JPH1036613A - Heat-resistant masterbatch resin, heat-resistant resin molding and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat-resistant masterbatch resin which, when blended with an ABS resin and injection molded, can give a molding having excellent characteristics by compounding a maleimde copolymer, a graft ABS copolymer, and an AS copolymer. SOLUTION: This masterbatch resin comprises 50-75wt.% maleimide copolymer having a wt. average mol.wt. of 100,000-135,000, 25-50wt.% graft ABS copolymer, and 0-20wt.% AS copolymer. When the resin contains 25-37.5wt.% maleimide copolymer having a wt. average mol.wt. of 60,000-100,000 and 25-37.5wt.% maleimide copolymer having a wt. average mol.wt. of 135,000-200,000, a molding excellent in the balance between appearance and impact resistance can be obtd. A heat-resistant color masterbatch resin is obtd. by compounding the resin with a colorant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant masterbatch resin, a heat-resistant color masterbatch resin, a heat-resistant resin molded article using the same, a heat-resistant color resin molded article, and a method for producing the same. By using the method, a heat-resistant ABS resin molded article can be easily obtained, and molding of all fields such as automobile parts, electric / electronic parts, home appliance parts, miscellaneous goods, etc. in which the heat-resistant ABS resin has been conventionally used. The method of the invention can be applied to the body.

[0002]

2. Description of the Related Art Heretofore, as means for improving the heat resistance of ABS resins, α-methylstyrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene-N-phenylmaleimide copolymer, styrene -N
There is known a method in which a heat-resistant copolymer having high heat resistance, such as a phenylmaleimide-acrylonitrile copolymer, and having miscibility with an ABS resin is kneaded and mixed with the ABS resin.

Conventionally, when these heat-resistant copolymers are kneaded and mixed with an ABS resin, they are mixed using a kneader such as a single-screw extruder, a twin-screw extruder or a Banbury mixer to obtain desired heat resistance and other properties. A resin pellet having the above physical properties was obtained, and the obtained resin pellet was shaped by means such as injection molding to prepare a molded article.

In order to obtain a colored molded article, a pigment and a pigment dispersant are added when kneading and mixing the heat-resistant copolymer and the ABS resin to obtain heat-resistant colored resin pellets. Molding or mixing the color masterbatch and heat-resistant resin pellets at the time of molding.

[0005] This conventional method has three main disadvantages. One is that, in order to obtain molded products having different heat resistance levels and different colors, different resin pellets depending on the heat resistance level, different colored pellets or colored color master batches depending on the color are required. There was complicated variety management and inventory management. The second is that the ABS resin is particularly deteriorated due to the kneading operation, resulting in a decrease in impact strength. Thirdly, the kneading operation and coloring are very costly, which is economically disadvantageous.

[0006]

It is an object of the present invention to simultaneously solve the three main disadvantages mentioned above,
A method in which an ABS resin and a specific heat-resistant masterbatch resin or a heat-resistant color masterbatch resin are directly molded by an injection molding machine to produce a molded article, and a heat-resistant masterbatch resin or a heat-resistant material that enables this method. The purpose of the present invention is to provide a color masterbatch resin.

According to the method of the present invention, by changing the mixing ratio of the ABS resin and the specific heat-resistant masterbatch resin or the heat-resistant color masterbatch resin,
Since various molded products having desired heat resistance can be easily obtained without kneading operation and can be simultaneously colored, it is not necessary to have several raw material resins and colored resins. Further, since no kneading operation is performed, a molded article having a small heat history and excellent impact strength can be obtained.

[0008]

That is, the present invention relates to a maleimide-based copolymer (a) having a weight average molecular weight of 100,000 to 1350, 50 to 75% by weight, and an ABS-based graft copolymer (b). 25 to 50% by weight and AS copolymer (c) 0
It is a heat-resistant masterbatch resin characterized by containing about 20% by weight.

Further, the present invention is a heat-resistant resin molded product obtained by injection-molding the above-mentioned heat-resistant master batch resin (A ₁ ) and the ABS resin (B). Further, the present invention relates to the above-mentioned heat-resistant masterbatch resin (A ₁ ) and ABS
This is a method for producing a heat-resistant resin molded article, which comprises injection-molding the base resin (B) as it is.

[0010] Another invention of the present invention relates to a method for producing a polymer having a weight average molecular weight of 10
Maleimide copolymer (a) 50 having a mass of 10,000 to 1350,000
75% by weight, ABS-based graft copolymer (b) 25-
50% by weight and 0 to 20% by weight of the AS copolymer (c)
And the total amount of (a), (b) and (c) is 10
A heat-resistant color masterbatch resin comprising 0.1 to 20 parts by weight of a colorant (d) and 0 to 10 parts by weight of a colorant dispersant (e) based on 0 parts by weight.

