WO2008026554A1

WO2008026554A1 - Resin composition and molded body thereof

Info

Publication number: WO2008026554A1
Application number: PCT/JP2007/066583
Authority: WO
Inventors: Kouichi Shimizu; Masamichi Endo; Tetsuya Shinmura
Original assignee: Denki Kagaku Kogyo Kabushiki Kaisha
Priority date: 2006-08-28
Filing date: 2007-08-27
Publication date: 2008-03-06
Also published as: CN101506299A; JPWO2008026554A1; KR20090055559A; TW200831591A; CN101506299B

Abstract

Disclosed is a resin composition having an excellent balance among heat resistance, impact resistance and molding workability, while being excellent in strength of a thin portion. Also disclosed is a molded body of such a resin composition. Specifically disclosed is a resin composition containing 5-40% by mass of the component (A) described below, 30-75% by mass of the component (B) described below, and 10-50% by mass of the component (C) described below. Component (A): a maleimide copolymer containing an aromatic vinyl monomer residue, an unsaturated dicarboxylic acid imide derivative residue and an unsaturated dicarboxylic acid anhydride monomer residue, and having a weight average molecular weight of 90,000-130,000 Component (B): a vinyl copolymer containing an aromatic vinyl monomer residue and a vinyl cyanide monomer residue, and having a weight average molecular weight of 100,000-160,000 Component (C): a graft copolymer obtained by graft-copolymerizing a monomer mixture containing an aromatic vinyl monomer and a vinyl cyanide monomer to a rubbery polymer

Description

Specification

Resin composition and molded body thereof

Technical field

The present invention relates to a resin composition containing a maleimide copolymer and a molded product thereof.

Background art

Conventionally, as a resin composition excellent in heat resistance, impact resistance and molding processability, a resin composition having a maleimide copolymer, a bull aromatic copolymer and a graft copolymer has been known (patent) Reference 1).

However, when the resin composition is highly required to have high strength at the thin wall portion, the strength is insufficient and measures such as devising the molded product design may be necessary.

Patent Document 1: Japanese Patent Application Laid-Open No. 8-183890

Disclosure of the invention

Problems to be solved by the invention

[0004] An object of the present invention is to provide a resin composition excellent in the strength of the thin-walled portion and having an excellent balance of heat resistance, impact resistance, and moldability, and a molded product thereof.

Means for solving the problem

[0005] The gist of the present invention is as follows.

(1) Component (A) 5-40% by mass, (B) Component 30-75% by mass, and (C) Component 1 shown below

A resin composition comprising 0 to 50% by mass.

Component (A): 40-80% by mass of aromatic bule monomer residue, 10-60% by weight of unsaturated dicarboxylic imide derivative, and 2% by weight of unsaturated dicarboxylic anhydride monomer residue A maleimide copolymer having a weight average molecular weight of 90,000 to 130,000, including a full (but not including 0).

Ingredient (B): Resin containing 67 to 78% by weight of aromatic bule monomer residue and 22 to 33% by weight of cyanide bur monomer residue and having a weight average molecular weight of 100,000 to 160,000 Polymer.

Component (C): a rubber-like polymer 30-70 wt%, aromatic Bulle monomer 50 to 80 weight ^_0/0, And a graft copolymer obtained by graft polymerization of 30 to 70% by mass of a monomer mixture containing 20 to 40% by mass of cyanide bule monomer.

(2) The resin composition according to (1), comprising 10 to 30% by mass of component (A), 40 to 65% by mass of component (B), and 20 to 40% by mass of component (C). .

(3) In the component (A), the aromatic bulle monomer strength is S styrene, the unsaturated dicarboxylic imide derivative is N-phenylmaleimide, and the unsaturated dicarboxylic acid anhydride monomer is maleic anhydride. The resin composition according to the above (1) or (2), which is an acid.

(4) In any one of the above (1) to (3), in the component (B), the aromatic butyl monomer is styrene and the vinyl cyanide monomer is acrylonitrile. Resin composition.

(5) The resin composition according to any one of (1) to (4), wherein the rubber-like polymer in the component (C) is a butadiene polymer and / or a butadiene-styrene copolymer. object.

(6) In any one of the above (1) to (5), in the component (C), the aromatic butyl monomer power is S styrene, and the vinyl cyanide monomer is acrylonitrile. Resin composition.

(7) The component (A) contains an unsaturated dicarboxylic acid anhydride monomer residue in an amount of 0.;! To 1.5% by mass. The resin composition described in 1.

