JP2005298776A - Heat resistance-imparting material and resin composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a heat-resistant ABS-based resin having a composition of specific components, capable of widely choosing molding condition widths in injection molding, scarcely generating odor when molded and capable of providing a product having good appearance, and to provide its molded product. <P>SOLUTION: The resin composition is obtained by kneading and mixing a heat-resistance-imparting material having a specific Tg and a specific parameter with an ABS(acrylonitrile-butadiene styrene)-based resin having a specific rubber component content. The heat-resistance-imparting material is composed of (a) 85-60 mass% aromatic vinyl-maleimide-based copolymer having a specific weight average molecular weight and (b) 15-40 mass% AS-based copolymer having a specific weight-average molecular weight and containing AN (acrylonitrile) and ST (styrene) in a specific ratio. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a heat resistance imparting material for improving the heat resistance of a resin and a resin composition using the same, and in particular, by using the heat resistance imparting material of the present invention, a heat resistant ABS resin composition can be easily and efficiently used. In addition, it can be applied to the fields of automobile parts, electrical / electronic parts, general merchandise, etc. because of its excellent appearance and excellent physical properties.

Conventionally, a heat-resistant ABS resin modified with a maleimide copolymer is prepared by kneading and mixing a maleimide copolymer and an ABS graft copolymer and an AS copolymer at the same time, or by mixing a maleimide copolymer and an ABS resin. A heat-resistant ABS resin modified with a maleimide copolymer was produced by kneading and mixing (for example, see Patent Document 1).
In this case, there was a risk that the dispersibility of the maleimide copolymer would be insufficient unless a twin screw extruder with strong kneading properties was used as an extrusion condition for obtaining a heat-resistant ABS resin modified with maleimide. There were gas generation and odor problems due to thermal decomposition with shearing heat generation accompanying the extrusion production conditions in the factory. Further, when the maleimide copolymer is insufficiently dispersed, there is a drawback that it is difficult to obtain good physical properties such as a decrease in appearance and hair strength on the surface of the molded product when it is molded.

  For this reason, in order to eliminate these drawbacks, a method of kneading and mixing a heat-resistant masterbatch resin and an ABS resin has been proposed. However, in these production methods, the heat resistance imparting effect of the heat resistant masterbatch resin for obtaining the heat resistant resin composition is insufficient, so that it is necessary to blend a large amount of the heat resistant masterbatch resin (for example, Patent Documents). 2, see Patent Document 3).

Japanese Patent Publication No. 2-41544 JP 7-316384 A JP 10-36614 A

  When producing a heat-resistant ABS resin from a resin and a specific masterbatch resin composition, the present invention has less gas generation and odor during extrusion production, and the production extrusion conditions and the resulting resin pellets are molded. The present invention is to provide a heat-resistant masterbatch resin composition that can provide a heat-resistant ABS-based resin having a good appearance with a wide range of molding conditions, less odor during molding, and a molded body thereof. .

That is, the present invention is an aromatic vinyl-maleimide copolymer (a) having a weight average molecular weight of 110,000 to 160,000 (85) to 60% by mass, a weight average molecular weight of 130,000 to 170,000, and an acrylonitrile content. It consists of 15-40 mass% AS type copolymer (b) which is 21-29 mass%, the glass transition temperature of the high temperature side of this resin composition is 140-170 degreeC, and is calculated by the said Formula 1. A heat resistance imparting material (A) characterized in that a parameter k value is 0.4 to 0.6, and an ABS resin, an AES resin having a rubber component content of 11% to 25% by mass, A heat-resistant composition (C) obtained by kneading and mixing 90% to 50% by mass of one or more resins (B) selected from the group consisting of an AAS resin and an MBS resin, and a molded product thereof It is about.
Here, ABS resin, AES resin, AAS resin, and MBS resin are abbreviated as resin hereinafter.

  In the present invention, the aromatic vinyl-maleimide copolymer (a) is preferably an aromatic vinyl monomer of 40 to 70% by mass, an unsaturated dicarboxylic imide derivative of 23 to 59.9% by mass, and an unsaturated dicarboxylic acid. A heat-resistant composition (C) using a heat-resistance imparting material (A) which is a copolymer comprising 0.01 to 7% by mass of an acid anhydride monomer, and an aromatic vinyl-maleimide copolymer (a ) And AS copolymer (b) kneaded and mixed, the composition (C) has a residual styrene monomer content of 300 ppm or less in the heat-resistance imparting material (A).

