JPH0680847A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition comprising an imidized copolymer, a graft copolymer, a specific copolymer, and an organosiloxane compound in specific amounts, excellent in heat resistance and moldability, and useful as a material for sports goods. CONSTITUTION:The objective composition comprises (A) 10-90wt.% of an imidized copolymer comprising a rubbery polymer, an aromatic vinyl monomer residue, an unsaturated dicarboxylic acid imide monomer residue, an unsaturated dicarboxylic acid anhydride residue, and the other vinyl monomer residue, (B) 10-90wt.% of a graft extruded polymer produced by copolymerizing an aromatic vinyl monomer, a vinyl cyanide monomer, a copolymerizable vinyl monomer and a rubbery polymer, (C) 10-80wt.% of a copolymer comprising an aromatic vinyl monomer, a vinyl cyanide monomer, and a copolymerizable vinyl monomer, the total amount of the components A, B, and C being 100 pts.wt., and 0.05-2 pts.wt. of a compound of the formula (R1-R4 are methyl, H, phenyl, etc.; n>=10).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having improved moldability, thin-walled part strength and heat resistance. More specifically, the present invention relates to a thermoplastic resin composition containing an imidized copolymer having an unsaturated dicarboxylic acid imide monomer residue, a moldability and a thin wall containing a specific polyorganosiloxane compound. The present invention relates to a thermoplastic resin composition having excellent part strength and heat resistance.

[0002]

2. Description of the Related Art Conventionally, a so-called ABS resin in which a mixture of styrene and acrylonitrile is graft-copolymerized with a rubber-like polymer is known. However, ABS resin
There are drawbacks such as heat resistance, for example, low heat deformation temperature and large heat shrinkage. For example, improvement of heat resistance is required for automobile parts and the like, and various improvement methods have been proposed. As one of the improvement methods, for example, aromatic vinyl monomers, vinyl cyan monomers, copolymers of N-aromatic substituted maleimides, and aromatic vinyl monomers in the presence of a conjugated diolefin rubber are used. A resin composition composed of a monomer and a graft copolymer obtained by copolymerizing a vinyl cyan monomer has been proposed (US Pat. No. 3,642,949).
No.).

However, in this resin composition, the heat resistance of the obtained resin composition is improved as the ratio of the N-aromatic substituted maleimide in the copolymer is increased, but the strength of the thin portion of the molded product is improved. Has the drawback of decreasing. Then, in order to improve the strength of the thin portion of the molded product, it is usually considered to increase the rubber content, but the resin composition with the increased rubber content shows almost no improvement in the strength of the thin portion of the molded product, There is a drawback that the product and heat resistance are reduced.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic resin composition in which the above drawbacks have been improved, heat resistance is good, and moldability and strength of thin portions are also good.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned drawbacks, the inventor has found the following resin composition and found that the object can be achieved. That is, the present invention comprises (A) component: a rubbery polymer 0 to 40% by weight, an aromatic vinyl monomer residue 30 to 69% by weight, an unsaturated dicarboxylic acid imide monomer residue 30 to 60% by weight, Unsaturated dicarboxylic acid anhydride residue 0
~ 15 wt% and other vinyl monomer residues 0-40
10% to 90% by weight of imidized copolymer (B) Component: 5 to 80% by weight of rubbery polymer, 40 to 80% by weight of aromatic vinyl monomer, 2 to 40 of vinyl cyanide monomer weight%
And 0 to 40% by weight of vinyl monomer copolymerizable with these
Graft copolymer obtained by copolymerizing 20 to 95% by weight of a monomer consisting of 10 to 90% by weight (C) Component: 60 to 90% by weight of aromatic vinyl monomer, 10 to 40% of vinyl cyanide monomer % By weight, 10 to 80% by weight of a copolymer consisting of 0 to 40% by weight of a vinyl monomer copolymerizable therewith
(D) component: 0.05 to 2 parts by weight of a polyorganosiloxane compound represented by the following general formula [Chemical Formula 2] per 100 parts by weight of the total amount of the (A) component, the (B) component and the (C) component. And a thermoplastic resin composition.