(8) The component (A) further comprises a butyl monomer residue copolymerizable with the aromatic butyl monomer, the unsaturated dicarboxylic acid imide derivative, and the unsaturated dicarboxylic acid anhydride monomer. 6. The resin composition according to any one of (1) to (7) above, which is a maleimide copolymer containing 18% by mass or less of a group.

(9) The component (B) is a bulle copolymer further containing 10% by mass or less of the bulle monomer copolymerizable with the aromatic bulle monomer and the cyanated bulle monomer. 2. The resin composition according to 1 above, wherein the! / Of (1) to (8) is a deviation force.

(10) In the component (C), the monomer mixture to be graft-polymerized has a butyl monomer residue copolymerizable with the aromatic vinyl monomer and the cyanated butyl monomer. 2. The resin composition according to item 1, comprising not more than% by mass of (1) to (9). (11) A molded article comprising the resin composition according to any one of (1) to (; 10).

(12) The molded body according to (11), wherein the molded body is an injection molded body.

The invention's effect

[0006] According to the present invention, a resin composition excellent in the strength of the thin-walled portion and having an excellent balance of heat resistance, impact resistance, and moldability can be obtained by blending a specific component at a specific ratio. Furthermore, a molded body using the resin composition can be suitably used for automobile parts, electrical / electronic machine parts, precision machine parts, office equipment parts, heat appliances and the like due to these excellent features.

BEST MODE FOR CARRYING OUT THE INVENTION

[0007] The maleimide copolymer of component (A) will be described. In the present invention, the residue means a corresponding repeating unit in a polymer obtained by polymerizing a monomer or a derivative.

Component (A) contains an aromatic butyl monomer residue, an unsaturated dicarboxylic imide derivative residue, and an unsaturated dicarboxylic anhydride monomer residue, and has a weight average molecular weight of 90,000 to 130,000. This is a maleimide copolymer.

As the production method of component (A), as a first production method, a monomer mixture of an aromatic butyl monomer, an unsaturated dicarboxylic acid imide derivative, and an unsaturated dicarboxylic acid anhydride monomer is co-polymerized. As a second method, after copolymerizing a monomer mixture of an aromatic butyl monomer and an unsaturated dicarboxylic acid anhydride monomer, an unsaturated dicarboxylic acid anhydride in the copolymer Examples thereof include a method in which a monomer unit residue is reacted with ammonia and / or a primary amine (imidation reaction) to be converted into an unsaturated dicarboxylic acid imide derivative unit. The maleimide copolymer of component (A) can also be obtained by the method of V and deviation.

[0008] The aromatic bur monomer constituting the component (A) is not particularly limited. For example, styrene-based monomers such as styrene, α-methylstyrene, butyltoluene, t-butylstyrene, and chlorostyrene. Monomer. One or more of these monomers can be used. Particularly preferred is styrene.

[0009] The unsaturated dicarboxylic imide derivative constituting the component (A) is not particularly limited, and examples thereof include maleimide, N-methylmaleimide, N-ethylmaleimide, and N-cyclohex Xyl maleimide, N ferromaleimide, N naphthyl maleimide, glutarimide and the like. Particularly preferred is N phenylmaleimide.

[0010] The unsaturated dicarboxylic acid anhydride monomer constituting the component (A) is not particularly limited, and examples thereof include maleic acid, itaconic acid, citraconic acid, and aconitic acid, respectively. It is done. These monomers can be used alone or in combination of two or more. Particularly preferred is maleic anhydride.

[0011] The maleimide copolymer of component (A) can be further copolymerized with the aromatic bulle monomer, the unsaturated dicarboxylic imide derivative, and the unsaturated dicarboxylic anhydride monomer. It can also contain a bull monomer residue. Such copolymerizable butyl monomer is not particularly limited, and examples thereof include cyanide butyl monomers such as acrylonitrile and methatalonitrile, methyl acrylate ester, ethyl acrylate ester, and propyl acrylate ester. Acrylic acid esters, methyl methacrylate esters, methacrylic acid ester monomers such as ethyl methacrylate, butylcarboxylic acid monomers such as acrylic acid and methacrylic acid, attalinoleamide, methacryloleamide, N— Examples include bull force rubazole. These monomers can be used alone or in combination of two or more. Preferred are methyl acrylate, acrylic acid and methacrylic acid. In addition, unsaturated dicarboxylic acid anhydride monomer is also listed as a copolymerizable bull monomer in the first production method, and in the second production method, the unsaturated dicarboxylic acid anhydride that remains without being converted to an imide group. Groups can also be introduced into the copolymer.

[0012] In the case of the above-mentioned first production method, bulk suspension polymerization, solution polymerization, and bulk polymerization are used. In the case of the second production method, suspension polymerization, emulsion polymerization, solution polymerization, bulk polymerization, and the like are known. Use the polymerization method.