  The heat-resistance imparting material (A) of the present invention can be easily dispersible in the resin (B), and can be used as a masterbatch resin composition. When heat-resistant ABS resin is produced using this, there is little generation of gas and odor during extrusion production, wide range of extrusion production conditions, and wide range of molding conditions in injection molding, less odor during molding A product with good appearance can be obtained. Further, by defining the aromatic vinyl-maleimide resin used for the production of the masterbatch resin composition, a heat-resistant ABS resin having an excellent physical property balance can be obtained. Therefore, it is possible to provide products of excellent quality to various fields such as automobile parts, electric / electronic parts, home appliances, and miscellaneous goods for which heat-resistant ABS resins have been conventionally used.

  The aromatic vinyl-maleimide copolymer (a) used for the heat resistance imparting material (A) will be described.

  As a first production method, an aromatic vinyl monomer, an unsaturated dicarboxylic imide derivative, and, if necessary, a monomer mixture comprising a copolymerizable vinyl copolymer are copolymerized, A maleimide copolymer can be obtained.

  As a second production method, after copolymerizing a monomer mixture comprising an aromatic vinyl monomer, an unsaturated dicarboxylic acid anhydride, and other copolymerizable vinyl monomers as necessary, ammonia and / or Examples include a method in which a primary amine is reacted to convert an acid anhydride group into an imide group, and an aromatic vinyl-maleimide copolymer can be obtained by any method.

  As the aromatic vinyl monomer used in either of the first production method and the second production method, styrene such as styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, t-butylstyrene, chlorostyrene, etc. A monomer is mentioned, Among these, styrene is especially preferable.

  Examples of unsaturated dicarboxylic imide derivatives used in the first production method include N-alkylmaleimides such as maleimide, N-methylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, and N-arylmaleimide (as aryl groups, And maleimide derivatives such as phenyl, chlorophenyl, methylphenyl, methoxyphenyl, tribromophenyl, etc.). Among these, N-phenylmaleimide is particularly preferable. These derivatives can also be used as a mixture of two or more.

  Examples of the unsaturated dicarboxylic acid anhydride used in the second production method include anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid. Among these, maleic anhydride is particularly preferable.

Further, in any of the first production method and the second production method, other copolymerizable vinyl monomers include vinyl cyanide monomers such as acrylonitrile and methacrylonyl, methyl acrylate, and ethyl acrylic acid. Acrylic ester monomers such as esters, methacrylic ester monomers such as methyl methacrylic acid and ethyl methacrylate, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic amides and methacrylic amides Monomer.
In the first production method, maleic anhydride is also mentioned, and in the second production method, the maleic anhydride groups remaining without being converted into maleimide groups can be introduced into the copolymer.

  Ammonia and primary amine used in the second production method may be either anhydrous or in an aqueous solution. Examples of primary amines include alkylamines such as methylamine, ethylamine, butylamine, cyclohexylamine, and aniline. , Aromatic amines such as toluidine, chloraniline, methoxyaniline, tribromoaniline and the like, among which aniline is particularly preferable.

  In the case of the first production method, a known polymerization method can be used for any of suspension polymerization, emulsion polymerization, solution polymerization, bulk polymerization and the like. As the second production method, bulk-suspension polymerization, solution polymerization, bulk polymerization and the like can be suitably employed.

  The aromatic vinyl-maleimide copolymer (a) is composed of 40 to 70% by weight of an aromatic vinyl monomer, 23 to 59.99% by weight of an unsaturated dicarboxylic acid imide derivative and 0% of an unsaturated dicarboxylic acid anhydride monomer. A copolymer comprising 0.01 to 7% by mass is preferred. When the unsaturated dicarboxylic acid imide derivative is less than 23% by mass, the effect of imparting heat resistance is low, the compatibility with other components such as an AS copolymer is inferior, and impact resistance is reduced. On the other hand, if the unsaturated dicarboxylic imide derivative exceeds 59.9 mass, the strength is lowered, and the compatibility with other components such as an AS copolymer is also lowered. A more preferable range is 40 to 65% by mass of an aromatic vinyl monomer, 28 to 59.99% by mass of an unsaturated dicarboxylic imide derivative, and 0.01 to 7% by mass of an unsaturated dicarboxylic acid anhydride monomer. A particularly preferable range is 40 to 65% by mass of an aromatic vinyl monomer, 30 to 58% by mass of an unsaturated dicarboxylic acid imide derivative, and 2 to 5% by mass of an unsaturated dicarboxylic acid anhydride monomer. When the unsaturated dicarboxylic acid anhydride monomer is 0% by mass, the impact strength is slightly lowered when the aromatic vinyl-maleimide copolymer (a) is used as the heat resistant resin (B). . In particular, when a large amount is added to impart high heat resistance, the impact strength is significantly reduced. Further, when the unsaturated dicarboxylic acid anhydride monomer exceeds 7% by mass, the thermal stability is deteriorated, and the amount of gas generated at the time of heat processing increases, and the aromatic vinyl-maleimide copolymer (a) is used. The molded product of the heat resistant resin (B) that has been burned is likely to cause appearance defects such as streak defects.