[0006]

[Chemical 2] (R _{1 to} R ₄ are hydrogen, methyl group, phenyl group, carbon number of main chain
(Selected from epoxy end groups of 10 or less, amine end groups of 10 or less carbon atoms in the main chain)

First, the imidized copolymer as the component (A) and a method for producing the same will be described. As the method for producing the component (A) copolymer, an aromatic vinyl monomer, an unsaturated dicarboxylic acid imide monomer, in the presence of the rubber-like polymer necessary for the first production method,
Aromatic vinyl monomer, unsaturated dicarboxylic acid in the presence of a rubbery polymer, if necessary, as a second production method in which an unsaturated dicarboxylic acid anhydride and a vinyl monomer mixture copolymerizable therewith are copolymerized The polymer obtained by copolymerizing an anhydride and a vinyl monomer mixture copolymerizable therewith is reacted with ammonia and / or a primary amine to form an acid anhydride group.
Examples thereof include a method of converting 40 to 100 mol% into an imide group, and an imidized copolymer can be obtained by any method.

As the aromatic vinyl monomer used in the method for producing the component (A) copolymer, there are styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene and chlorostyrene, and styrene monomers thereof. It is a substituted monomer, and among these, styrene is particularly preferable.

Examples of unsaturated dicarboxylic acid imide monomers include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N-hydroxyphenylmaleimide and N-methylphenylmaleimide.
-Methoxyphenylmaleimide, N-chlorophenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-cyclohexylmaleimide, N-cyclohexylmaleimide and other maleimide derivatives, and N-methylitaconic acid imide and N-phenylitaconic acid imide, etc. The itaconic acid imide derivative and the like are listed, and among these, N-phenylmaleimide is particularly preferable.

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

The component (A) can be copolymerized with a vinyl monomer copolymerizable therewith. Examples of the copolymerizable vinyl monomer include vinyl cyanide monomers such as acrylonitrile, methacrylonitrile and α-chloroacrylonitrile, acrylic acid ester monomers such as methyl acrylic acid ester and ethyl acrylic acid ester, and methyl methacrylate. Examples thereof include methacrylic acid ester monomers such as acid esters and ethyl methacrylic acid esters, vinylcarboxylic acid monomers such as acrylic acid and methacrylic acid, and acrylic acid amides and methacrylic acid amides. Among these, acrylonitrile and methacrylic acid are included. Monomers such as esters, acrylic acid and methacrylic acid are preferred.

The temperature of the imidization reaction is about 80 to 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 are deteriorated due to thermal decomposition of the polymer.

The amount of acid anhydride residue is adjusted by the molar equivalent of ammonia and / or primary amine added to the acid anhydride group.

As the solvent for imidization in a solution state, there are acetone, methylethylketone, methylisobutylketone, acetophenone, tetrahydrofuran, dimethylformamide and the like. Of these, methylethylketone and methylisobutylketone are preferable. The non-aqueous medium for imidization in suspension in the non-aqueous medium includes aliphatic hydrocarbons such as heptane, hexane, pentane, octane, 2-methylpentane, cyclopentane and cyclohexane.

Next, the graft copolymer as the component (B) and the method for producing the same will be described. The rubber-like polymer used as the component (B) is a polymer consisting of butadiene or a vinyl monomer copolymerizable therewith, an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer or an acrylic ester. There is a polymer composed of a vinyl monomer which can be homopolymerized or copolymerizable therewith.

The aromatic vinyl monomer used as the component (B) is a styrene monomer such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene or chlorostyrene and a substituted monomer thereof. Of these, monomers such as styrene and α-methylstyrene are particularly preferable.

As the vinyl cyanide monomer, there are acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like, and acrylonitrile is particularly preferable. In addition, as vinyl monomers copolymerizable with these, acrylic acid esters such as methyl acrylic acid ester, ethyl acrylic acid ester and butyl acrylic acid ester, and methacrylic acid ester monomers such as methyl methacrylic acid ester and ethyl methacrylic acid ester are used. Examples thereof include monomers, vinylcarboxylic acid monomers such as acrylic acid and methacrylic acid, and acrylic acid amide and methacrylic acid amide. Of these, methyl methacrylate, acrylic acid and methacrylic acid are particularly preferable.