[0013] In the second production method, ammonia or primary amine used in the imidization reaction may be in an anhydrous state or an aqueous solution. The primary amine is not limited, and examples thereof include alkylamines such as methylamine, ethylamine and cyclohexylamine, and aromatic amines such as aniline, toluidine and naphthylamine. These monomers can be used alone or in combination of two or more. Particularly preferred is aniline.

[0014] When the imidization reaction is performed in a solution state or a suspension state, an ordinary reaction vessel such as When it is carried out in a massive molten state, where it is preferable to use a clave or the like, an extruder equipped with a devolatilizer can be used.

[0015] The temperature of the imidization reaction is about 80 to 350 ° C, preferably 100 to 300 ° C. When the temperature is lower than 80 ° C, the reaction takes a long time for the reaction rate to be slow, which is not practical. On the other hand, when the temperature exceeds 350 ° C, the physical properties of the polymer deteriorate due to thermal decomposition. A tertiary amine such as triethylamine is preferably used as the catalyst which may be used during the imidation reaction.

[0016] The weight average molecular weight of the component (A) is 90,000 to 130,000, preferably 100,000 to 120,000.

If it is less than 90,000, the impact strength of the resulting resin composition is lowered, and if it exceeds 130,000, the strength of the thin part of the obtained resin composition is not sufficiently improved.

[0017] The aromatic bur monomer residue used in the component (A) is preferably 40 to 80% by mass, more preferably 40 to 60% by mass. If it is less than 40% by mass, the moldability is reduced.

If it exceeds 0% by mass, the heat resistance decreases.

Moreover, unsaturated dicarboxylic imide derivative residue is 10-60 mass%, More preferably

It is 10-59 mass%, More preferably, it is 35-55 mass%. If it is less than 10% by mass, the heat resistance is not sufficiently improved. If it exceeds 60% by mass, the impact strength of the resin composition will be greatly reduced.

The unsaturated dicarboxylic acid anhydride monomer residue is less than 2% by mass (however, 0% by mass is not included), preferably 0.;! To 1.9% by mass, particularly preferably 0. 3 ~; 1. 1% by mass. When the unsaturated dicarboxylic acid anhydride monomer residue is 2% by mass or more or not contained, the strength of the thin portion is not significantly improved.

Further, the above-mentioned butyl monomer residues copolymerizable with these are preferably contained in an amount of 18% by mass or less, more preferably 10% by mass or less. If the copolymerizable butyl monomer residue exceeds 18% by mass, the compatibility with other components decreases, impact resistance tends to decrease, and delamination occurs when formed into a molded body. It becomes easy to do.

[0018] The bull copolymer of component (B) will be described below.

Component (B) is a bulle copolymer containing an aromatic bulle monomer residue and a cyanide bur monomer residue and having a weight average molecular weight of 100,000 to 160,000. The aromatic bull monomer used in component (B) is not particularly limited, but those listed as aromatic bull monomers used in component (A) can be used. It can be the same or different. Styrene is preferred.

Although it does not specifically limit as a cyanide bur monomer, For example, an alicyclic nitrile, a metathalonitrile, (alpha) -kuroguchi acrylonitrile is mentioned. These monomers can be used alone or in combination of two or more. Acrylonitrile is preferred.

In addition, the component (ii) can further contain a bull monomer copolymerizable with the aromatic bull monomer and the cyanated bull monomer. The copolymerizable bull monomer is not particularly limited! /, But those described as the copolymerizable bull monomer used for the component (Α) can be used, and the component (Α) It may be the same as or different from the one used for.

[0019] A preferable aromatic bule monomer residue in the component (ii) is 67 to 78% by mass, and more preferably 69 to 76% by mass. If it is less than 67% by mass, the moldability deteriorates, and if it exceeds 78% by mass, the heat resistance decreases, which is not preferable.

Moreover, a preferable cyanide bur monomer residue is 22-33 mass%, More preferably, it is 24-31 mass%. If it is less than 22% by mass or more than 33% by mass, the compatibility with the component (ii) is reduced, and when the obtained resin composition is molded, it is easy to cause appearance defects such as delamination and impact strength. It also causes a decrease.

In addition, the butyl monomer residue copolymerizable with these is preferably 10% by mass or less, more preferably 5% by mass or less. When the content of the copolymerizable butyl monomer residue exceeds 10% by mass, the compatibility with the component (ii) and the component (C) is lowered, and the resulting resin composition is made into a molded body. Occasionally, an appearance defect phenomenon of delamination easily occurs and also causes a drop in impact strength.