  The aromatic vinyl-maleimide copolymer (a) may be one aromatic vinyl-maleimide copolymer having a weight average molecular weight of 110,000 to 160,000, or two or more aromatics having different weight average molecular weights. If the mixture is a combination of vinyl-maleimide copolymers, and the weight average molecular weight of the mixture is in the range of 110,000 to 160,000, the mixture of the aromatic vinyl-maleimide copolymers can be used. it can.

  The aromatic vinyl-maleimide copolymer (a) has a weight average molecular weight of 110,000 to 160,000, more preferably 120,000 to 150,000. The masterbatch resin composition for improving heat resistance obtained by using an aromatic vinyl-maleimide copolymer having a weight average molecular weight exceeding 160,000 has poor dispersibility in the resin (B), and is heat resistant ABS. As the base resin, the flowability is deteriorated and the appearance is easily deteriorated, and the applicable ABS base resin is limited. Further, when an aromatic vinyl-maleimide copolymer having a weight average molecular weight of less than 110,000 is used, the impact resistance as a heat-resistant ABS resin is poor.

  The AS copolymer (b) will be described. The AS copolymer is a copolymer composed of an aromatic vinyl monomer, a vinyl cyanide monomer, and other copolymerizable vinyl monomers used as necessary.

  Examples of the aromatic vinyl monomer include the same monomer species listed as the aromatic vinyl monomer used in the aromatic-maleimide copolymer (a). Among these, styrene and / or Or α-methylstyrene is particularly preferred.

  Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile. Among these, acrylonitrile is particularly preferable.

  Other copolymerizable vinyl monomers include acrylate monomers such as methyl acrylate, ethyl acrylate and butyl acrylate, and methacrylic esters such as methyl methacrylic acid and ethyl methacrylic ester. Monomers, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, monomers such as acrylic amide and methacrylic acid amide, and N- such as N-methylmaleimide, N-butylmaleimide and N-cyclohexylmaleimide Examples thereof include maleimide derivatives such as alkylmaleimide and N-arylmaleimide (the aryl group includes, for example, phenyl, chlorophenyl, methylphenyl, methoxyphenyl, tribromophenyl and the like). Among these, monomers such as acrylic acid ester, methacrylic acid ester, acrylic acid and methacrylic acid are preferable.

The AS copolymer (b) is composed of 79 to 71% by mass of aromatic vinyl monomer units, 21 to 29% by mass of vinyl cyanide monomer units, and 0 to 4% of other vinyl monomer units that can be copolymerized. % Copolymer is preferred. If the vinyl cyanide component is less than 21% by mass, the compatibility with the aromatic-maleimide copolymer is inferior, and when it is made into a heat-resistant ABS resin, appearance defects such as defective hairlines occur in the molded product. Impact strength is inferior. Even if the vinyl cyanide component exceeds 29% by mass, the compatibility with the aromatic-maleimide copolymer is poor, and when it is made into a heat-resistant ABS resin, appearance defects such as hairline defects occur in the molded product. A more preferable range is 75 to 71% by mass of an aromatic vinyl monomer and 25 to 29% by mass of a vinyl cyanide monomer. The aromatic vinyl monomer is particularly preferably 75 to 71.1% by mass, and the vinyl cyanide monomer is 25 to 28.9% by mass. The weight average molecular weight of the AS copolymer is 130,000 to 170,000. preferable. More preferably, it is the range of 140,000 to 160,000. If it is less than 130,000, the impact strength when heat-resistant ABS is achieved is poor. If it exceeds 170,000, the dispersibility in ABS resin is inferior, and the appearance of the heat-resistant ABS is poor. Moreover, the moldability as heat-resistant ABS is also inferior.

  The AS copolymer (b) can be produced by a usual polymerization method. Examples thereof include polymerization methods such as bulk polymerization, suspension polymerization, solution polymerization, and emulsion polymerization.

