residue, and 0 to 20 mol% other vinyl monomer residue
0.1% by weight or more of a copolymer consisting of 0 to 100 parts by weight I
Component (B): the rubber-like polymer contains an aromatic vinyl monomer, a vinyl cyanide monomer, or another vinyl monomer copolymerizable with these monomers. This is a thermoplastic resin composition characterized by comprising 30 to 65% by weight of a graft copolymer obtained by copolymerizing polymers and 30 to 65% by weight of component (C): polyamide.

The present invention will be explained in detail below.

First, a copolymer containing an unsaturated dicarboxylic acid derivative as component (A) and a method for producing the same will be explained.

In the present invention, the proportion of unsaturated dicarboxylic acid anhydride residues in the copolymer containing the unsaturated dicarboxylic acid imide derivative of component (A) is 1% in the so-called matrix phase excluding the rubbery polymer. One feature is that the content is within the range of ~10 mol%.

As for the method for producing the copolymer of component (A), as a first production method, an aromatic vinyl monomer, an unsaturated dicarboxylic acid imide derivative, an unsaturated dicarboxylic acid anhydride monomer, in the presence of a rubbery polymer if necessary, As a second production method, aromatic vinyl monomers and unsaturated dicarboxylic acid anhydride monomers are copolymerized in the presence of a rubbery polymer if necessary. A method of converting an acid anhydride group into an imide group by reacting ammonia and/or a primary amine (imidization reaction) with a polymer obtained by copolymerizing a polymer and a vinyl monomer mixture copolymerizable with these. can be mentioned.

Examples of aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene,
Examples include styrene monomers such as chlorostyrene and substituted monomers thereof, and among these, styrene is particularly preferred.

Examples of unsaturated dicarboxylic acid imide derivatives include maleimide, N-methylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-arylmaleimide (aryl groups include, for example, phenyl, 4-diphenyl, 1-naphthyl, Maleimide derivatives such as 2-chlorophenyl, 4-bromophenyl and other monomers and dihalophenyl isomers, 2,4,6-dribromophenyl, methoxyphenyl, etc.), N-methylitaconimide.

Examples include itaconic acid imide derivatives such as N-phenyl itaconic acid imide, and N-phenyl maleimide is particularly preferred.

Examples of the unsaturated dicarboxylic anhydride monomer include anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, with maleic anhydride (maleic anhydride) being particularly preferred.

Vinyl monomers copolymerizable with these include vinyl monomer residues other than aromatic vinyl monomer residues, unsaturated dicarboxylic acid imide derivative residues, and unsaturated dicarboxylic acid anhydride monomer residues. The group is composed of, for example, vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, acrylic acid ester monomers such as methyl acrylic ester and ethyl acrylic ester, methyl methacrylic ester, Examples include methacrylic acid ester monomers such as ethyl methacrylic acid ester, acrylic acid amide, methacrylic acid amide, etc. Among these, monomers such as acrylonitrile and methacrylic acid ester are preferred.

Examples of rubbery polymers include butadiene polymers, copolymers of butadiene and copolymerizable vinyl monomers, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, and butadiene and aromatic vinyl monomers. Block copolymers of acrylic esters, acrylic ester polymers, and copolymers of acrylic esters and vinyl monomers copolymerizable therewith are used.

Furthermore, in the second production method, ammonia and primary amine used in the imidization reaction may be in either an anhydrous state or an aqueous solution state. Examples of primary amines include alkyl amines such as methylamine, ethylamine, butylamine, and cyclohexylamine; aromatic amines such as chloro- or bromo-substituted alkyl amines; aniline, tolylamine, and naphthylamine; Examples include halogen-substituted aromatic amines such as substituted aniline, and among these, aniline is particularly preferred.

Furthermore, when the imidization reaction is carried out in a solution or suspension state, it is preferable to use a normal reaction vessel, such as an autoclave, and when it is carried out in a bulk molten state, an extruder equipped with a devolatilization device is used. Good too. Further, a catalyst may be present during imidization, and for example, a tertiary amine or the like is preferably used.

The temperature of the imidization reaction is usually about 80 to 350°C, preferably 100 to 300°C. If the temperature is less than 80°C, the reaction rate is slow (reaction takes a long time and is not practical), while if it exceeds 350°C, the physical properties deteriorate due to thermal decomposition of the polymer.