The method for producing the graft copolymer as the component (B) is to prepare an aromatic vinyl monomer in the presence of 5 to 80% by weight of a rubbery polymer.
Graft copolymerization of 40 to 80% by weight, 0 to 40% by weight of vinyl cyanide monomer and 20 to 95% by weight of a monomer mixture consisting of 0 to 40% by weight of a vinyl monomer copolymerizable therewith can get. As the polymerization method, any known polymerization technique can be adopted, and examples thereof include aqueous heterogeneous polymerization such as suspension polymerization and emulsion polymerization, bulk polymerization, solution polymerization and precipitation polymerization of a produced polymer in a non-solution. is there.

Next, the copolymer of the component (C) will be described. As the aromatic vinyl monomer used as the component (C), styrene, α-methylstyrene, vinyltoluene,
It is a styrene monomer such as t-butylstyrene or chlorostyrene and a substituted monomer thereof, and among these, styrene and α-methylstyrene are particularly preferable.

The vinyl cyanide monomer includes acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, etc., and acrylonitrile is particularly preferable.

Vinyl monomers copolymerizable with these include acrylic acid ester monomers such as methyl acrylic acid ester, ethyl acrylic acid ester and butyl acrylic acid ester, and methyl methacrylic acid ester and ethyl methacrylic acid ester. Methacrylic acid ester monomer,
Examples thereof include vinylcarboxylic acid monomers such as acrylic acid and methacrylic acid, and acrylic acid amides, methacrylic acid amides, acenaphthylene, N-vinylcarbazole and N-alkyl-substituted maleimides, N-aromatic-substituted maleimides, and the like.

Next, the polyorganosiloxane compound as the component (D) will be described. The polyorganosiloxane compound used in the present invention is represented by the general formula [Chemical Formula 3].

[0023]

[Chemical 3] (R _{1 to} R ₄ are hydrogen, methyl group, phenyl group, carbon number of main chain
(Selected from epoxy end groups of 10 or less, amine end groups of 10 or less carbon atoms in the main chain)

Specific examples of the polyorganosiloxane compound include straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil and methylhydrogen silicone oil, and functional groups such as epoxy groups and amino groups at side chains or terminal positions. Examples thereof include modified silicone oil.

The present invention comprises the component (A) imidized copolymer 10 to
90% by weight, preferably 10 to 60% by weight, (B) component graft copolymer 10 to 90% by weight, preferably 10 to 60% by weight, (C)
Component copolymer 10 to 80% by weight, preferably 10 to 50% by weight
The resin composition contains the component (D) in an amount of 0.05 to 2 parts by weight based on 100 parts by weight of the total amount of the components (A), (B) and (C).

The component (A) imidized copolymer is prepared from the component (A) to
If it is less than 10% by weight in the component (C) resin composition, the heat resistance is not sufficiently improved, and if it exceeds 90% by weight, the heat resistance is high but the impact resistance is lowered, which is not preferable.

The graft copolymer as the component (B) is (A)
If less than 10% by weight of the resin composition of components (C), the impact resistance is low, and if more than 90% by weight, the rigidity is lowered, which is not preferable.

The thermoplastic resin which is the component (C) is not preferable because the heat resistance is lowered when it exceeds 80% by weight in the resin composition of the components (A) to (C).

If the polyorganosiloxane compound as the component (D) is less than 0.05 parts by weight with respect to 100 parts by weight of the resin composition of the components (A) to (C), the effect of improving the strength of the thin portion is not sufficient. If it exceeds 2 parts by weight, the effect of improving the strength of the thin portion disappears, which is not preferable.

The method for mixing the resin composition of the present invention is not particularly limited, and known means can be used. Examples of the means include a Banbury mixer, a tumbler mixer, a mixing roll, and a single-screw or twin-screw extruder.

As a mixing form, there are methods such as ordinary melt mixing, multi-step melt kneading using master pellets, and blending in a solution to obtain a resin composition.

The resin composition of the present invention contains a stabilizer, a flame retardant, a plasticizer, a lubricant, an ultraviolet absorber and a colorant, and a filler such as talc, silica, clay, mica and calcium carbonate, if necessary. It is also possible to add.

