JPS63165450A - Heat-resistant resin composition containing blended colorant having excellent thermal stability - Google Patents

Abstract

PURPOSE:To obtain the titled composition having excellent thermal stability as well as extremely low degree of thermal discoloration at high temperatures, by blending a resin composition consisting of a resin containing imide groups, etc., with a specific amount of a specific colorant. CONSTITUTION:A composition obtained by blending 100pts.wt. resin composition consisting of (A) a resin containing imide groups in side chains or (B) the composition (A) and other thermoplastic resins and/or elastomers, e.g. polystyrene, maleic anhydride-styrene copolymer, etc., with (C) a colorant of C.I. Pigment Red 149 and, if necessary, (D) 0.0001-30pts.wt. one or more colorants selected from C.I. Pigment Red 101, C.I. Pigment Yellow 37, C.I. Pigment Blue 15, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a colorant-containing heat-resistant resin composition that shows extremely little change in color tone under high-temperature heating and has excellent thermal stability.

<Prior art> In recent years, maleimide monomer components and glutarimide monomers have been used as copolymer components to improve the heat resistance of polystyrene, polymethyl methacrylate, acrylonitrile-styrene copolymers, ABS resins, etc. The development of resins incorporating body components is actively underway. (For example, JP-A-57-98586, JP-A-57-100104, JP-A-58-129043, JP-A-58-71928, JP-A-6O-20904) <Problems to be solved by the invention> However,
Resins incorporating imide monomer components have improved heat resistance, so resins containing ordinary imides, especially colorants, may have poor thermal stability depending on the type of colorant, regardless of whether it is an organic or inorganic colorant. Some are bad and cause significant discoloration.

Additionally, the resin itself often deteriorates significantly along with the discoloration. Such a tendency is remarkable when the resin is allowed to remain at high temperature in the molding machine.

Means for Solving the Problems> The present inventors solved the above problems and obtained a colorant-containing resin composition that is resistant to discoloration or deterioration during molding at high temperatures and has excellent thermal stability. I thought about it as much as possible. As a result,
It was discovered that discoloration and resin deterioration are thought to be due to the interaction between the imide groups in the resin and the colorant, and they have already discovered a resin composition containing a specific colorant.
A patent application has been filed. (Japanese Patent Application No. 61-101488 and Japanese Patent Application No. 61-192189) Subsequently, as a result of intensive studies on coloring agents with excellent thermal stability, a specific coloring agent was discovered and the present invention was achieved.

That is, the first invention of the present invention provides a resin composition comprising a resin (A) containing an imide group in a side chain or the resin (A) and another thermoplastic resin and/or an elastomer (B), Color index (The 5ociet
y of Dyers and Colourists
(UK) and The American As5oc
ation of Textile Chemists
A colorant-containing heat-resistant resin composition with excellent heat stability, characterized in that it is formulated with a colorant (C) whose name is Pigment Red 149, which is listed in [as indicated by Pigment Red 149] and Co1orists (USA)]. This is what we provide.

Furthermore, the second invention provides a resin containing an imide group in the side chain (
A) or a resin composition consisting of the resin (A) and another thermoplastic resin and/or elastomer (B),
Color index (The 5ocjety of
Dyers and Coursists (UK) and The American Association
of TextileChemists and
Colorant (C) whose name is Pigment Red 149 according to Colorists (USA)
and the name or number listed in the color index above is Pigment Red iot, Pigment Red 1
02, Pigment Red 108, Pigment Red 12
2. Solvent Red 1111 Solvent Red 151
1 Solvent Red 179, Pigment Orange 20,
Solvent Orange 60. pigment yellow 37,
Pigment Yellow 58, Pigment Yellow 183.
Solvent Yellow 33, Pigment Brown 6, Pigment Brown 7, Pigment Brown 11, Pigment Brown 24, Pigment Green 14, Pigment Green 19, Pigment Green 36, Pigment Blue 15, Pigment White 4, Pigment White 6, Pigment White 7, Pigment White 21,
Pigment Black 1O1 Disperse Violet 2
A colorant-containing heat-resistant resin composition with excellent heat stability, characterized in that it is blended with one or more colorants (D) selected from the colorants No. 6 and No. 77500. It provides:

The present invention will be explained in detail below.