The copolymer of component (A) consists of 0 to 30 parts by weight, preferably 0 to 20 parts by weight, of a rubbery polymer and 30 to 65 mol%, preferably 40 to 65 mol%, of aromatic vinyl monomer residues. unsaturated dicarboxylic acid imide derivative residue 30 to 50 mol%, preferably 35 to 45 mol%, unsaturated dicarboxylic anhydride monomer residue 1 to 10 mol%, preferably 2 to 8 mol%,
It is a copolymer consisting of 70 to 100 parts by weight of monomer residues composed of 0 to 20 mol% of vinyl monomer residues other than these.

If the amount of the rubbery polymer exceeds 30 parts by weight, heat resistance, moldability and dimensional stability will be impaired.

If the amount of aromatic vinyl monomer residue is less than 30 mol%, moldability and dimensional stability will be impaired, and if it exceeds 65 mol%, heat resistance will decrease.

The amount of unsaturated dicarboxylic acid imide derivative residue is 30 mol%
If it is less than 50 mol %, heat resistance will be impaired, and if it exceeds 50 mol %, moldability and dimensional stability will be deteriorated.

Furthermore, if the amounts of aromatic vinyl monomer residues and unsaturated dicarboxylic acid imide derivative residues are not within the above composition range, (A)
The function of the component copolymer as a compatibilizer is reduced.

The amount of unsaturated dicarboxylic anhydride monomer residues is important;
If it is less than mol%, the compatibility between the polyamide and the graft copolymer will be insufficient, and the impact strength and impact strength of the final composition will decrease.
Toughness decreases. If it exceeds 10 mol%, the reaction with the terminal amino groups in the polyamide becomes excessive, which not only impairs the surface appearance (but also reduces fluidity, impact strength, and toughness). When observed with an electron microscope, a homogeneous phase of the copolymer containing an unsaturated dicarboxylic acid imide derivative (A) and the graft copolymer (B) is present in the polyamide matrix of the (C) component with a particle size of 0. It can be confirmed that the particles exist in finely dispersed form as particles of 1 to 1 μm.

It is presumed that because of this morphology, the thermoplastic resin composition of the present invention has excellent impact resistance, chemical resistance, toughness, fluidity, and surface appearance. In order to form such a morphology, the amount of unsaturated dicarboxylic anhydride monomer residues needs to be in the range of 1 to 10 mol%.

In addition, the carboxyl group of monocarboxylic acid is a functional group that has reactivity with the terminal amino group of polyamide, but when monocarboxylic acid is used instead of unsaturated dicarboxylic acid anhydride, the toughness and fluidity are inferior. .

In addition, if the amount of vinyl monomer residues other than aromatic vinyl monomer residues, unsaturated dicarboxylic acid imide derivative residues, and unsaturated dicarboxylic acid anhydride monomer residues exceeds 20 mol%, dimensional stability will occur. properties and heat resistance are impaired.

Next, the graft copolymer which is component (B) of the present invention is:
Copolymerizing a rubbery polymer with an aromatic vinyl monomer, a vinyl cyanide monomer, or such monomers and other vinyl monomers that can be copolymerized with these monomers. Examples of the rubbery polymer include the same rubbery polymers exemplified as component (A).

Examples of aromatic vinyl monomers include styrene, α-
Examples include styrene monomers such as methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene, and substituted monomers thereof.

Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile.

Vinyl monomers that can be copolymerized with these are vinyl monomers other than aromatic vinyl monomers and vinyl cyanide monomers, such as acrylic ester monomers such as methyl acrylate ester and ethyl acrylate ester. Examples include methacrylic acid ester monomers such as methyl methacrylic acid ester, ethyl methacrylic acid ester, acrylic acid amide, methacrylic acid amide, and unsaturated dicarboxylic acid imide derivatives exemplified as component (A).

The preferred composition of the graft copolymer as component (B) is 30 to 70 parts by weight, preferably 40 to 60 parts by weight, of a rubbery polymer and 35 to 65 mol%, preferably 45 to 65 mol%, of an aromatic vinyl monomer. 65 mol%, vinyl cyanide monomer 35~
Monomers consisting of 55 mol%, preferably 40 to 50 mol%, and 0 to 20 mol%, preferably 0 to 10 mol% of other vinyl monomers copolymerizable with these monomers. Examples include those containing 30 to 70 parts by weight of residue.

Next, the polyamide used for component (C) includes, for example, nylon-6, nylon-6,6, nylon-4,6 nylon-6.10, nylon-12, nylon-11,
Examples include nylon-6, 7, and copolymers or mixtures thereof.