The present invention is also a heat-resistant color resin molded article obtained by injection-molding the heat-resistant color masterbatch resin (A ₂ ) and the ABS resin (B). Further, the present invention is a method for producing a heat-resistant color resin molded article, wherein the heat-resistant color masterbatch resin (A ₂ ) and the ABS resin (B) are injection-molded as they are.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a maleimide-based copolymer (a) having a weight average molecular weight of from 100,000 to 1350,000
5% by weight, ABS-based graft copolymer (b) 25 to 50
Heat-resistant masterbatch resin (A ₁ ) containing 0 to 20% by weight of the AS-based copolymer (c) and a maleimide-based copolymer (a) having a weight-average molecular weight of 100,000 to 1350,000 50-75% by weight, ABS-based graft copolymer (b) 25-50% by weight and AS-based copolymer (c)
0 to 20% by weight, and (a), (b),
The colorant (d) is added to the colorant (d) in an amount of 100 parts by weight based on the total amount of (c).
20 parts by weight of a colorant dispersant (e) 0 thermostable color masterbatch resin (A ₂₎ containing parts, and the heat-resistant master batch resin (A ₁₎ or a heat resistant color masterbatch resin (A ₂ ) and ABS
This is a method for producing a heat-resistant resin molded article or a heat-resistant color resin molded article by directly injection-molding the base resin (B).

In particular, as the maleimide copolymer (a), (a) + (b) + of the heat resistant masterbatch resin (A ₁ ) or the heat resistant color masterbatch resin (A ₂ )
In 100 parts by weight of the total amount of (c), 25 to 37.5% by weight of a maleimide-based copolymer having a weight-average molecular weight of 60,000 to 100,000 and a maleimide-based copolymer having a weight-average molecular weight of 135,000 to 200,000. When the polymer is used in combination with 25 to 37.5% by weight, a heat-resistant resin molded article or a heat-resistant color resin molded article having an excellent balance between appearance and impact resistance can be obtained.

Hereinafter, the present invention will be described in detail. First, the maleimide-based copolymer (a) that can be used for the heat-resistant master batch resin (A ₁ ) or the heat-resistant color master batch resin (A ₂ ) of the present invention will be described.

As a first production method, an aromatic vinyl monomer,
A maleimide-based copolymer can be obtained by a method of copolymerizing a mixture of an unsaturated dicarboxylic acid imide derivative and, if necessary, other copolymerizable vinyl monomers.

As a second production method, an aromatic vinyl monomer,
After copolymerizing a mixture of an unsaturated dicarboxylic anhydride and, if necessary, other copolymerizable vinyl monomers, ammonia and / or a primary amine are reacted to convert the acid anhydride group to an imide group. A conversion method is mentioned, and a maleimide-based copolymer can be obtained by any of the methods.

The aromatic vinyl monomer used in any of the first production method and the second production method includes styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, t-butylstyrene and chlorostyrene. And styrene monomers and their substituted monomers, among which styrene is particularly preferred.

Examples of the 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 (aryl group). Examples thereof include maleimide derivatives such as phenyl, chlorophenyl, methylphenyl, methoxyphenyl, and tribromophenyl. Of these, N-phenylmaleimide is particularly preferred. These derivatives can also be used as a mixture of two or more.

Examples of the unsaturated dicarboxylic anhydride used in the second production method include anhydrides of maleic acid, itaconic acid, citraconic acid, aconitic acid, etc. Among them, maleic anhydride is particularly preferred.

Other copolymerizable vinyl monomers used in both the first production method and the second production method include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and methyl acrylate. Esters, acrylate monomers such as ethyl acrylate, methacrylate monomers such as methyl methacrylate and ethyl methacrylate, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide And monomers such as methacrylamide. In the first production method, maleic anhydride can also be mentioned, and in the second production method, a maleic anhydride group remaining without being converted to a maleimide group can be introduced into the copolymer.

The ammonia and the primary amine used in the second production method may be either anhydrous or in an aqueous solution. Examples of the primary amine include methylamine, ethylamine, butylamine, cyclohexylamine and the like. And aromatic amines such as aniline, toluidine, chloraniline, methoxyaniline, and tribromoaniline. Of these, 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. In the case of the second production method, bulk-suspension polymerization, solution polymerization, bulk polymerization, and the like can be suitably employed.

The maleimide-based copolymer (a) comprises 40 to 70% by weight of an aromatic vinyl monomer unit, 30 to 60% by weight of an unsaturated dicarboxylic acid imide derivative unit and 0 to 50% of other copolymerizable vinyl monomer units. -20% by weight. If the ratio is out of this range, the compatibility with other components becomes poor, and the impact resistance is lowered. A more preferred range is
45 to 65% by weight of an aromatic vinyl monomer unit, 35 to 55% by weight of an unsaturated dicarboxylic acid imide derivative unit and 0 to 15% by weight of another copolymerizable vinyl monomer unit.

The maleimide copolymer (a) used in the present invention may be a single maleimide copolymer having a weight average molecular weight of 100,000 to 1350, or two or more maleimide copolymers having different weight average molecular weights. A mixture obtained by combining a series copolymer, wherein the weight average molecular weight of the mixture is 100,000 to 1
If it is in the range of 35,000, a mixture of the maleimide-based copolymer can be used.