The heat imparting material (A) has a glass transition temperature in the range of 140 to 170 ° C. Preferably it is 145-165 degreeC, Most preferably, it is 150-165 degreeC. When the glass transition temperature is less than 140 ° C., the heat resistance is low, so when used as a masterbatch resin composition, a large amount of an expensive masterbatch resin composition needs to be added in order to obtain a desired heat-resistant ABS resin. It is not economical. Moreover, when it exceeds 170 degreeC, there exists a restriction | limiting in the extrusion conditions for adding a masterbatch resin composition and obtaining heat-resistant ABS type resin, and the molding conditions at the time of injection-molding the obtained heat-resistant ABS type resin. In order to disperse the aromatic vinyl-maleimide copolymer into the ABS resin well, if the cylinder temperature of the extruder or molding machine is set high, the rubbery polymer in the ABS copolymer will be thermally deteriorated and impact resistance It causes a decline in sex. In order to prevent this, if the cylinder temperature of the extruder and the molding machine is set low, the dispersion of the aromatic vinyl-maleimide copolymer to the ABS resin becomes insufficient, and it tends to cause poor appearance.
In addition, the impact strength is reduced.

Further, in the heat resistance imparting material (A) of the present invention, the parameter k value calculated from the following formula 2 needs to be 0.4 to 0.6. More preferably, the parameter k value is 0.4 to 0.59, particularly preferably 0.4 to 0.56. If the parameter k value is less than 0.4, the kneading and mixing properties of the aromatic-maleimide copolymer (a) and the AS copolymer (b) cannot be sufficiently obtained, resulting in variations in strength and rigidity characteristics. In addition, it is not preferable because molding appearance defects such as defective hairlines occur. On the other hand, when the parameter k value exceeds 0.6, the kneading state is severe and heat generation due to shearing during kneading is likely to occur, and the amount of residual monomer in depolymerization and the like increases, which is not preferable in terms of quality.

The heat resistance-imparting material (A) is a resin composition comprising an aromatic-maleimide copolymer (a) 85 to 60% by mass and an AS copolymer (b) 15 to 40% by mass.
When the aromatic-maleimide copolymer is less than 60% by mass, the heat resistance as the masterbatch resin composition is insufficient. On the other hand, if the aromatic-maleimide copolymer exceeds 85% by mass, the dispersibility of the heat-resistant masterbatch resin in the ABS resin becomes insufficient, and the impact strength or moldability is lowered to obtain good physical properties. I can't.

  The residual styrene concentration of the heat-resistance-imparting material (A) is not particularly specified, but it is preferably 300 ppm or less because of environmental problems such as odor during extrusion production and processing and molding. Especially preferably, it is 250 ppm or less. The residual styrene concentration was quantified by ordinary gas chromatography.

  Examples of the resin (B) include ABS (acrylonitrile-butadiene-styrene) resin, heat-resistant ABS resin (acrylonitrile-butadiene-styrene-α-methylstyrene), AES resin (acrylonitrile-EPDM-styrene) resin, AAS (acrylonitrile-acrylate-). Styrene) resin and MBS resin (methyl methacrylate) -butadiene-styrene.

  Moreover, as a rubber-containing component amount in resin (B), 11 mass%-29 mass% are good, and 11 mass%-25 mass% are preferable. More preferably, it is 12 mass%-28 mass%, Most preferably, it is 13 mass%-20 mass%. When the rubber content in the resin (B) is less than 11% by mass, the resulting heat resistant ABS resin has low impact resistance. When the rubber content of the resin (B) exceeds 25% by mass, the moldability and heat resistance of the resulting heat-resistant ABS resin are lowered.

  The mixing of the heat resistance-imparting material (A) and the resin (B) is not particularly defined, but kneading and mixing are preferable, and the composition (C) of the present invention can be obtained. As the kneading and mixing means, a single screw extruder and a twin screw extruder can be suitably used. In particular, when the masterbatch resin composition of the present invention is used, the dispersibility in the resin (B) is good even if a single screw extruder with weak kneading properties is used. Moreover, well-known apparatuses, such as a Henschel mixer and a tumbler mixer, can be used for the preliminary mixing before kneading with an extruder.

  The heat resistance imparting material (A) and the heat resistant resin composition (composition (C)) obtained by kneading and mixing it with the resin (B) include an antioxidant, an ultraviolet absorber, a colorant, a plasticizer, a lubricant, Flame retardants, glass fibers, carbon fibers, calcium carbonate, talc, mica and the like can be added according to the purpose.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these Examples. All parts and% in the examples are expressed on a mass basis.

