JP2786890B2 - Thermoplastic resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having improved moldability, light discoloration resistance and heat resistance. More specifically, the present invention relates to a thermoplastic resin composition containing a polymer having an unsaturated dicarboxylic acid imide monomer residue.

(Prior art) Conventionally, a so-called ABS resin obtained by graft copolymerizing a mixture of styrene and acrylonitrile with a rubber-like polymer has been known. However, it has disadvantages such as heat resistance, for example, low heat deformation temperature and large heat shrinkage. There is a demand for improvement of heat resistance in, for example, automotive parts, and various improvement methods have been proposed.

For example, an aromatic vinyl monomer or vinyl cyan monomer
-Obtained by copolymerizing an aromatic vinyl monomer and a vinylcyan monomer in the presence of a copolymer obtained by copolymerizing a monomer mixture containing an aromatic substituted maleimide and a conjugated diolefin rubber. A resin composition comprising a graft copolymer has been proposed (UPS3642949).

However, in this resin composition, the N-
As the ratio of the aromatic-substituted maleimide increases, the heat resistance of the obtained resin composition improves, but there is a drawback that the moldability decreases. In order to improve the moldability, a lubricant is usually added. In this case, the moldability is improved, but there is a disadvantage that the light discoloration resistance is reduced.

(Problem to be Solved by the Invention) An object of the present invention is to provide a thermoplastic resin composition which has eliminated such drawbacks, has good heat resistance, and has good moldability and light discoloration resistance.

(Means for Solving the Problems) The inventors of the present invention have made intensive studies in order to solve the above-mentioned drawbacks, and as a result, have found that the following resin composition was invented to achieve the object.

That is, the present invention relates to: (A) component: 0 to 39% by weight of rubbery polymer, 30 to 69% by weight of aromatic vinyl monomer residue, 30 to 60% by weight of unsaturated dicarboxylic acid imide monomer residue A component (B), 10 to 89.9% by weight of an imidized copolymer comprising 1 to 20% by weight of an unsaturated dicarboxylic anhydride monomer residue and 0 to 39% by weight of a vinyl monomer residue other than these. : 5 to 80% by weight of rubbery polymer, 40 to 80% by weight of aromatic vinyl monomer, 0 to 40% by weight of vinyl cyanide monomer and 0 to 40% by weight of vinyl monomer copolymerizable therewith % Of a graft copolymer obtained by copolymerizing 20 to 95% by weight of a monomer mixture consisting of 10% to 89.9% by weight of a thermoplastic resin other than the components (A) and (B). And (D) component: a hydroxy fatty acid having 10 or more carbon atoms in the main chain.
0.1 to 20% by weight of a thermoplastic resin composition.

First, the imidized copolymer of the component A and its production method will be described.

(A) As a method for producing the component copolymer, an aromatic vinyl monomer, an unsaturated dicarboxylic acid imide monomer, and a vinyl copolymerizable with these, in the presence of a rubbery polymer, if necessary as a first method. Method of copolymerizing monomer mixture, second
If necessary, a polymer obtained by copolymerizing an aromatic vinyl monomer, an unsaturated dicarboxylic anhydride and a vinyl monomer mixture copolymerizable therewith in the presence of a rubbery polymer with ammonia and / or There is a method in which a primary amine is reacted to convert 40 to 100 mol% of an acid anhydride group into an imide group, and an imidized copolymer can be obtained by any method.

(A) Component Copolymer As the aromatic vinyl monomer used in the first production method, styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene, and substituted monomers thereof And styrene is particularly preferred among these.

Examples of unsaturated dicarboxylic imide monomers include maleimide, N-methylmaleimide, N-butylmaleimide,
-Phenylmaleimide, N-methylphenylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-chlorophenylmaleimide,
N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-cyclohexylmaleimide, maleimide derivatives such as N-isopropylmaleimide, N-methylitaconimide, itaconic imide derivatives such as N-phenylitaconimide, and the like. Of these, N-phenylmaleimide is particularly preferred.