The maleimide copolymer (a) used in the present invention has a weight average molecular weight of 100,000 to 13.5.
The use of a maleimide copolymer having a molecular weight of preferably 10,000 to 130,000 has an effect of improving the balance between appearance and impact resistance. Further, as the maleimide-based copolymer (a) used in the present invention, the component [(a) + (b) + (c) in the heat-resistant master batch resin (A ₁ ) or the heat-resistant color master batch resin (A ₂ ) )] Includes a maleimide-based copolymer 2 having a weight average molecular weight of 60,000 to 100,000.
5 to 37.5% by weight and a weight average molecular weight of 135,000 to 20
By using 25 to 37.5% by weight of a maleimide-based copolymer in combination, a heat-resistant resin molded article or a heat-resistant color resin molded article having a better balance between appearance and impact resistance is obtained. I can do it. Weight average molecular weight 1
A heat-resistant masterbatch resin (A ₁ ) or a heat-resistant color masterbatch resin (A ₂ ) obtained by using more than 350,000 maleimide-based copolymers alone cannot be dispersed with a high-flow type ABS resin. Poor appearance and poor appearance. Further, a heat-resistant masterbatch resin (A) obtained by using a maleimide-based copolymer having a weight average molecular weight of less than 100,000 alone.
₁ ) or heat-resistant color masterbatch resin (A ₂ )
Even a high-flow type ABS resin has good appearance but poor impact resistance.

Next, the ABS-based graft copolymer (b) will be described. The ABS-based graft copolymer (b) is
Graft copolymer obtained by copolymerizing a monomer mixture consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and optionally other copolymerizable vinyl monomers in the presence of a rubbery polymer It is.

Examples of the rubbery polymer include a butadiene polymer, a butadiene-styrene copolymer, an ethylene-propylene copolymer, an ethylene-propylene-gen copolymer, and an acrylate copolymer.

As the aromatic vinyl monomer, styrene,
Styrene monomers such as α-methylstyrene, vinyltoluene, p-methylstyrene, t-butylstyrene, chlorostyrene and the like and substituted monomers thereof are exemplified, and among these, styrene is particularly preferred.

Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, etc. Among them, acrylonitrile is particularly preferable.

Other copolymerizable vinyl monomers include acrylate monomers such as methyl acrylate, ethyl acrylate and butyl acrylate, methyl methacrylate and ethyl methacrylate. A methacrylate monomer,
Vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid; monomers such as acrylamide and methacrylamide; and N such as maleimide, N-methylmaleimide, N-butylmaleimide and N-cyclohexylmaleimide.
And maleimide derivatives such as -alkylmaleimide and N-arylmaleimide (aryl groups include, for example, phenyl, chlorophenyl, methylphenyl, methoxyphenyl, tribromophenyl and the like). Among these, monomers such as acrylic acid esters, methacrylic acid esters, acrylic acid and methacrylic acid are particularly preferred.

The ABS-based graft copolymer (b) is prepared in the following manner: in the presence of 30 to 70 parts by weight of a rubbery polymer, 65 to 80% by weight of an aromatic vinyl monomer and 20 to 20 parts by weight of a vinyl cyanide monomer. It is obtained by graft copolymerizing 30 to 70 parts by weight of a monomer mixture composed of 35% by weight and 0 to 10% by weight of another copolymerizable vinyl monomer. If the ratio is out of this range, the compatibility with other components is inferior, and the impact resistance is reduced.
A more preferred range is that in the presence of 40 to 60 parts by weight of the rubbery polymer, 70 to 75% by weight of an aromatic vinyl monomer, 25 to 30% by weight of a vinyl cyanide monomer, and other copolymerizable vinyl monomers. The range is obtained by graft copolymerizing 40 to 60 parts by weight of a monomer mixture composed of 0 to 5% by weight of a monomer.

In the graft copolymerization, it is usually difficult to graft the entire amount of the monomer onto the rubbery polymer, and an ungrafted copolymer is produced as a by-product. In the present invention, not only the true graft copolymer in which the ungrafted copolymer is positively separated and removed, but also the graft polymerization containing the ungrafted copolymer may be used, and the ungrafted copolymer may be used as the graft copolymer. Can be.

The graft ratio of the graft copolymer is as follows:
It is represented by [(weight of copolymer grafted on rubbery polymer / weight of rubbery polymer) × 100 (%)], and the range of the graft ratio is preferably 30 to 100%. When the graft ratio is less than 30%, the rubber-like polymer is likely to agglomerate, resulting in poor appearance, and the impact resistance is reduced. When the graft ratio exceeds 100%, the moldability is reduced. . A more preferred range of the graft ratio is 40 to 65%.

For the graft polymerization, any known polymerization techniques can be employed, for example, aqueous heterogeneous polymerization such as suspension polymerization, emulsion polymerization, bulk polymerization, solution polymerization, and precipitation polymerization of the resulting polymer in a poor solvent. Etc. Emulsion polymerization is preferred because it is easy to control the rubber particle size that affects the strength.

Next, AS which can be used if necessary
The system copolymer (c) will be described. The AS copolymer is a copolymer composed of an aromatic vinyl monomer unit, a vinyl cyanide monomer unit, and other copolymerizable vinyl monomer units used as required.

Examples of the aromatic vinyl monomer include AB described above.
The same monomer species as those exemplified as the aromatic vinyl monomer used in the method for producing the S-based graft copolymer (b) are exemplified, and among these, styrene and α-methylstyrene are particularly preferred.

Examples of the vinyl cyanide monomer include A
The same monomer species as those exemplified as the vinyl cyanide monomer used in the method for producing the BS-based graft copolymer (b) can be mentioned, and among these, acrylonitrile is particularly preferred.