(1) Raw material resin (a) Aromatic vinyl-maleimide copolymer (a)
Reference examples of the maleimide copolymer (a) used are shown below.
Reference Example 1 (Production of copolymer SMI-1)
In an autoclave equipped with a stirrer, 60 parts of styrene, 0.1 part of α-methylstyrene dimer and 100 parts of methyl ethyl ketone were charged, the inside of the system was replaced with nitrogen gas, the temperature was raised to 85 ° C., and maleic anhydride 40 And a solution of 0.15 part of benzoyl peroxide in 200 parts of methyl ethyl ketone were continuously added over 8 hours. After the addition, the temperature was kept at 85 ° C. for an additional 3 hours. As a result of sampling a part of the viscous reaction liquid and quantifying the unreacted monomer by gas chromatography, the polymerization rate was 99% styrene and 98% maleic anhydride. 36 parts of aniline and 0.6 part of triethylamine were added to the copolymer solution obtained here and reacted at 140 ° C. for 7 hours. The reaction solution was supplied to a vented twin screw extruder and devolatilized to obtain a maleimide copolymer. From the C-13 NMR analysis, the conversion ratio of anhydrous maleic group to imide group was 94%. This maleimide-based copolymer is a copolymer containing 51% of N-phenylmaleimide units as unsaturated dicarboxylic imide derivatives, 47% of styrene units, and 2% of maleic anhydride units, and this was designated as SMI-1. .

Reference Example 2 (Production of copolymer SMI-2)
A weight average molecular weight of 120,000 consisting of 51% N-phenylmaleimide units, 47% styrene units and 2% maleic anhydride units was prepared in the same manner as in Production Example 1 except that 0.2 parts of α-methylstyrene dimer was used. A copolymer was obtained. This was designated as copolymer SMI-3.

Reference Example 3 (Production of copolymer SMI-3)
A weight average molecular weight of 70,000 consisting of 51% N-phenylmaleimide units, 47% styrene units and 2% maleic anhydride units was prepared in the same manner as in Production Example 1 except that 1.5 parts of α-methylstyrene dimer was used. A copolymer was obtained. This was designated as copolymer SMI-2.

Reference Example 4 (Production of copolymer SMI-4)
A weight average molecular weight of 190,000 consisting of 51% N-phenylmaleimide units, 47% styrene units and 2% maleic anhydride units was prepared in the same manner as in Production Example 1 except that 0.02 part of α-methylstyrene dimer was used. A copolymer was obtained. This was designated as copolymer SMI-4.

Reference Example 5 (Production of copolymer SMI-5)
In an autoclave equipped with a stirrer, 49 parts of styrene, 1.7 parts of α-methylstyrene dimer and 100 parts of methyl ethyl ketone were charged, and the system was purged with nitrogen gas, then the temperature was raised to 85 ° C. and maleic anhydride 51 And a solution of 0.15 part of benzoyl peroxide in 200 parts of methyl ethyl ketone were continuously added over 8 hours. After the addition, the temperature was kept at 85 ° C. for an additional 3 hours. As a result of sampling a part of the viscous reaction liquid and quantifying the unreacted monomer by gas chromatography, the polymerization rate was 99% styrene and 98% maleic anhydride. 46 parts of aniline and 0.7 part of triethylamine were added to the copolymer solution obtained here and reacted at 140 ° C. for 7 hours. The reaction solution was supplied to a vented twin screw extruder and devolatilized to obtain a maleimide copolymer. From the C-13 NMR analysis, the conversion ratio of the anhydrous maleic group to the imide group was 95%. This maleimide copolymer is a copolymer containing 62% N-phenylmaleimide units as unsaturated dicarboxylic imide derivatives, 36% styrene units, and 2% maleic anhydride units, and this was designated as SMI-5. .

Reference Example 6 (Production of copolymer SMI-6)
In an autoclave equipped with a stirrer, 81 parts of styrene, 0.1 part of α-methylstyrene dimer and 100 parts of methyl ethyl ketone were charged, and the system was replaced with nitrogen gas. The temperature was then raised to 85 ° C., and maleic anhydride 19 And a solution of 0.15 part of benzoyl peroxide in 200 parts of methyl ethyl ketone were continuously added over 8 hours. After the addition, the temperature was kept at 85 ° C. for an additional 3 hours. As a result of sampling a part of the viscous reaction liquid and quantifying the unreacted monomer by gas chromatography, the polymerization rate was 99% styrene and 98% maleic anhydride. To the copolymer solution obtained here, 17 parts of aniline and 0.3 part of triethylamine were added and reacted at 140 ° C. for 7 hours. The reaction solution was supplied to a vented twin screw extruder and devolatilized to obtain a maleimide copolymer. From the C-13 NMR analysis, the conversion ratio of anhydrous maleic group to imide group was 94%. This maleimide-based copolymer is a copolymer containing 28% of N-phenylmaleimide units as unsaturated dicarboxylic imide derivatives, 71% of styrene units and 2% of maleic anhydride units, and this was designated as SMI-6. .