(A) component contained in the thermoplastic resin composition of the present invention,
The ratio of component (B) and component (C) is 0.1 of component (A)
% by weight or more and less than 10% by weight, preferably 1 to 9% by weight,
(B) component 30-65% by weight, preferably 35-60% by weight, component (C) 30-65% by weight, preferably 35-65% by weight
It is 60% by weight. If the content of component (A) is less than 0.1% by weight, not only the impact strength will decrease, but also delamination will occur in the molded product.
If it exceeds 10% by weight, toughness and fluidity will decrease. (B)
If the content is less than 30% by weight, the impact strength will decrease, and if it exceeds 65% by weight, the chemical resistance, heat resistance, and fluidity will decrease. (
If component C) is less than 30% by weight, chemical resistance, heat resistance, and fluidity will decrease, and if it exceeds 65% by weight, impact strength will decrease.

In order to obtain the thermoplastic resin composition of the present invention, component (A),
The method of mixing component (B) and component (C) is not particularly limited, and any known means can be used. Examples of such means include a Banbury mixer, a tumbler mixer, a mixing roll, and a single-screw or twin-screw extruder. Mixing forms include normal melt mixing, multi-stage melt mixing using master pellets, etc., and solution blending.

The thermoplastic resin composition of the present invention further includes antioxidants, flame retardants, antistatic agents, ultraviolet absorbers, plasticizers, lubricants, fillers such as glass fibers, carbon fibers, and calcium carbonate, colorants, It is also possible to add metal powder or the like.

Also, other resins and elastomers may be added depending on the purpose. Specific examples include resins such as AS resin, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, and polyphenylene ether, and elastomers such as acrylic rubber, ethylene propylene rubber, and styrene-butadiene rubber. In particular, AS resin is preferably used because it has good compatibility with the thermoplastic resin composition of the present invention. The amount of these other resins and elastomers added is preferably 50 parts by weight or less, preferably 0 to 25 parts by weight, based on 100 parts by weight of the thermoplastic resin composition.

[Example] The present invention will be explained in more detail with reference to Examples below. Note that all parts and percentages in the examples are expressed on a weight basis.

Examples 1 to 9 and Comparative Examples 1 to 5 (1) Unsaturated dicarboxylic acid imide copolymer (component A) 100 parts of styrene was placed in an autoclave equipped with a stirrer, and the inside of the stirrer system was replaced with nitrogen gas. After that, temperature 80
heated to ℃. To this, 67 parts of maleic anhydride and 0.2 parts of benzoyl peroxide were added to 300 parts of methyl ethyl ketone.
The solution was added over 8 hours. After addition, add 4 more
The polymerization reaction was completed while maintaining the temperature at 80°C.

Next, 1.2 parts of triethylamine and 60 parts of aniline were added, and an imidization reaction was carried out at 150° C. for 10 hours. The reaction solution was cooled to 100° C., and the reaction solution was purged into a stainless steel vat. Next, vacuum drying was performed at 180° C. for 3 hours, and after removing the solvent, pulverization was performed to obtain a powdery copolymer. C--C-13 moiety analysis showed that the conversion rate of maleic anhydride groups to imide groups was 91.8 mol%, and the content of imide derivative residues in the copolymer was 37.0 mol%. This copolymer was designated as A-1. Other unsaturated dicarboxylic acid imide copolymers (A-2 to A-4 and A-6) were also used, except that the conversion rate of maleic anhydride groups to imide groups was adjusted by adjusting the amount of aniline added. was prepared in the same manner as A-1.

Next, a method for producing an unsaturated dicarboxylic acid imide copolymer containing a rubbery polymer will be described.

100 parts of styrene in an autoclave equipped with a stirrer,
After adding 50 parts of methyl ethyl ketone and 24 parts of polybutadiene rubber cut into small pieces (Asahi Kasei Co., Ltd., NF35AS) and purging the system with nitrogen gas, the mixture was stirred at room temperature all day and night to dissolve the rubber. After the temperature was set to 80° C., a solution of 67 parts of maleic anhydride and 0.3 parts of benzoyl peroxide dissolved in 400 parts of methyl ethyl ketone was continuously added over 8 hours. After the addition, the temperature was maintained at 80° C. for an additional 4 hours to complete the polymerization reaction. After the imidization reaction, it was produced in the same manner as A-1.

The unsaturated dicarboxylic acid imide copolymer containing this rubbery polymer is designated as A-5, and the compositions of A-1 to A-6 are shown in Table 1.