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

Further, a vinyl monomer copolymerizable therewith may be copolymerized. Examples of the copolymerizable vinyl monomer include vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile; acrylate monomers such as methyl acrylate and ethyl acrylate; and methyl methacrylate. Acid esters, methacrylate monomers such as ethyl methacrylate,
There are vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amide, methacrylic acid amide and the like, and among these, monomers such as acrylonitrile, methacrylic acid ester, acrylic acid and methacrylic acid are preferable.

The temperature of the imidation reaction is about 80-350 ° C, preferably 100-300 ° C. When the temperature is lower than 80 ° C., the reaction rate is low, and the reaction requires a long time, which is not practical. On the other hand, when the temperature exceeds 350 ° C., the physical properties of the polymer decrease due to thermal decomposition.

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

Solvents for imidization in a solution state include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, tetrahydrofuran, dimethylformamide, etc. Among them, methyl ethyl ketone and methyl isobutyl ketone are preferred. The non-aqueous medium used 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 of the component (B) and its production method will be described.

The rubbery polymer used as the component (B) is a polymer consisting of butadiene alone or a vinyl monomer copolymerizable therewith, an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer or an acrylic ester alone. Alternatively, there is a polymer comprising a vinyl monomer copolymerizable therewith.

As the aromatic vinyl monomer used for the component (B), styrene, α-methylstyrene, vinyltoluene, t-
Styrene monomers such as butylstyrene and chlorostyrene, and substituted monomers thereof, and among these, monomers such as styrene and α-methylstyrene are particularly preferred.

Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like, and acrylonitrile is particularly preferable. Examples of the vinyl monomer copolymerizable therewith include acrylate esters such as methyl acrylate, ethyl acrylate and butyl acrylate, and methacrylate monomers such as methyl methacrylate and ethyl methacrylate. And vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide and methacrylamide. Of these, methyl methacrylate, acrylic acid, and methacrylic acid are particularly preferred.

The method for preparing the graft copolymer (B) is as follows: 40 to 80% by weight of an aromatic vinyl monomer, 0 to 40% by weight of a vinyl cyanide monomer and 5 to 80% by weight of a rubbery polymer. It is obtained by graft copolymerizing 20 to 95% by weight of a monomer mixture composed of 0 to 40% by weight of a copolymerizable vinyl monomer. As the polymerization, 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 the produced polymer in a non-solution.

Next, the thermoplastic resin composition of the component (C) will be described.

The thermoplastic resin that can be used as the component (C) is (A)
A resin having good compatibility with the imidized copolymer as the component and the graft copolymer as the component (B), for example, 30 to 90% by weight of an aromatic vinyl monomer, 0 to 90% by weight of a vinyl cyanide monomer. 50
A copolymer obtained by copolymerizing a monomer mixture consisting of 0% by weight and 0 to 50% by weight of a vinyl monomer copolymerizable therewith,
Polycarbonate, polybutylene terephthalate, polyethylene terephthalate, 6,6-nylon, 6-nylon, 12-nylon, polyphenylene oxide, styrene-grafted polyphenylene oxide, and polyphenylene oxide, and the like. Resins can be used.

As the aromatic vinyl monomer used for the component (C), styrene, α-methylstyrene, vinyltoluene, t-
Styrene monomers such as butylstyrene and chlorostyrene, and substituted monomers thereof, of which styrene and α-methylstyrene are particularly preferred.

As the vinyl cyanide monomer, acrylonitrile,
There are methacrylonitrile, α-chloroacrylonitrile and the like, and acrylonitrile is particularly preferable.

As vinyl monomers copolymerizable with these, acrylate monomers such as methyl acrylate, ethyl acrylate and butyl acrylate,
Methacrylic acid ester monomers such as methyl methacrylic acid ester and ethyl methacrylic acid ester, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide, methacrylamide, acenaphthylene, N-vinylcarbazole, N-alkyl Substituted maleimides, N-aromatic substituted maleimides and the like can be mentioned.

Next, hydroxy fatty acids having 10 or more carbon atoms in the main chain used as the component (D) in the present invention will be described.

The carbon atom having a hydroxyl group of the hydroxy fatty acid used in the present invention is not particularly limited, and the hydroxyl group may be located anywhere except for carbon constituting the carboxylic acid group.