Reference Example 7 (Production of copolymer SMI-7)
A copolymer having a weight average molecular weight of 140,000 consisting of 52% N-phenylmaleimide units, 47% styrene units and 1% maleic anhydride units was obtained in the same manner as in Production Example 1 except that 37 parts of aniline was used. The conversion ratio of anhydrous maleic group to imide group was 97%. This was designated as copolymer SMI-7.

Reference Example 8 (Production of copolymer SMI-8)
A copolymer having a weight average molecular weight of 142,000 comprising 49% of N-phenylmaleimide units, 47% of styrene units and 4% of maleic anhydride units was obtained in the same manner as in Production Example 1, except that 33 parts of aniline was used. The conversion ratio of anhydrous maleic group to imide group was 90%. This was designated as copolymer SMI-8.

Reference Example 9 (Production of copolymer SMI-9)
A copolymer having a weight average molecular weight of 140,000 consisting of 53% N-phenylmaleimide units and 47% styrene units was obtained in the same manner as in Production Example 1 except that 38 parts of aniline was used. The conversion ratio of anhydrous maleic group to imide group was 100%. This was designated as copolymer SMI-9.

Reference Example 10 (Production of copolymer SMI-10)
A copolymer having a weight average molecular weight of 140,000 consisting of 43% N-phenylmaleimide units, 47% styrene units and 10% maleic anhydride units was obtained in the same manner as in Production Example 1 except that 26 parts of aniline were used. The conversion ratio of anhydrous maleic group to imide group was 73%. This was designated as copolymer SMI-10.

    Table 1 shows the component composition ratio of the maleimide copolymer (a) used above and the weight average molecular weight determined by gel permeation chromatography (GPC).

The GPC measurement was performed under the following conditions.
Equipment: “SYSTEM-21” manufactured by Shodex
Column; PLgel MIXED-B
Temperature: 40 ° C
Solvent; Tetrahydrofuran detection; RI
Concentration: 0.2%
Injection volume: 100 μl
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.

(B) AS copolymer (c)
Reference examples of the AS copolymer (c) used are shown below.
Reference Example 6 (Production of AS copolymer AS-1)
In a reaction vessel equipped with a stirrer, 74 parts of styrene, 26 parts of acrylonitrile, 2.5 parts of tricalcium phosphate, 0.26 parts of t-dodecyl mercaptan, 0.2 part of t-butyl peroxyacetate and 250 parts of water were charged. 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%. 200 parts of a 5% aqueous hydrochloric acid solution was added to the obtained reaction solution for precipitation, and after dehydration and drying, a white bead copolymer was obtained. This was designated as copolymer AS-1.
Table 2 shows the component composition ratio of the used AS-based copolymer (c) and the weight average molecular weight determined by GPC measurement.
Reference Example 7 (Production of AS copolymer AS-2)
An AS copolymer was obtained in the same manner as in Reference Example 6 except that 71.5 parts of styrene and 28.5 parts of acrylonitrile were used. This was designated as copolymer AS-2.
Table 2 shows the component composition ratio of the used AS-based copolymer (c) and the weight average molecular weight determined by GPC measurement.
Reference Example 8 (Production of AS copolymer AS-2)
An AS copolymer was obtained in the same manner as in Reference Example 6 except that 75 parts of styrene and 20 parts of acrylonitrile were used. This was designated as copolymer AS-3.
Table 2 shows the component composition ratio of the used AS-based copolymer (c) and the weight average molecular weight determined by GPC measurement.
Reference Example 9 (Production of AS copolymer AS-3)
An AS copolymer was obtained in the same manner as in Reference Example 6 except that 75 parts of styrene and 35 parts of acrylonitrile were used. This was designated as copolymer AS-4.
Table 2 shows the component composition ratio of the used AS-based copolymer (c) and the weight average molecular weight determined by GPC measurement.
Reference Example 10 (Production of AS copolymer AS-4)
An AS copolymer was obtained in the same manner as in Reference Example 6 except that the amount of t-dodecyl mercaptan was changed to 0.50 part. This was designated as copolymer AS-5.
Table 2 shows the component composition ratio of the used AS-based copolymer (c) and the weight average molecular weight determined by GPC measurement.
Reference Example 11 (Production of AS Copolymer AS-6)
An AS copolymer was obtained in the same manner as in Reference Example 6 except that the amount of t-dodecyl mercaptan was changed to 0.10 parts. This was designated as copolymer AS-6.
Table 2 shows the component composition ratio of the used AS-based copolymer (c) and the weight average molecular weight determined by GPC measurement.