The other copolymerizable vinyl monomers include the same monomers as those described above as the other copolymerizable vinyl monomers used in the method for producing the ABS graft copolymer (b). Seeds can be mentioned.

The AS copolymer (c) contains 65 to 80% by weight of an aromatic vinyl monomer unit, 20 to 35% by weight of a vinyl cyanide monomer unit and 0 to 50% of another copolymerizable vinyl monomer unit. It is a copolymer consisting of 10 to 10% by weight. If the ratio is out of this range, the compatibility with other components is inferior, and the impact resistance is reduced. A more preferred range is from 68 to 78% by weight of an aromatic vinyl monomer unit and 22% by weight of a vinyl cyanide monomer unit.
-32% by weight and 0-10% by weight of other copolymerizable vinyl monomer units.

The AS copolymer (c) can be produced by a usual polymerization method. For example, polymerization methods such as suspension polymerization, solution polymerization, and emulsion polymerization are employed.

The composition of the heat-resistant masterbatch resin (A ₁ ) of the present invention may be a maleimide copolymer (a) 50 to
75% by weight, ABS graft copolymer (b) 25 to 5
0% by weight and 0 to 20% by weight of the AS copolymer (c). More preferred compositions are 55 to 70% by weight of the maleimide-based copolymer (a), 30 to 45% by weight of the ABS-based graft copolymer (b), and 0% of the AS-based copolymer (c).
-10% by weight.

The composition of the heat-resistant color masterbatch resin (A ₂ ) of the present invention may be a maleimide copolymer (a) 50 to
75% by weight, ABS graft copolymer (b) 25 to 5
0% by weight and 0 to 20% by weight of the AS copolymer (c), and the total amount of (a), (b) and (c) is 100
It is a composition containing 0.1 to 20 parts by weight of the colorant (d) and 0 to 10 parts by weight of the colorant dispersant (e) with respect to parts by weight, and more preferably, a maleimide-based copolymer (a). 55 to 70% by weight, 30 to 45% by weight of the ABS-based graft copolymer (b) and 0 of the AS-based copolymer (c)
To 10 parts by weight, and the colorant (d) is 0.1 to 20 parts by weight based on 100 parts by weight of the total of (a), (b) and (c).
The composition contains parts by weight and 0 to 5 parts by weight of the colorant dispersant (e).

Next, the colorant (d) and the colorant dispersant (e) used in the present invention will be described. In the present invention, the colorant (d) is not particularly limited, but it is preferable to use a heat-resistant pigment, dye, or other processed colorant, and among them, pigments and dyes are particularly preferable.

The pigments and dyes used in the present invention are not particularly limited, but pigments and dyes having good heat resistance are desirable. For example, pigments include titanium oxide, titanium yellow, red petals, ultramarine, phthalocyanine, quinacridone,
Dyes include perylene, isoindolinone, and carbon black, and examples of dyes include perinone and anthraquinone.

The colorant dispersant (e) may be any as long as it has a function of dispersing the colorant. Among the colorant dispersants, specific examples of pigments and dye dispersants include fatty acid metal salts, fatty acid amides, fatty acid esters and the like.
Those having relatively good compatibility with the S resin are desirable.

In order to obtain desired heat-resistant resin molded products and heat-resistant color resin molded products, heat-resistant masterbatch resin (A ₁ ) and heat-resistant color masterbatch resin (A ₂ )
The higher the heat resistance, the smaller the amount of addition and the more economically advantageous. Therefore, the content of the maleimide-based copolymer is large, and A
If the amount of the BS-based graft copolymer is smaller, the heat resistance is higher, and the economic effect is higher. However, if the ABS-based graft copolymer is less than 25% by weight, the heat-resistant masterbatch resin (A ₁ ) or the heat-resistant color masterbatch resin (A ₂₎
And the ABS resin (B) are not preferably dispersed because the dispersion becomes uneven and the appearance is likely to be poor. If the total amount of the maleimide-based copolymer is less than 50% by weight, the heat-resistant masterbatch resin (A ₁ ) or the heat-resistant color masterbatch resin (A ₂ ) is used in a large amount, which is not preferable because the economic effect is reduced. Also, the AS copolymer was 20% by weight.
If the amount exceeds the range, the impact resistance of the heat-resistant resin molded article and the heat-resistant color resin molded article obtained by injection molding is undesirably reduced.

Further, in the heat-resistant masterbatch resin (A ₁ ) of the present invention or in the component [(a) + (b) + (c)] of the heat-resistant color masterbatch resin (A ₂ ), The polymer (a) has a weight average molecular weight of 100,000 to 1
50-75% by weight of a 35,000 maleimide copolymer
It is important to use Further, a maleimide copolymer having a weight average molecular weight of 60,000 to 100,000 is used.
By using 5% by weight and 25-37.5% by weight of a maleimide copolymer having a weight average molecular weight of 135,000 to 200,000 in combination, the balance between appearance and impact resistance is further improved. A heat-resistant resin molded article and a heat-resistant color resin molded article can be obtained.