Further, the hydroxy fatty acid of the component (D) includes hydroxyundecylic acid, hydroxylauric acid, hydroxytridecylic acid, hydroxymyristic acid, hydroxypentadecylic acid, hydroxypalmitic acid, hydroxyheptadecylic acid, hydroxystearic acid, hydroxybehenic acid And the like.

Further, when the imidized copolymer as the component (A) is less than 10% by weight in the resin composition, the heat resistance is not sufficiently improved, and
If it exceeds 9.9% by weight, heat resistance is high, but impact resistance is undesirably reduced.

The graft copolymer as the component (B) is contained in the resin composition.
If it is less than 10% by weight, the impact resistance is low, and if it exceeds 89.9% by weight, the rigidity is undesirably reduced.

The thermoplastic resin as the component (C) has a content of 79.9% in the resin composition.
If the amount is more than 10% by weight, heat resistance is undesirably lowered.

When the content of the hydroxy fatty acid as the component (D) is less than 0.1% by weight in the resin composition, the moldability is not sufficiently improved, and when it exceeds 20% by weight, the moldability is improved, but the heat resistance is lowered, which is not preferable. .

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

As a mixing form, there is a method of obtaining a composition by ordinary melt mixing, multi-stage melt kneading using master pellets or the like, blending in a solution, and the like.

The composition of the present invention may further contain a stabilizer, a flame retardant, a plasticizer, a lubricant, an ultraviolet absorber, a colorant, and a filler such as talc, silica, clay, mica, and calcium carbonate.

(Examples) Hereinafter, the present invention will be described with reference to examples. All parts and percentages in the examples are expressed on a weight basis.

(Experimental example 1) Production of component (A) 60 parts of styrene and 50 parts of methyl ethyl ketone were charged into an autoclave equipped with a stirrer, the system was purged with nitrogen gas, and the temperature was raised to 85 ° C. Part and benzoyl peroxide 0.15 part in methyl ethyl ketone 250
The solution dissolved in the part was added continuously over 8 hours. After the addition the temperature was kept at 85 ° C. for a further 3 hours. As a result of sampling a part of the viscous reaction solution and quantifying the degree of polymerization by gas chromatography, styrene 99%, maleic anhydride
99%. To the copolymer solution obtained here, 34 parts of aniline and 0.3 part of triethylamine were added at 0.90 molar equivalents relative to maleic anhydride, and reacted at 140 ° C. for 7 hours. 200 parts of methyl ethyl ketone was added to the reaction solution, cooled to room temperature, poured into 1500 parts of vigorously stirred methanol, separated by filtration, and dried to obtain an imidized copolymer. C-13 NMR analysis revealed that the maleic anhydride monomer residue was 3.1% by weight. This was designated as polymer A-1.

(Experimental Example 2) Production of component (A) 60 parts of styrene, 100 parts of methyl ethyl ketone, and 10 parts of polybutadiene cut into small pieces were charged into an autoclave equipped with a stirrer, and stirred at room temperature for 24 hours to dissolve the rubber. Then, the inside of the system was replaced with nitrogen gas, and the temperature was raised to 85 ° C. 40 parts of maleic anhydride and benzoyl peroxide 0.
A solution prepared by dissolving 15 parts in 250 parts of methyl ethyl ketone was continuously added in 8 hours. 85 ° C for additional 3 hours after addition
Kept. As a result of sampling a part of the viscous reaction solution and quantifying the unreacted monomer by gas chromatography, the polymerization rate was 98% for styrene and 98% for maleic anhydride. The copolymer solution obtained here 36.1 parts of aniline 0.95 equivalents to maleic anhydride, triethylamine 0.
3 parts were added and reacted at 140 ° C. for 7 hours. 200 parts of methyl ethyl ketone was added to the reaction solution, cooled to room temperature, poured into 1500 parts of vigorously stirred methanol to obtain a rubber-modified imidized copolymer which was precipitated, filtered and dried. This was polymer A-2
And

(Experimental Example 3) Production of Component (A) Polymerization was carried out 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, to give an imidized copolymer A-3. Obtained.