[0020] The component (ii) can be produced by an ordinary polymerization method. Examples of the production method include suspension polymerization, solution polymerization, emulsion polymerization and the like.

The weight average molecular weight of component (ii) is 100,000 to 160,000, preferably 120,000 to 150,000. If it is less than 100,000, the impact strength and thin part strength of the resulting resin composition are reduced, and if it exceeds 160,000, the moldability of the resulting resin composition is lowered and the strength of the thin part is reduced. [0021] The graft copolymer of component (C) will be described.

Component (C) is a graft copolymer obtained by graft-polymerizing a rubber-like polymer with a monomer mixture containing an aromatic bulle monomer and a cyanated bully monomer.

The rubbery polymer used for component (C) is not particularly limited as long as it is a graft-polymerizable rubber. For example, it can be copolymerized with butadiene such as a butadiene polymer or a butadiene-styrene copolymer. A copolymer with a bulle monomer, an ethylene propylene copolymer, an ethylene propylene copolymer, an acrylic rubber, and the like may be mentioned. These may be used alone or in combination of two or more. In the case of butadiene-styrene copolymer, the butadiene monomer is preferably 60% by mass or more! /.

[0022] The aromatic bur monomer used in the component (C) is not particularly limited.

What was described as a precursor of the aromatic bur monomer residue used for A) component can be used, and may be the same as that used for (A) component and (B) component, or may be different. Styrene is preferred.

Preferable! /, (B) The aromatic bulle monomer in the monomer mixture is 50 to 80% by mass, more preferably 60 to 80% by mass. If the aromatic bulle monomer is less than 50% by weight, the moldability is lowered, and if it exceeds 80% by weight, the impact resistance is lowered.

[0023] Although the cyanated butyl monomer used in the component (C) is not particularly limited,

Those described as precursors of cyanide bur monomer residues used for component B) can be used and may be the same as or different from those used for component (B). Atalylonitrile is preferred.

Component (C) The cyanide butyl monomer in the monomer mixture is preferably 20 to 40% by mass, more preferably 24 to 31% by mass. If the cyanide butyl monomer is less than 20% by mass or more than 40% by mass, the compatibility of the component (C) with the component (A) decreases, and the resulting resin composition is molded into a molded product. In addition, the appearance failure phenomenon of delamination easily occurs, and the impact strength is reduced.

[0024] The copolymerizable bull monomer used in component (C) is not particularly limited, but V, a precursor of a copolymerizable bull monomer residue used in component (A). Can be used, either the same or different from those used for component (A) or component (B) Good. Preferred are methyl acrylate, acrylic acid and methacrylic acid.

The amount of copolymerizable butyl monomer in component (C) monomer mixture is preferably 20% by mass or less, particularly preferably 10% by mass or less. If the copolymerizable bulle monomer exceeds 20% by mass, the compatibility with other components will decrease, and impact resistance will tend to decrease, and delamination will occur when the resulting resin composition is molded. The appearance defect phenomenon is likely to occur.

[0025] In the production of the graft polymer as component (C), any known polymerization technique can be used. For example, aqueous heterogeneous polymerization such as suspension polymerization and emulsion polymerization, bulk polymerization, solution polymerization, and the produced polymer is precipitated heterogeneous polymerization and combinations thereof strength ^s in a poor solvent.

[0026] Graft rubber particle diameter, graft ratio, and weight average molecular weight of the ungrafted copolymer in the component (C) are not particularly limited, but the graft rubber particle diameter is from 0 .;! To 0.8 111. The range of 0.2 to 0.6 m is more preferable from the viewpoint of impact resistance. The graft ratio is 20 to 80%, particularly preferably 30 to 70%. If the graft ratio is less than 20%, the rubbery polymer is likely to aggregate, so that a defective appearance phenomenon is likely to occur, resulting in a reduction in impact resistance, and if it exceeds 80%, a molding processability is reduced. The ungrafted copolymer has a weight average molecular weight in the range of 50,000 to 200,000, particularly preferably in the range of 60,000 to 140,000, which provides a good balance between impact resistance and moldability.

[0027] Component (C) is a mixture of the above-mentioned aromatic bulle monomer, cyanated bulur monomer monomer, and, if necessary, a copolymerizable bur monomer. the 70 wt%, which is graft polymerized to the rubber-like polymer 30-70 weight%, particularly preferably, the mixture 40 to 60 weight ^_0/0, rubber-like polymer 40-60 weight ⁰ / ₀ is graft polymerized. If the rubber-like polymer is less than 30% by mass, the impact resistance of the resin composition is lowered, and if it exceeds 70% by mass, the molding processability is lowered, and the resulting resin composition is liable to cause an appearance defect phenomenon.