Next, the heat-resistant resin molded article or the heat-resistant color resin molded article of the present invention is obtained by combining the above-mentioned heat-resistant master batch resin (A ₁ ) or the heat-resistant color master batch resin (A ₂ ) with an ABS resin ( B) can be obtained by injection molding. The ABS-based resin (B) used in the present invention generally comprises an ABS-based graft copolymer (b) and an AS-based copolymer (c) having the component composition ratios exemplified above. Limited to the same ABS-based graft copolymer (b) and AS-based copolymer (c) used in the production of the heat-resistant masterbatch resin (A ₁ ) or the heat-resistant color masterbatch resin (A ₂ ) Instead, commercially available ABS resin pellets can be suitably used.

Specific examples of commercially available ABS resin (B) include ABS (acrylonitrile-butadiene-styrene) resin, heat-resistant ABS (acrylonitrile-butadiene-styrene-α-methylstyrene) resin, and AES (acrylonitrile-EPDM-styrene). ) Resins, AAS (acrylonitrile-acrylate-styrene) resins, MBS (methyl methacrylate-butadiene-styrene) resins, and the like, but are not limited thereto.

The heat-resistant masterbatch resin (A ₁ ) or the heat-resistant color masterbatch resin (A ₂ ) of the present invention
The mixing ratio of the heat-resistant masterbatch resin (A ₁ ) or the heat-resistant color masterbatch resin (A ₂ ), the ABS-based resin (B), the heat-resistant resin molded product or the heat-resistant resin The compounding ratio can be changed according to the temperature level of each heat resistance of the colored resin molded article, and the range is not limited. In general, heat-resistant master batch resin (A ₁₎ or a heat resistant color masterbatch resin (A ₂₎ is 5 to 55% by weight ABS resin (B) is preferably 95 to 45 wt%.

The heat-resistant masterbatch resin (A ₁ ) or the heat-resistant color masterbatch resin (A ₂ ) of the present invention
And the ABS resin (B) are directly molded by an injection molding machine, the cylinder setting temperature of the injection molding machine is 26
By setting the temperature to 0 ° C. to 300 ° C., more preferably 260 ° C. to 280 ° C., a molded article having more excellent impact resistance and appearance can be obtained.

As a method of supplying the heat-resistant masterbatch resin (A ₁ ) or the heat-resistant color masterbatch resin (A ₂ ) and the ABS resin (B) to an injection molding machine, a known method such as a tumbler mixer or a V blender is used. A method of supplying a pre-blended product using an apparatus or a method of separately and quantitatively supplying both resins to a hopper of an injection molding machine can also be adopted. It is not particular about the supply method.

The heat-resistant masterbatch resin (A ₁ ) or the heat-resistant color masterbatch resin (A ₂ ) of the present invention
An antioxidant, an ultraviolet absorber, a plasticizer, a lubricant and the like can be blended according to the purpose. When the heat-resistant master batch resin (A ₁ ) or the heat-resistant color master batch resin (A ₂ ) and the ABS resin (B) are supplied to the injection molding machine, these additives can be supplied simultaneously. However, it is more preferable to use a masterbatch of these additives.

[0054]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. All parts and percentages in the examples are expressed on a weight basis.

(1) Raw Material Resin (a) Maleimide Copolymer (a) A production example of the maleimide copolymer (a) used below is shown. Production Example 1 Production Example of Copolymer SMI-1 In an autoclave equipped with a stirrer, 60 parts of styrene, α
-After charging 0.03 part of methylstyrene dimer and 100 parts of methylethylketone and purging the system with nitrogen gas,
The temperature was raised to 85 ° C., and 40 parts of maleic anhydride and 0.15 part of benzoyl peroxide were added to methyl ethyl ketone 2
The solution dissolved in 00 parts was continuously added in 8 hours. After the addition, the temperature was kept at 85 ° C. for a further 3 hours. A part of the viscous reaction solution was sampled, and the unreacted monomer was quantified by gas chromatography. As a result, the polymerization rate was 99% for styrene and 98% for maleic anhydride. 38 parts of aniline and 0.6 parts of triethylamine were added to the obtained copolymer solution 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-based copolymer. C-13 NMR analysis revealed that the conversion of the acid anhydride group to the imide group was 93%. This maleimide-based copolymer was a copolymer containing 51% of an N-phenylmaleimide unit as an unsaturated dicarboxylic acid imide derivative, and was referred to as a copolymer SMI-1. According to gel permeation chromatography (GPC) analysis, the polystyrene equivalent weight average molecular weight was 170,000.
The GPC measurement was performed using “SHOD” manufactured by Showa Denko KK
The weight average molecular weight in terms of polystyrene was determined using "EX GPC SYSTEM-21" and a calibration curve prepared using polystyrene having a standard molecular weight.

Production Example 2 Production Example of Copolymer SMI-2 N-phenylmaleimide unit 51 was prepared in the same manner as in Example 1 except that 1.5 parts of α-methylstyrene dimer was used.
%, A styrene unit of 47% and a maleic anhydride unit of 2%, having a weight average molecular weight of 70,000. This was designated as copolymer SMI-2.

Production Example 3 Production Example of Copolymer SMI-3 N-phenylmaleimide unit 51 was prepared in the same manner as in Example 1 except that 0.2 part of α-methylstyrene dimer was used.
%, A styrene unit of 47% and a maleic anhydride unit of 2% having a weight average molecular weight of 120,000. This was designated as copolymer SMI-3.