Table (2) Graft copolymer CB component) 80 parts of polybutadiene latex (solid content 50%, average particle size 0.35μ, gel content 90%), 1 part sodium stearate, sodium formaldehyde sulfoxylate 0.1 part of tetrasodium ethylenediamine atraacetic acid, 0.003 part of ferrous sulfate, and 200 parts of water were charged into an autoclave purged with nitrogen gas. After heating the temperature to 65°C, monomer mixture 5 consisting of 30% acrylonitrile and 70% styrene
0 parts, 0.3 parts of t-dodecylmercabutane, and 0.2 parts of cumene hydroperoxide were continuously added over 4 hours.
Further, after the addition was completed, polymerization was carried out at 65° C. for 2 hours. The grafting rate was 80% and the 3 polymerization rate was 98%. After adding an antioxidant to the obtained latex, salting out with calcium chloride,
After washing with water and drying, a white powdery copolymer was obtained. This graft copolymer was designated as B-1.

Also, instead of 50 parts of a monomer mixture consisting of 30% acrylonitrile and 70% styrene, 25% acrylonitrile, 65% styrene, and 1 methyl methacrylate were used.
B-1 except that 50 parts of a monomer mixture consisting of 0% was used.
A graft copolymer obtained in the same manner as above was designated as 8-2.

The grafting rate of B-2 was 78%, and the polymerization rate was 97%.

(3) Polyamide (component C) The following nylon-6, nylon-12, and nylon-66 obtained by melt polymerization were used.

C-1) Nylon-6; Concentrated sulfuric acid obtained from ε-caprolactam Relative viscosity of 2.65 Nylon-6°C-2) Nylon-12,12-Aminododecanoic acid Concentrated sulfuric acid relative viscosity 2. Nylon-66 with a relative viscosity of 2.55 (4) Other thermoplastic resins (D Component) D-1) Acrylonitrile-styrene copolymer resin having a weight average molecular weight of 115,000 and containing 30% acrylonitrile.

Component (A), component (B), component (C), and component (D) are blended in the ratio shown in Table 2, and this blend is
250℃ in a 2-axis circumferential rotation extruder with m/m devolatilization device
It was extruded and pelletized. In addition, the blend contains octadecyl-3-(3',5'-di-t) as an antioxidant.
-butyl-4'-hydroxyphenyl)propionate and N-N'-hexamethylenebis(3°5-di-t-
butyl)-hydroxy-hydrocinnamamide, respectively.
It was made to contain 25 parts. Using this pellet, a test piece for measuring physical properties was prepared at 240° C. using an injection molding machine, and various physical properties were measured. The results are shown in Table 2.

The methods for measuring the various physical properties in Table 2 are as follows.

Heat resistance: According to ASTM D-648, using an injection molded product with a thickness of 174'', the heat deformation temperature (
HDT) was measured.

Impact strength: In accordance with ASTM D-256, notched isots were measured using 1/8-thick injection molded products. The ambient temperature was 23℃.

Fluidity: Melt flow rate (MFR) was measured at a temperature of 265° C. and a load of 10 kg in accordance with ASTM D-1238.

Toughness: In accordance with ASTM D-638, a tensile test was performed on an injection molded article having a thickness of 1/8'', and the elongation at break (Ei!) was measured.

Chemical resistance: As shown in FIG. 1, an ASTM D-6381 dumbbell was bent, kerosene was applied to the dumbbell, and it was observed after being left at room temperature for 24 hours. Dumbbells with no cracks or crazes were rated ○, and those with these were rated X.

Molded product appearance: The surface appearance of the injection molded ASTM D-6381 dumbbell was visually determined. Those with no abnormality were rated as ○, and those with surface peeling were rated as ×.

[Effects of the Invention] As explained above, the thermoplastic resin composition of the present invention has excellent heat resistance, impact strength, toughness, and fluidity, and
Good chemical resistance and molded product appearance. In particular, the thermoplastic resin composition of the present invention has high impact strength and toughness (elongation),
It has excellent toughness and has extremely high practical value as a material for various industrial parts and sporting goods.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram showing a method for testing the chemical resistance of a resin composition. 1...Jig

Claims (1)

Scope of Claims Component (A): 0 to 30 parts by weight of rubbery polymer, 30 to 65 mol% of aromatic vinyl monomer residue, 30 to 50 mol% of unsaturated dicarboxylic acid imide derivative residue, Monomer residue 7 composed of 1 to 10 mol% of saturated dicarboxylic anhydride monomer residue and 0 to 20 mol% of other vinyl monomer residues
0.1% by weight or more of a copolymer consisting of 0 to 100 parts by weight1
Less than 0% by weight, component (B): rubbery polymer, aromatic vinyl monomer, vinyl cyanide monomer, or other vinyl monomer copolymerizable with these monomers. 1. A thermoplastic resin composition comprising 30 to 65% by weight of a graft copolymer obtained by copolymerizing polyamide and 30 to 65% by weight of component (C): polyamide.