[0028] In the graft polymerization, it is usually difficult for the whole amount of the monomer to be grafted onto the rubber-like polymer, and a non-grafted copolymer is produced as a by-product. In the present invention, not only a true graft copolymer from which a non-grafted copolymer has been positively separated and removed, but also a graft polymerization containing a non-grafted copolymer can be used as a graft copolymer. It can be handled. [0029] The compounding ratio of the component (A), the component (B), and the component (C) in the resin composition of the present invention is as follows. The component (A) is 5 to 40% by mass, and the component (B) is 30 to 75% by mass. %, Component (C) is 10 to 50% by mass. Among these, (A) component, (B) component, and (C) component and the compounding ratio are (A) component 10-30 mass%, (B) component 40-65 mass%, (C) component. Is preferably 20 to 40% by mass.

When the component (A) is less than 5% by mass, the heat resistance of the resulting resin composition is significantly reduced, and when it exceeds 40% by mass, the strength of the thin-walled portion is significantly reduced.

If the component (B) is less than 30% by mass, the fluidity or thin part strength of the resulting resin composition will be significantly reduced, and if it exceeds 75% by mass, the thin part strength will be reduced.

If the component (C) is less than 10% by mass, the strength of the thin part of the resulting resin composition will be reduced, and if it exceeds 50% by mass, the heat resistance and fluidity will be reduced.

[0030] The resin composition of the present invention can be obtained by using an ordinary melt-kneading apparatus. As a melt-kneading apparatus that can be suitably used, a single-screw extruder, a combined type co-rotation or a combined type different direction There are screw extruders such as rotary twin screw extruders, non- or incompletely integrated twin screw extruders, Banbury mixers, kneaders and mixing rolls.

[0031] The resin composition contains a stabilizer, a plasticizer, a lubricant, an antioxidant, an ultraviolet absorber, a light stabilizer, glass fiber, carbon fiber, an inorganic filler, a colorant and the like as long as the effects of the present invention are not impaired. Can be blended.

Example

[0032] The present invention will be further described below with reference to Examples and Comparative Examples, but these are illustrative only and do not limit the contents of the present invention. In the examples and comparative examples, parts and percentages are! /, Based on mass unless otherwise specified.

[0033] Production of maleimide copolymer (A) component

In an autoclave equipped with a stirrer, 60 parts of styrene, 0-3 parts of α-methylstyrene dimer, and 100 parts of methyl ethyl ketone were charged, and the system was purged with nitrogen gas, and then the temperature was raised to 85 ° C and anhydrous. A solution prepared by dissolving 40 parts of maleic acid and 0.15 part of benzoyl peroxide in 200 parts of methyl ethyl ketone was continuously added in 8 hours. The temperature was kept at 85 ° C for an additional 3 hours after the addition. To the copolymer solution thus obtained, 38 parts of aniline and 0.6 part of triethylamine were added and reacted at 140 ° C. for 7 hours. Supply the reaction solution to a vented twin screw extruder, The maleimide copolymer was obtained by devolatilization. From the C-13 NMR analysis, the conversion of acid anhydride groups to imide groups was 94 mol%. This maleimide copolymer is a copolymer containing 51.1% of N-phenylmaleimide units as unsaturated dicarboxylic imide derivatives, 47.0% of styrene units, and 1.9% of maleic anhydride units. Was Copolymer A-1. For other maleimide copolymers A-2 to A-10, the conversion rate of maleic anhydride to imide groups is adjusted by adjusting the addition amount of aniline, and the addition amount of α-methylstyrene dimer is adjusted. This was prepared in the same manner as Α-1, except that the weight average molecular weight was adjusted. The component composition and weight average molecular weight are shown in Table 1.

[0034] In an autoclave equipped with a stirrer, 47 parts of styrene, 0-6 parts of α-methylstyrene dimer and 100 parts of methyl ethyl ketone were charged, and the system was replaced with nitrogen gas, and the temperature was raised to 90 ° C. A solution prepared by dissolving 53 parts of N-phenylmaleimide and 0.15 part of benzoyl peroxide in 200 parts of methyl ethyl ketone was continuously added in 6 hours. The temperature was kept at 90 ° C for an additional 3 hours after the addition. The reaction solution was supplied to a twin screw extruder with a vent and devolatilized to obtain a maleimide copolymer. This maleimide copolymer is a copolymer containing 53.0% of N-phenylmaleimide units and 47.0% of styrene units as an unsaturated dicarboxylic imide derivative, which is referred to as copolymer A-11. did. Ingredient composition and weight average molecular weight are shown in Table 1.