Table 1 shows the compositional ratio of the maleimide-based copolymer (a) used and the weight-average molecular weight determined by gel permeation chromatography (GPC).
Shown in

[0059]

[Table 1]

(B) ABS Graft Copolymer (b) An example of the production of the ABS graft copolymer (b) used below is shown. Production Example 4 Production Example of Copolymer G-1 Polybutadiene latex 1 was placed in a reaction vessel equipped with a stirrer.
14 parts (solid content 35%, weight average particle size 0.25 μm, gel content 90%), styrene-butadiene latex 15
Parts (solid content 67%, weight average particle size 0.5 μm, gel content 15%), sodium stearate 1 part, sodium formaldehyde sulfoxylate 0.1 part, tetrasodium ethylenediamine tetraacetic acid 0.03 Department,
0.003 part of ferrous sulfate and 150 parts of pure water were charged and the temperature was heated to 50 ° C., and a monomer mixture 50 of 70% styrene and 30% acrylonitrile was added thereto.
Parts, t-dodecyl mercaptan 0.2 part, kimene hydroperoxide 0.15 part continuously added in 6 hours,
After the addition, the temperature was raised to 65 ° C. and polymerization was performed for 2 hours. The conversion reached 97%. After 0.3 part of Irganox 1076 was added to the obtained latex, 300 parts of a 5% aqueous solution of calcium chloride was added, coagulated, washed and dried to obtain a graft copolymer as a white powder. This was designated as copolymer G-1.

Table 2 shows the component composition ratio, graft ratio and weight-average molecular weight of the ungrafted copolymer of the ABS graft copolymer (b) used above.

[0062] These values are obtained by setting a certain amount of sample at a temperature of 25 ° C.
After swelling in a solvent methyl ethyl ketone (MEK) for 24 hours, the supernatant solution obtained by centrifugation was used as an ungrafted copolymer, and the weight average molecular weight by GPC measurement and the composition analysis by gel tar nitrogen quantitative analysis were performed. The MEK-insoluble matter precipitated by centrifugation was taken out, and the solvent was completely dried and removed. Then, the rubbery polymer component was obtained by a halogen addition method, and the graft ratio was obtained by the following formula (1).
The ratio of butadiene rubber to styrene-butadiene rubber in the rubbery polymer component was the ratio charged during production.

[0063]

(Equation 1)

[0064]

[Table 2]

(C) AS-based copolymer (c) A production example of the AS-based copolymer (c) used below is shown. Production Example 5 Production Example of Copolymer AS-1 In a reactor equipped with a stirrer, 70 parts of styrene, 30 parts of acrylonitrile, 2.5 parts of tribasic calcium phosphate, 0.5 parts of t-dodecyl mercaptan, 0.5 parts of benzoyl peroxide 0 .2 parts and water 250 parts were charged, and the temperature was raised to 70 ° C. to start polymerization. Seven hours after the start of the polymerization, the temperature was increased to 75.
The temperature was raised to ℃ and kept for 3 hours to complete the polymerization. The conversion is 9
Reached 7%. A 5% hydrochloric acid aqueous solution 200 was added to the obtained reaction solution.
A part was added and precipitated, and after dehydration and drying, a white bead-like copolymer was obtained. This was designated as copolymer AS-1.

Table 3 shows the component composition ratio of the AS copolymer (c) used and the weight average molecular weight measured by GPC.

[0067]

[Table 3]

(2) Heat-resistant masterbatch resin
(A ₁ ), a heat-resistant color master batch resin (A ₂ ) A twin-screw extruder manufactured by Toshiba Machine Co., Ltd. to prepare a heat-resistant master batch resin (A ₁ ) and a heat resistant color master batch resin (A ₂ ). With TEM-35B (screw diameter 37 mm, L / D = 32), set cylinder temperature 2
The kneading and mixing were performed under the conditions of 80 ° C., a screw rotation speed of 200 rpm, and a raw material feed amount of 20 kg / hr.

The prepared heat-resistant masterbatch resin (A ₁ ) and the heat-resistant color masterbatch resin (A ₂ )
Is shown in Table-4. The prepared heat-resistant master batch resin (A ₁ ) and the heat-resistant color master batch resin (A ₂ ) were respectively referred to as MB-1 to MB-11.

[0070]

[Table 4]

(Note) (1) The colors of MB-10 and MB-11 are brown, and the pigments used are titanium oxide, titanium yellow, red stalks, and carbon black. (2) EBS indicates ethylene bis stearamide.

(3) ABS Resin (B) A temperature of 220 ° C. and a load of 1 according to ASTM D-1238.
The melt flow rate measured under the condition of 0 kg is 40
(G / 10 minutes) commercially available high flow type ABS resin “QF (manufactured by Denki Kagaku Kogyo Co., Ltd.)” (hereinafter referred to as ABS-
1) was used.