(2) Manufacturing method of heat resistance imparting material (A) In order to create a heat resistance imparting material, a cylinder temperature of 280 with a twin-screw extruder TEM-35B (screw system 37 mm, L / D = 32) manufactured by Toshiba Machine Co., Ltd. Kneading and mixing were performed under the conditions of ° C., screw rotation speed of 200 rpm, and raw material feed rate of 20 kg / hr.

Table 3 shows the blending ratio of the heat-resistance imparting material thus prepared and the glass transition temperature on the high temperature side. The glass transition temperature was measured with a DSC measuring instrument “DSC-220C” (manufactured by Seiko Electronics Co., Ltd.). The heat resistance imparting material resin was previously pressed and molded on a thin plate having a thickness of 5 mm, and then used for measurement. The heat resistance imparting material resin was used by accurately weighing 10 mg.
The measurement conditions are as follows.
Temperature range: room temperature to 200 ° C
Temperature increase rate: 10 ° C / min
Atmosphere: Nitrogen flow

(3) Manufacturing method of resin (B) Resin (B) used when manufacturing the following heat resistant resin composition formed by kneading and mixing the masterbatch resin composition and resin (B) is an ABS graft. It was produced by kneading the copolymer and AS resin.

(C) ABS graft copolymer (b)
Reference examples of the ABS graft copolymer (b) used are shown below.
Reference Example 5 (Production of ABS Graft Copolymer G-1)
In a reaction vessel equipped with a stirrer, 114 parts of polybutadiene latex (solid content 35%, weight average diameter 0.3 μm, gel content 90%), styrene-butadiene latex 15 parts (solid content 67%, weight average diameter 0.5 μm) , Gel content 15%), sodium stearate 1 part, sodium formaldehyde sulfoxylate 0.2 part, tetrasodium ethylenediamine tetraacetic acid 0.01 part, ferrous sulfate 0.005 part, and pure water 150 parts are charged and the temperature is heated to 50 ° C., and 50 parts of a monomer mixture composed of 70% styrene and 30% acrylonitrile, 1.0 part t-dodecyl mercaptan, and 0.15 part cumene hydroperoxide are added. The addition was continued over time, and after addition, the temperature was raised to 65 ° C. and polymerization was conducted for 2 hours. The polymerization rate reached 97%. 0.3 parts of Irganox 1076 (manufactured by Ciba Specialty Chemicals Co., Ltd.) is added to the obtained latex, and then 300 parts of 5% aqueous calcium chloride solution is added to coagulate, rinse with water, and dry to obtain a graft copolymer as a white powder. It was. This was designated as copolymer G-1.

  The AS resin described above was used as the AS resin.

The kneading and mixing for preparing the resin (B) composition was performed by a single screw extruder FS40-28 (screw diameter 40 mm, L / D = 32) manufactured by Ikekai Iron Works, cylinder set temperature 220 ° C., screw rotation speed 100 rpm, It was manufactured under the condition of a discharge rate of 20 kg / hr.
Table 4 shows details of the prepared resin (B).

The component composition ratio was measured using pyrolysis gas chromatography.
Thermal decomposition apparatus: JPS-220 manufactured by Nippon Analytical Industries
Thermal decomposition temperature: 590 ° C
Gas chromatography: 5890SERIESII made by Hewlett-Packard
Column: Micropolar column DB-5
Carrier gas: He pressure 2 psi
Temperature condition: held at 50 ° C. for 5 minutes, then heated to 250 ° C. at 18 ° C./minute, held at 250 ° C. for 7 minutes Detection: FID
0.3 mg is weighed and measured. The peak area ratio of the detected three components was taken.

(4) Manufacturing method of heat-resistant resin composition modified with masterbatch resin composition The kneading and mixing for preparing the heat-resistant resin composition is a single screw extruder FS40-28 (screw diameter 40 mm, L / D = 32) at a cylinder set temperature of 260 ° C., a screw speed of 100 rpm, and a discharge rate of 20 kg / hr.

  The blending ratio and physical properties of the heat-resistant composition (C) prepared according to the present invention are shown in Table 5 as Examples 1 to 7 and Comparative Examples 1 to 19.