[0035] [Table 1]

Bull copolymer (B) Component production

In a reaction vessel equipped with a stirrer, 71.5 parts of styrene, 28.5 parts of acrylonitrile, 2.5 parts of calcium triphosphate, 0.33 parts of tododecyl mercaptan, t-butyl peroxyacetate 0 2 parts and 250 parts of water were charged and the temperature was raised to 70 ° C. to initiate polymerization. Seven hours after the start of polymerization, the temperature was raised to 75 ° C. and maintained for 3 hours to complete the polymerization. The polymerization rate reached 97%. To the resulting reaction solution, 200 parts of a 5% aqueous hydrochloric acid solution was added for precipitation, followed by dehydration and drying to obtain a white bead copolymer. The composition of this copolymer was 72.0% styrene, 28.0% attaryl nitrile, and the weight average molecular weight was 130,000, and this was designated as copolymer B-1. For other bur copolymers B-2 to B-5, the composition ratio of styrene and acrylonitrile is adjusted by adjusting the addition amount of styrene and acrylonitrile, and the weight average molecular weight is adjusted by adjusting the addition amount of tododecyl mercaptan. It was manufactured in the same manner as B-1, except that the amount of was adjusted. The component composition and the weight average molecular weight are shown in Table 2. [0037] [Table 2]

Table 2

[0038] Production of graft copolymer (C) component

In a reaction vessel equipped with a stirrer, 126 parts of polybutadiene latex (solid content 35%, average particle size 0 · 3 111, gel content 90%), 17 parts of styrene monobutadiene latex (solid content 67%, average particle size 0. δ μ ΐη ^ gel content 15%), sodium stearate 1 part, sodium formaldehyde sulfoxylate 0.2 part, tetrasodium ethylenediamine tetraacetic acid 0.01 part, ferrous sulfate 0 005 parts and 150 parts of pure water were heated to a temperature of 50 ° C. To this, 45 parts of a monomer mixture consisting of 75% styrene and 25% acrylonitrile, 1.0 part t-dodecyl mercaptan, cumenehide 0.15 part of mouth peroxide was continuously added over 6 hours, and after addition, the temperature was raised to 65 ° C. and polymerization was conducted for 2 hours. The polymerization rate reached 97%. Antioxidant (Irganox 1076 manufactured by Ciba Specialty Chemical Co., Ltd.) 0 · 3 parts was added to the obtained latex, then 300 parts of 5% calcium chloride aqueous solution was added, coagulated, washed with water, dried and grafted as a white powder. A copolymer was obtained. This was designated as copolymer C1.

[0039] Next, in order to measure the graft ratio of C 1 and the molecular weight of the ungrafted copolymer, 3 g of C 1 was swollen in a methyl ethyl ketone solution, and it was not grafted in the centrifuged supernatant solution. When the molecular weight of the styrene acrylonitrile copolymer was measured by gel permeation chromatography, the weight average molecular weight was 150,000. The composition of the gel fraction (graft copolymer and rubbery polymer) precipitated by centrifugation was analyzed by Kjeldahl nitrogen quantitative analysis and pyrolysis gas chromatography, and the weight of the graft copolymer was measured from the amounts of styrene and acrylonitrile. Also, polybutadiene rubber was analyzed by bromine addition method to determine the weight of the rubbery polymer. The weight of the graft copolymer thus determined The graft ratio was found to be 47% from the following formula based on the amount and the weight of the rubber-like polymer.

Graft ratio = (Graft copolymer weight / Rubber polymer weight) X 100 (%)

[0040] Examples;! -13

Blend the maleimide copolymer (A) component, the bull copolymer (B) component, and the graft copolymer (C) component so that the blends shown in Table 3 and Table 4 are obtained. The resin composition was obtained by extruding at 280 ° C. with a twin-screw extruder (L / D = 32) rotating in the same direction with a devolatilizer and pelletizing. In addition, octadecyl-3- (3,5-ditertbutyl-4-hydroxyphenyl) propionate (Ciba Specialty) as an antioxidant for 100 parts by weight of the blend of component (A), component (B), and component (C) 'Chemicals Co., Ltd., IRGANOX 10 76) 0.5 part by weight was contained. Using the obtained pellets, test pieces for measuring physical properties were prepared by an injection molding machine, and various physical properties were measured. The results are shown in Tables 3 and 4.