Examples 1 to 4 and Comparative Examples 1 to 7 The heat-resistant masterbatch resin (A ₁ ) and the heat-resistant color masterbatch resin (A ₂ ) were at a temperature of 110 ° C. for 3 hours, and the ABS resin (B) was After drying at a temperature of 80 ° C. for 3 hours, the tumbler mixer was prepared by mixing the heat-resistant masterbatch resin (A ₁ ) or the heat-resistant color masterbatch resin (A ₂ ) and the ABS resin (B) in the ratio shown in Table-5. Was mixed for 5 minutes and supplied to an injection molding machine. As an injection molding machine, injection molding was performed with an open nozzle using an injection molding machine K-125 manufactured by Kawaguchi Iron Works Co., Ltd. The molding conditions are as follows.

Cylinder set temperature; 260 ° C. Injection pressure; Minimum filling pressure + 5 Kg / cm ² G Injection speed; 70% Mold temperature; 60 ° C. Screw; Full flight screw Heat resistant masterbatch resin (A ₁ ) or heat resistant color master The test pieces for evaluation were molded under the above molding conditions at the compounding ratio shown in Table 5 with the batch resin (A ₂ ) and the ABS resin (B), and the IZOD impact strength, Vicat softening point,
The appearance was evaluated and the results are also shown.

The measuring conditions and appearance evaluation of physical properties are as follows. (1) According to ASTM D256, the IZOD impact strength of a notched test piece having a thickness of 1/4 inch was measured at a measurement temperature of 2
The measurement was performed at 3 ° C. and a measurement humidity of 50% RH. (2) The Vicat softening point is in accordance with JIS K7206,
Using a 1/4 inch test piece, 5 kg load, heating rate 5
It was measured at 0 ° C./hr.

(3) Appearance evaluation: 120 mm long, 40 mm wide
mm, wall thickness 3mm, 2m at 40mm intervals from the gate side
m, 1 mm three-stage plate was used. The gate of this molded product is provided with a side gate on the side surface of a portion having a thickness of 3 mm. If the heat-resistant masterbatch resin or the heat-resistant color masterbatch resin is not uniformly dispersed in the ABS resin, a hairline-shaped appearance defect occurs. In addition, gloss is low when finely dispersed even if dispersed to some extent evenly. Appearance evaluation was evaluated as follows: x when the defect phenomenon was apparent at a glance, x when the defect phenomenon could be found by staring, x when there was no defect phenomenon but low gloss, and x when there was no defect phenomenon and good gloss without the defect phenomenon. ◎.

[0077]

[Table 5]

In Examples 1 to 4 of the present invention, a heat-resistant masterbatch resin (A ₁ ) or a heat-resistant color masterbatch resin (A ₂ ) and a high-flow type ABS resin (B) were mixed with an extruder or the like. And a desired heat-resistant resin molded article or heat-resistant color resin molded article is obtained by directly molding without kneading operation. In addition, comparing Example 1 and Example 3, Example 1 using a maleimide-based copolymer having a weight average molecular weight of 170,000 and a weight average molecular weight of 70,000 was more effective.
The balance between impact strength and appearance is better than using a maleimide copolymer having a weight average molecular weight of 120,000 alone.

In Comparative Example 1, since the maleimide-based copolymer in the heat-resistant masterbatch resin MB-4 used was a maleimide-based copolymer having a weight average molecular weight of 70,000, the impact strength was inferior. . In Comparative Examples 2, 5 and 7, the heat-resistant masterbatch resin MB-
5, MB-8 and heat-resistant color masterbatch resin M
Since the maleimide-based copolymer in B-11 is a single maleimide-based copolymer having a weight average molecular weight of 170,000, dispersion of a heat-resistant masterbatch resin or a heat-resistant color masterbatch resin and a highly fluid type ABS resin is performed. And poor appearance.

In Comparative Example 3, the maleimide copolymer in the heat-resistant masterbatch resin MB-6 used was a maleimide copolymer having a weight average molecular weight of 170,000 and a maleimide copolymer having a weight average molecular weight of 70,000. Although combined with coalescence,
Since the weight-average molecular weight exceeds 13,000, there is no effect of the combined use, and poor appearance appears.

In Comparative Example 4, the maleimide copolymer in the heat-resistant masterbatch resin MB-7 used was a maleimide copolymer having a weight average molecular weight of 170,000 and a maleimide copolymer having a weight average molecular weight of 70,000. Although combined with coalescence,
The impact strength is inferior because the weight average molecular weight is smaller than 100,000. In Comparative Example 6, the impact resistance was poor because the AS-based copolymer in the heat-resistant masterbatch resin MB-9 used exceeded 20% by weight.

[0082]

According to the molding method of the present invention using the heat-resistant masterbatch resin or the heat-resistant color masterbatch resin of the present invention, the heat-resistant masterbatch resin or the heat-resistant color masterbatch resin is mixed with the ABS resin. By directly molding with an injection molding machine, a heat-resistant resin molded article or a heat-resistant colored resin molded article having excellent impact strength and appearance can be obtained economically and advantageously. It can be applied to injection molding parts in all fields such as automobile parts, electric / electronic parts, home electric parts, and miscellaneous goods, which have been used.

Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C08L 55/02 LME C08L 55/02 LME // (C08L 35/00 55:02 25:12) B29K 55:02 (72) Inventor Susumu Miyashita Toyo Ink Manufacturing Co., Ltd. 2-3-13 Kyobashi, Chuo-ku, Tokyo

Claims (14)

[Claims] 1. A maleimide-based copolymer (a) having a weight-average molecular weight of 100,000 to 13,000, 50 to 75% by weight, AB
25 to 50% by weight of S-based graft copolymer (b) and A
A heat-resistant masterbatch resin comprising 0 to 20% by weight of the S-based copolymer (c). 2. The heat-resistant masterbatch resin (A ₁ ) has a weight average molecular weight of 60,000 or more in the maleimide-based copolymer (a).
It is characterized by containing 25 to 37.5% by weight of a maleimide copolymer having a weight of 100,000 and 25 to 37.5% by weight of a maleimide having a weight average molecular weight of 1350 to 200,000. The heat-resistant masterbatch resin according to claim 1. 3. The maleimide-based copolymer (a) contains 40 to 70% by weight of an aromatic vinyl monomer unit, 30 to 60% by weight of an unsaturated dicarboxylic acid imide derivative unit and other copolymerizable vinyl monomer units. The copolymer comprising 0 to 20% by weight, the ABS graft copolymer (b) is a rubbery polymer 3
In the presence of 0 to 70 parts by weight, the aromatic vinyl monomer 65 to 65
A copolymer obtained by graft copolymerization of 30 to 70 parts by weight of a monomer mixture comprising 80% by weight, 20 to 35% by weight of a vinyl cyanide monomer and 0 to 10% by weight of another copolymerizable vinyl monomer. The polymer and the AS-based copolymer (c) contain 65 to 80% by weight of an aromatic vinyl monomer unit, 20 to 35% by weight of a vinyl cyanide monomer unit, and 0 other copolymerizable vinyl monomer units. The heat-resistant masterbatch resin according to claim 1, wherein the heat-resistant masterbatch resin comprises a copolymer consisting of 10 to 10% by weight. 4. A heat-resistant resin molded product obtained by injection-molding the heat-resistant masterbatch resin (A ₁ ) according to claim ₁ and an ABS resin (B). 5. An ABS resin as the ABS resin (B),
Heat resistant ABS resin, AES resin, AAS resin and MBS
The heat-resistant resin molded article according to claim 4, wherein one or more resins selected from the group consisting of resins are used. 6. A heat-resistant resin molded article, wherein the heat-resistant masterbatch resin (A ₁ ) and the ABS resin (B) according to claim 1 are injection-molded as they are. Manufacturing method. 7. An ABS resin as the ABS resin (B),
Heat resistant ABS resin, AES resin, AAS resin and MBS
The method for producing a heat-resistant resin molded product according to claim 6, wherein one or more resins selected from the group consisting of resins are used. 8. A maleimide copolymer (a) having a weight-average molecular weight of 100,000 to 1350, 50 to 75% by weight, AB
25 to 50% by weight of S-based graft copolymer (b) and A
0 to 20% by weight of the S-based copolymer (c), and 0.1 to 20 parts by weight of the colorant (d) based on 100 parts by weight of the total of (a), (b) and (c) And a colorant dispersant (e) in an amount of 0 to 10 parts by weight. 9. The method according to claim 1, wherein the maleimide-based copolymer (a) is (a)
+ (B) + (c) 25 to 3 maleimide copolymers having a weight average molecular weight of 60,000 to 100,000 in 100 parts by weight of the total amount
9. The heat-resistant color masterbatch resin according to claim 8, comprising 7.5% by weight and 25 to 37.5% by weight of a maleimide copolymer having a weight average molecular weight of 135,000 to 200,000. . 10. A maleimide-based copolymer (a) comprising 40 to 70% by weight of an aromatic vinyl monomer unit, 30 to 60% by weight of an unsaturated dicarboxylic acid imide derivative unit and other copolymerizable vinyl monomer units. A copolymer consisting of 0 to 20% by weight and an ABS graft copolymer (b) are mixed with an aromatic vinyl monomer 65 in the presence of 30 to 70 parts by weight of a rubbery polymer.
~ 80 wt%, vinyl cyanide monomer 20 ~ 35 wt%
And other copolymerizable vinyl monomers 0 to 10% by weight
Copolymer obtained by graft copolymerization of 30 to 70 parts by weight of a monomer mixture comprising: and an AS-based copolymer (c)
Consists of a copolymer comprising 65 to 80% by weight of an aromatic vinyl monomer unit, 20 to 35% by weight of a vinyl cyanide monomer unit and 0 to 10% by weight of another copolymerizable vinyl monomer unit. The heat-resistant color masterbatch resin according to claim 8, wherein: 11. The heat-resistant color masterbatch resin (A ₂ ) according to claim 8 and ABS.
A heat-resistant color resin molded product obtained by injection-molding the base resin (B). 12. The ABS resin (B) includes ABS resin, heat-resistant ABS resin, AES resin, AAS resin and M
The heat-resistant color resin molded article according to claim 11, wherein one or more resins selected from the group consisting of BS resins are used. 13. The heat-resistant color masterbatch resin (A ₂ ) according to claim 8 and ABS.
A method for producing a heat-resistant color resin molded product, which comprises injection-molding a resin (B) as it is. 14. The ABS resin (B) includes ABS resin, heat-resistant ABS resin, AES resin, AAS resin and M
14. The method for producing a heat-resistant color resin molded article according to claim 13, wherein one or more resins selected from the group consisting of BS resins are used.