[0033]

EXAMPLES The present invention will be described below with reference to examples. All "parts" and "%" in the examples are expressed on a weight basis. Experimental Example 1 (A) Production of Component Imidized Copolymer 60 parts of styrene and 50 parts of methyl ethyl ketone were charged into an autoclave equipped with a stirrer, the system was replaced with nitrogen gas, and the temperature was raised to 85 ° C. A solution prepared by dissolving 40 parts of maleic acid and 0.15 part of benzoyl peroxide in 250 parts of methyl ethyl ketone was continuously added over 8 hours. After addition
The temperature was kept at 85 ° C for a further 3 hours. A part of the viscous reaction liquid was sampled and the polymerization rate was quantified by gas chromatography. As a result, styrene 99%, maleic anhydride
It was 99%. 34 parts of aniline and 0.3 part of triethylamine, which are 0.90 molar equivalents to maleic anhydride, were added to the copolymer solution thus obtained, and the mixture was reacted at 140 ° C. for 7 hours. To the reaction solution was added 200 parts of methyl ethyl ketone, cooled to room temperature, poured into 1500 parts of vigorously stirred methanol to precipitate,
It was filtered and dried to obtain an imidized copolymer. From C-13 NMR analysis, the maleic anhydride monomer residue was 3.1% by weight. This was designated as Polymer A-1.

Experimental Example 2 (A) Preparation of Component Imidized Copolymer In an autoclave equipped with a stirrer, 60 parts of styrene, 100 parts of methyl ethyl ketone, and 10 parts of polybutadiene cut into small pieces were charged, and the mixture was stirred at room temperature for a whole day and night. Was dissolved, the inside of the system was replaced with nitrogen gas, and the temperature was raised to 85 ° C.
A solution prepared by dissolving 40 parts of maleic anhydride and 0.15 part of benzoyl peroxide in 250 parts of methyl ethyl ketone was continuously added over 8 hours. After the addition, the temperature was kept at 85 ° C for a further 3 hours. A part of the viscous reaction liquid was sampled and the amount of unreacted monomer was quantified by gas chromatography. As a result, the polymerization rates were 98% for styrene and 98% for maleic anhydride. 0.95 equivalents of aniline to maleic anhydride in the obtained copolymer solution 36.1 parts, triethylamine 0.
3 parts was added and the reaction was carried out at 140 ° C for 7 hours. To the reaction solution, 200 parts of methyl ethyl ketone was added, cooled to room temperature, poured into 1500 parts of methanol with vigorous stirring, and precipitated, filtered and dried to obtain a rubber-modified imidized copolymer. This is polymer A-
It was set to 2.

Experimental Example 3 (A) Preparation of Component Imidized Copolymer Polymerization was conducted in the same manner as in Experimental Example 1 except that 60 parts of styrene in Experimental Example 1 was replaced with 55 parts of styrene and 5 parts of methyl methacrylate. Polymer A-3 was obtained. The polymerization rate is 98% styrene, 99% methyl methacrylate, 99% maleic anhydride.
%Met.

Experimental Example 4 Preparation of Component (B) Graft Copolymer 143 parts of polybutadiene latex (solid content 35%, weight average particle diameter 0.35μ, gel content 90%) potassium stearate 1
Part, sodium formaldehyde sulfoxylate 0.1
Parts, tetrasodium ethylenediaminetetraacetic acid 0.03 parts, ferrous sulfate 0.003 parts and water 150 parts
After heating to 50 ° C, 50 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile, 0.2 part of t-dodecyl mercaptan, 0.15 of Kyumen hydroperoxide.
Parts were added continuously for 6 hours, and after addition, the temperature was raised to 65 ° C.
Polymerized for hours. The polymerization rate reached 97% by gas chromatography analysis. After adding an antioxidant to the obtained latex, coagulation with calcium chloride, washing with water and drying were performed to obtain a graft copolymer as a white powder. This is polymer B
It was set to -1.