Various physical property measurement test methods were performed under the following conditions.
1) Charpy impact strength: Measured according to ISO 179 using an ISO multipurpose injection-molded test piece having a thickness of 4.0 mm, a width of 10.0 mm and a notch.
2) VSP (Vicat softening point): Measured according to ISO 306 at a load of 50 N using a test piece having a thickness of 4.0 mm.
3) MFR: Measured according to ISO 1133 at a temperature of 265 ° C. and a load of 98 N.

  The heat resistance imparting efficiency is evaluated by setting the Vicat softening point improvement by MB addition amount to +0.5 (° C.) / MB addition amount (%), and the assumed heat resistance improvement temperature calculated from the MB blending amount. The value obtained by adding the Vicat softening point of the ABS resin satisfying the above condition was defined as “target Vicat softening point”, and the case where the value was equal to or exceeded this value was indicated as “◯”, and the case where the value was lower than this was indicated as “X”.

  In the evaluation of strength development, along with the addition of MB, the case where the retention rate of the impact strength of the resin (B) alone, which is the MB compounding partner, is maintained or exceeded 70%, and the case where the impact strength is below is evaluated as x.

For the appearance evaluation, a plate having a length of 90 mm, a width of 55 mm, and a thickness of 2 mm was used. The gate of this molded product is installed in the center of the lateral surface.
The plate was formed using the Kawaguchi Iron Works K-125 under the following forming conditions.
Cylinder set temperature: 210 ° C
Injection pressure: Minimum filling pressure + 5kg / cm2G
Injection speed: 70%
Mold temperature: 50 ℃
When the masterbatch resin composition (A) is not uniformly dispersed in the ABS resin (B), a hairline-like appearance defect occurs in the heat-resistant composition (C). This failure phenomenon can be confirmed at a glance x, the failure reduction can be confirmed by △, and there is no defect phenomenon and the appearance is good.

  In Example 1 to Example 5 of the present invention, a heat-resistant ABS resin having desired physical properties is obtained by extruding a heat-resistant masterbatch resin and a general-purpose ABS resin using a single-screw extruder. The appearance evaluation is good even under molding conditions at a low cylinder temperature. There was a slight odor at the time of production of MB-15 and Comparative Example 11 using MB-15, and at the time of production of MB-21 and Comparative Example 19 using MB-21.

Claims (6)

Aromatic vinyl-maleimide copolymer (a) having a weight average molecular weight of 110,000 to 160,000 (85) to 60% by mass, a weight average molecular weight of 130,000 to 170,000, and an acrylonitrile content of 21 to 29% by mass A certain AS copolymer (b) consists of 15 to 40% by mass, the glass transition temperature on the high temperature side is 140 to 170 ° C., and the parameter k value calculated by the following equation 1 is 0.4 to 0.6. It is selected from the group consisting of ABS resin, AES resin, AAS resin, and MBS resin having a heat resistance imparting material (A) of 10 to 50 mass% and a rubber component content of 11 mass% to 25 mass% A composition (C) obtained by kneading and mixing one or more resins (B) 90 to 50% by mass.

Tg: Glass transition temperature (K) of the heat resistance imparting material
Tg1: Glass transition temperature (K) of AS copolymer (b)
Tg2: Glass transition temperature (K) of the aromatic vinyl-maleimide copolymer (a)
w1: Compounding ratio (mass%) of AS copolymer (b)
w2: Compounding ratio (% by mass) of the aromatic vinyl-maleimide copolymer (a) The aromatic vinyl-maleimide copolymer (a) is 40 to 70% by weight of an aromatic vinyl monomer, 23 to 59.9% by weight of an unsaturated dicarboxylic acid imide derivative, 0% of an unsaturated dicarboxylic acid anhydride monomer. A composition (C) using the heat-resistance-imparting material (A) according to claim 1, which is a copolymer comprising 0.01 to 7% by mass. The heat resistance-imparting material (A) according to claim 1 or 2, wherein the aromatic vinyl-maleimide copolymer (a) and the AS copolymer (b) are kneaded and mixed. The composition (C) according to claim 1 or 2, wherein the amount of residual aromatic vinyl monomer in the heat resistance imparting material (A) is 300 ppm or less. The aromatic vinyl monomer of the heat imparting material (A) is styrene, the unsaturated dicarboxylic imide derivative is N-phenylmaleimide, and the unsaturated dicarboxylic anhydride monomer is maleic anhydride. The composition (C) according to any one of claims 1, 2, and 4. The molded object which uses the composition (C) of any one of Claim 1, Claim 2, Claim 4, and Claim 5.