[0041] [Table 3]

Table 3

[0042] [Table 4] Size

[0043] Comparative Example 1 21

Same as the example except that the maleimide copolymer (A) component, the bull copolymer (B) component, and the graft copolymer (C) component were blended as shown in Table 5 and Table 6. A resin composition was prepared by the method described above and evaluated in the same manner as in the examples. The results are shown in Tables 5 and 6.

[0044] [Table 5]

Comparison example Comparison example comparison ratio proportional proportional comparison ratio ratio proportional proportional example comparison ratio

Body-copolymerization Iremima

Yes

''

Yes

®

Bi-system copolymerization (Luni

Yes

Copolymerization

load.

"Load. Heavy 265C 98N

Striking strength striker

Yes

Bi soft hatching top

. () c

Drop weight thin wall strength less than or less less than or less

Yes

卜卜卜

1 1 T 1 1 I

<<<<<

瞷

The evaluation and measurement methods for various physical properties are as follows.

(l) MFR (melt mass flow rate): Measured according to JIS K 7210 under a load of 220 ° C 98N or 265 ° C 98N. (2) Charpy impact strength: Measured according to JIS K 7111 using a notched specimen.

(3) Vicat softening temperature: Measured according to JIS K 7206 under 50N load.

(4) Thin falling weight surface strength: 120mm long and 40mm wide obtained by injection molding, the gate is installed at the center of the lateral side, and the vertical direction 0-40mm from the gate side is 3mm thick, 40-8 A test plate was a three-stage plate with an Omm portion having a thickness of 2 mm, 80-; The height at which the test piece breaks 50% when a falling tip of a 10.8 mm diameter hemisphere 100 g weight is dropped vertically from various heights to the center of the lmm surface of the test piece.

(5) Weight average molecular weight: The weight average molecular weight of component (A) and component (B) was calculated by GPC (gel permeation chromatography) measurement. The conditions are shown below.

Equipment: “SYSTEM-21” manufactured by Shodex

Column: PLgel MIXED— B

Temperature: 40 ° C

Solvent: Tetrahydrofuran

Detection: RI

Concentration: 0.2%

Injection volume: 100 1

Calibration curve: Standard polystyrene (manufactured by Polymer Laboratories) was used, and the relationship between elution time and elution amount was converted to molecular weight to obtain various average molecular weights.

(6) Component composition: The component composition ratio was measured using pyrolysis gas chromatography.

Pyrolysis device: JPS-220 manufactured by Nippon Analytical Industrial Co., Ltd.

Thermal decomposition temperature: 590 ° C

Gas chromatography: Hewlett-Packard 5890SERIESII

Column: Micropolar † raw column DB— 5

Carrier gas: He pressure 2psi

Temperature condition: Hold at 50 ° C for 5 minutes, then heat up to 250 ° C at 18 ° C / minute and hold at 250 ° C for 7 minutes Detection: FID

0. Weigh out 3mg and take the measurement. The peak area ratio of the three components detected was taken.

(7) Average particle size: Graft rubber particle size of component (C) is N4 type manufactured by Coulter. It was measured. The measurement conditions were a sample viscosity of 0. OlPoise, a refractive index of 1.17, and a temperature of 20 ° C. The solvent used is dimethylformamide.

As is clear from the results shown in Table 3 to Table 6, when Example 2 and Example 3 are different from Comparative Example 1 in which the weight average molecular weight of component (A) is different, the weight average molecular weight of component (A) is less than 90,000. Then, the strength of the thin part is inferior.

Further, when Example 1 and Example 6 are compared with Comparative Example 4, and Example 2 and Example 3 are compared with Comparative Example 2, when the weight average molecular weight of component (A) exceeds 130,000, the strength of the thin-walled portion is inferior.

Similarly, Example 3 and Comparative Example 4, Example 7 and Comparative Example 9, Example 8 and Comparative Example 10, Example 9 and Comparative Example 11, Example 10 and Comparative Example 12, Example 11 and Comparative Example 13, When Example 12 and Comparative Example 14 are compared, and Example 13 and Comparative Example 15 are compared, if the weight average molecular weight of component (A) exceeds 130,000, the moldability (MFR) decreases and the strength of the thin part deteriorates.

In addition, when Example 3 and Comparative Example 5 and Comparative Example 6 in which the weight average molecular weight of component (B) is different are compared, if the weight average molecular weight of component (B) is less than 100,000, the strength of the thin portion is inferior and exceeds 160,000. Molding processability is reduced and the strength of the thin part is inferior.

Comparing Example 3 with Comparative Example 7 and Comparative Example 8 in which the amount of the aromatic bulle monomer residue in component (B) and the amount of cyanide bulur monomer residue are different, Residue of monomeric residues exceeding 78% by weight and cyanide bule monomer residues less than 22% by weight, the strength of the thin-walled portion is inferior. If the residue exceeds 33% by mass, the fluidity decreases and the strength of the thin-walled part is inferior.