Experimental Example 5 (B) Preparation of Component Graft Copolymer The composition of the monomer mixture of Experimental Example 3 was changed from 70% styrene and 30% acrylonitrile to 65% styrene, 25% acrylonitrile and 10% methyl methacrylate. Polymerization and precipitation were carried out in the same manner as in Experimental Example 3 except that the graft copolymer B-2 was obtained. The polymerization rate of this was 98% when analyzed by gas chromatography.

Experimental Example 6 Preparation of Component (C) Component Copolymer 70 parts of styrene, 30 parts of acrylonitrile, 2.5 parts of potassium stearate, 0.5 parts of t-dodecyl mercaptan and 250 parts of water were heated to 70 ° C., and persulfuric acid was added thereto. 0.05 part of potassium was added to initiate polymerization. After 7 hours from the start of the polymerization, 0.03 part of potassium persulfate was further added, and the temperature was raised to 75 ° C. and kept for 3 hours to complete the polymerization. The polymerization rate reached 97%. The obtained latex was coagulated with calcium chloride, washed with water and dried to obtain a white powder copolymer. This is polymer C
And

Examples 1 to 4 and Comparative Examples 1 to 5 Polymers A-1, A-2 and A-3 as component A imidized copolymers, polymer B- as component B graft copolymers
1 and B-2, polymer C as a C component copolymer, D-1 and D as a D component polyorganosiloxane compound
-2 was mixed in the proportion shown in Table 1, extruded at 270 ° C. by an extruder with a vent, pelletized, and then injection molded at 270 ° C. to form a test piece. Table 1 shows the measurement results of various physical property values.

D-1: Dimethyl silicone oil (degree of polymerization n = 100) D-2: Diphenyl silicone oil (degree of polymerization n = 50) From the results shown in Table 1, the thermoplastic resin composition of the present invention is It can be seen that the material has excellent properties (heat distortion temperature), moldability (melt flow rate), and thin-walled part strength (1 mm thick falling weight strength).

[0041]

[Table 1]

Test methods for measuring physical properties 1) Heat distortion temperature (HDT) Load 18.6 kg / cm ² , conforming to ASTM D-648. 2) Melt flow rate (MFR) 265 ° C, load 10 kg, according to JIS K-6874. 3) Izod impact strength (Izod) 1/4 "notch, conforming to ASTM D-256. 4) Falling weight strength of thin-walled part Measured falling weight strength (50% breaking height) at the center of a 1 mm thick square plate The weight of the weight was 50 g, and the radius R of the tip was 5 mm.

[0043]

As described above, the thermoplastic resin composition of the present invention has excellent heat resistance and moldability, and
The thin portion of the molded product also has good strength, and is characterized by extremely high practical value as various industrial parts and sports equipment materials.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C08L 83:04) 8319-4J

Claims (1)

[Claims] 1. A component (A): 0 to 40% by weight of a rubber-like polymer,
Aromatic vinyl monomer residue 30 to 69% by weight, unsaturated dicarboxylic acid imide monomer residue 30 to 60% by weight, unsaturated dicarboxylic acid anhydride residue 0 to 15% by weight, and vinyl other than these Imidized copolymer consisting of 0 to 40% by weight of body residue 10 to 90
Weight% (B) Component: Rubber-like polymer 5-80% by weight, aromatic vinyl monomer 40-80% by weight, vinyl cyanide monomer 2-40% by weight
And 0 to 40% by weight of vinyl monomer copolymerizable with these
Graft copolymer obtained by copolymerizing 20 to 95% by weight of a monomer consisting of 10 to 90% by weight (C) Component: 60 to 90% by weight of aromatic vinyl monomer, 10 to 40% of vinyl cyanide monomer % By weight, 10 to 80% by weight of a copolymer consisting of 0 to 40% by weight of a vinyl monomer copolymerizable therewith
(D) component: 0.05 to 2 parts by weight of a polyorganosiloxane compound represented by the following general formula [Chemical Formula 1] per 100 parts by weight of the total amount of the components (A), (B) and (C). A thermoplastic resin composition comprising: [Chemical 1] (R _{1 to} R ₄ are hydrogen, methyl group, phenyl group, carbon number of main chain
(Selected from epoxy end groups of 10 or less, amine end groups of 10 or less carbon atoms in the main chain)