The polymerization rate is 98% styrene, 99% methyl methacrylate,
It was 99% maleic anhydride.

(Experimental example 4) Production of component (B) 143 parts of polybutadiene latex (solid content 35%, weight average particle size 0.35μ, gel content 90%), potassium stearate 1 part, sodium formaldehyde sulfoxylate 0 .
1 part, tetrasodium ethylenediaminetetraacetylic acid 0.03 part, ferrous sulfate 0.003 part and water 150 parts
The mixture was heated to 50 ° C., and 50 parts of a monomer mixture composed of 70% of styrene and 30% of acrylonitrile, 0.2 parts of t-dodecyl mercaptan, and 0.15 of cumene hydroperoxide were added thereto.
Parts were added continuously in 6 hours, and after the 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, it was coagulated with calcium chloride, washed with water and dried to obtain a graft copolymer as a white powder. This is polymer B-
It was set to 1.

(Experimental example 5) Production of component (B) The experiment was conducted except that the composition of the monomer mixture of Experimental example 4 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 Example 4 to obtain a graft copolymer B-2. The polymerization rate of the product was analyzed by gas chromatography and found to be 98%.

(Experimental example 6) Production of component (C) 75 parts of styrene, 30 parts of acrylonitrile, 2.5 parts of potassium stearate, 0.5 part of t-dodecylmercaptan and 250 parts of water were heated to 70 ° C, and 0.05 part of potassium persulfate was added thereto. It was added to start polymerization. Seven hours after the start of the polymerization, 0.03 part of potassium persulfate was further added, and the temperature was raised to 75 ° C. and maintained for 3 hours to complete the polymerization. The conversion reached 97%. The obtained latex was coagulated with calcium chloride, washed with water and dried to obtain a white powdery copolymer. This is polymer C
And

Examples 1 to 5 As component A, polymers A-1, A-2, or A-3,
The polymer B-1 or B-2 is used as the component B, the polymer C or polycarbonate (manufactured by Teijin Chemicals Ltd., Panlite K-1300W) and 12-hydroxystearic acid are mixed in the ratio shown in Table 1 as the component C. After extruding into pellets at 270 ° C. with a vented extruder, injection molding was performed at 270 ° C. to form test pieces. The results are shown in Table 1.

Comparative Example The physical properties were measured in the same manner as in Examples 1 to 5, except that ethylene-bis-stearyl amide (Kao Waggs EB-P) was used instead of 12-hydroxystearic acid used in Examples 1 to 5. The results are shown in Table 1.

Physical property measurement test method 1) Heat deformation temperature Load 18.6 kg / cm ² , according to ASTM D-648.

2) Melt flow rate: 265 ° C, load: 10 kg, according to JIS K7210.

3) Use a fade meter (black panel temperature)
(At 83 ° C, without rain) for 600 hours, and those with severe yellowing were rated as x, and those with little yellowing were rated as o.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-64-603 (JP, A) JP-A-63-35629 (JP, A) JP-A-53-106747 (JP, A) JP-A-59-1985 62655 (JP, A)

Claims (1)

(57) [Claims] (1) Component (A): 0 to 39% by weight of a rubbery polymer;
30 to 69% by weight of aromatic vinyl monomer residue, 30 to 60% by weight of unsaturated dicarboxylic acid imide monomer residue, 1 to 20% by weight of unsaturated dicarboxylic anhydride monomer residue and other Imidized copolymer consisting of 0 to 39% by weight of vinyl monomer residues
(B) component: 5 to 80% by weight of a rubbery polymer, 40 to 80% by weight of an aromatic vinyl monomer, 0 to 40% by weight of a vinyl cyanide monomer, and 10 to 89.9% by weight of a graft copolymer obtained by copolymerizing 20 to 95% by weight of a monomer mixture composed of 0 to 40% by weight of a polymerizable vinyl monomer, and component (C): component (A) and component (A). 0 to 79.9% by weight of a thermoplastic resin other than the component (B), and a component (D): a hydroxy fatty acid having 10 or more carbon atoms in the main chain.
0.1-20% by weight of a thermoplastic resin composition.