Comparing Example 3 and Comparative Example 3, Example 3, Example 4 and Comparative Example 22 with different amounts of unsaturated dicarboxylic acid anhydride monomer residues of component (A), the unsaturation of component (A) If the dicarboxylic acid anhydride monomer residue is 2% by mass or more or 0% by mass, the strength of the thin portion is inferior.

As shown in Comparative Example 16 and Comparative Example 17, when the component (A) is less than 5% by mass, the heat resistance is low, and when it exceeds 40% by mass, the Charpy impact strength and the strength of the thin portion are low. As shown in Comparative Example 18 and Comparative Example 19, when the component (B) is less than 30% by mass, the strength of the thin-walled portion is low, and when it exceeds 75% by mass, the Charpy impact strength and the strength of the thin-walled portion are low. Further, as shown in Comparative Example 20 and Comparative Example 21, if the component (C) is less than 10% by mass, the Charpy impact strength and the thin-walled portion strength are low, and if it exceeds 50% by mass, the heat resistance is low. As described above, a resin composition excellent in the balance of heat resistance, impact resistance and molding processability, in which the strength of the thin-walled portion is remarkably improved, can be obtained by blending specific components at a specific ratio.

Industrial applicability

The resin composition of the present invention is excellent in the strength of the thin-walled portion and excellent in the balance of heat resistance, impact resistance and molding processability. Applications are expected to be suitable for automotive parts, electrical / electronic machine parts, precision machine parts, office equipment parts, heat appliances, etc. The entire contents of the specification, claims and abstract of the Japanese Patent Application No. 2006-230001 filed on August 28, 2006 are cited herein as the disclosure of the specification of the present invention. Incorporated.

Claims

The scope of the claims

[1] A resin composition comprising 5 to 40% by mass of component (A), 30 to 75% by mass of component (B), and 10 to 50% by mass of component (C) shown below.

Component (A): Aromatic bule monomer residue 40-80% by mass, unsaturated dicarboxylic imide derivative residue 10-60% by mass, and unsaturated dicarboxylic anhydride monomer residue less than 2% by mass A maleimide copolymer having a weight average molecular weight of 90,000 to 130,000, including 0 (excluding 0).

Ingredient (B): A bulle system having a weight average molecular weight of 100,000 to 160,000, containing 67 to 78% by weight of aromatic bur monomer residue and 22 to 33% by weight of cyanide butyl monomer residue. Polymer.

Component (C): A monomer mixture containing 30 to 70% by mass of a rubber-like polymer, 50 to 80% by mass of an aromatic bulle monomer, and 20 to 40% by mass of a cyanated bulle monomer. A graft copolymer obtained by graft polymerization of mass%.

[2] In the component (A), the aromatic butyl monomer strength is S styrene, the unsaturated dicarboxylic acid imide derivative is N-phenylmaleimide, and the unsaturated dicarboxylic acid anhydride monomer is maleic anhydride. The resin composition according to claim 1, wherein

[3] The resin composition according to claim 1 or 2, wherein in the component (B), the aromatic butyl monomer is styrene and the vinyl cyanide monomer is acrylonitrile.

[4] The resin composition according to any one of [1] to [3], wherein the rubbery polymer in the component (C) is a butadiene polymer and / or a butadiene-styrene copolymer.

[5] The resin composition according to any one of claims 1 to 4, wherein the aromatic butyl monomer in the component (C) is styrene and the vinyl cyanide monomer is acrylonitrile. object

Yes

[6] The component (A) further contains a butyl monomer residue copolymerizable with the aromatic butyl monomer, the unsaturated dicarboxylic acid imide derivative, and the unsaturated dicarboxylic acid anhydride monomer. 6. The resin composition according to claim 1, which is a maleimide copolymer containing 18% by mass or less of a group;!

[7] The component (B) further comprises the aromatic bull monomer and the cyanide bull monomer. The resin composition according to any one of claims 1 to 6, which is a bulle copolymer containing 10% by mass or less of a bulle monomer residue copolymerizable with the polymer.

[8] In the component (C), the monomer mixture to be polymerized with the graph contains a butyl monomer residue copolymerizable with the aromatic bulu monomer and the cyanated bulu monomer. The resin composition according to any one of Claims 7 to 7, wherein the resin composition is contained in a mass% or less.

[9] A molded article comprising the resin composition according to any one of claims 8 to 8.

10. The molded body according to claim 9, wherein the molded body is an injection molded body.