0 Resin containing an imide group in the side chain (A) The resin (A) containing an imide group in the side chain used in the present invention is a resin containing an imide group in the side chain, such as a maleimide monomer component or a glutarimide monomer component. It is a polymer with imide groups. As the resin containing these imide groups, a copolymer of the imide monomer component and another copolymer component is usually preferably used. Also,
N-alkyl or N-aryl substitutions of maleimide and glutarimide groups can also be used. These N-substituents include methyl, ethyl, isopropyl, butyl, hexyl, octyl, lauryl, cyclohexyl, phenyl, 2.3- or 4-methylphenyl, 2.
．． 3 or 4-ethylphenyl, 2.3 or 4-butylphenyl, 2.6-dimethyl, 2,3 or 4-chlorophenyl, 2.3 or 4-bromophenyl, 2.5
-dichlorophenyl, 8.4-di')lorophenyl, 2
．． 5-dibromophenyl, 3,4-dibromophenyl,
214 t6-t+)chlorophenyl, 2.4.6
-tribromophenyl, 2,3 or 4-hydroxyphenyl, 2,3 or 4- or methoxyphenyl 2,3 or 4-carboxyphenyl, 4-nitrophenyl, 4-diphenyl, 1-naphthylphenyl, 4-cyano Examples include phenyl, 4-phenoxyphenyl, 4-benzylphenyl, 2-methyl-5-chlorophenyl, 2-methoxy-5-chlorophenyl, and the like. One or more types of these can be introduced into the resin.

There are no particular restrictions on the copolymerization components with maleimide and glutarimide components, but mainly aromatic vinyl monomers, unsaturated nitrile monomers, unsaturated carboxylic acids and their ester monomers, and olefins. Examples include components such as system monomers. One or more of these components can be introduced into the resin.

Examples of aromatic vinyl monomers include styrene, d-methylstyrene, α-chlorostyrene, p-1-butylstyrene, p-methylstyrene, O-chlorostyrene, p-chlorostyrene, and 2,5-dichlorostyrene. , 3,4-dichlorostyrene, p-bromostyrene, 0-bromostyrene, 2,5-dipromostyrene, 8,4-dipromostyrene, etc., and one or more of these can be used. Among these, styrene and α-methylstyrene are usually preferred.

Examples of unsaturated nitrile monomers include acrylonitrile,
Examples include methacrylonitrile, maleonitrile, and fumaronitrile, and one type or two or more types can be used. Among these, acrylonitrile is usually preferred.

Examples of unsaturated carboxylic acids and their ester monomers include (meth)acrylic acid and its methyl, ethyl, propyl, butyl, lauryl, cyclohexyl, 2-hydroxyethyl, glycidyl, and dimethylaminoethyl. Examples include ester monomers, maleic anhydride, itaconic anhydride, citraconic anhydride, himic anhydride, mono- and dialkyl esters thereof, and one type or two or more types thereof can be used. Among these, methacrylic acid, methyl methacrylate, maleic anhydride, etc. are usually preferred.

Olefinic monomers include ethylene, propylene,
Examples include butene-11pentene-1,4-methylpentene-1, and one or more types can be used. In addition to these, vinyl chloride, vinylidene chloride, tetrafluoroethylene, monochlorotrifluoroethylene,
Copolymer components include hexafluoropropylene, butadiene, acrylamide, methacrylamide, vinyl acetate, vinylpyrrolidone, vinylpyridine, vinylcarbazole, vinyl ether, vinylketone, coumaron, indene, acenaphthylene, 2-isopropenylnaphthalene, and the like.

There is no limit to the amount of imide group-containing components such as maleimide and glutarimide monomer components in the copolymer;
Usually, the range of 1 to 70% by weight is preferred. If the amount of the imide monomer component is less than 1% by weight, the effect of improving the heat resistance of the resin will be small, while if it exceeds 70% by weight, the processability will tend to deteriorate.A particularly preferred amount of the imide group-containing component is 3% by weight. ~60
Weight%.

These imide group-containing resins can be produced by various methods. For example, a method of directly copolymerizing a maleimide monomer and a copolymerizable monomer, a method of imidizing a polymer containing a maleamic acid monomer or a (meth)acrylamide monomer, and a method of imidizing a polymer containing a maleic acid monomer or a (meth)acrylamide monomer. There is a method of imidizing a polymer containing an acid, glutaric anhydride, or methacrylic acid by reacting it with ammonia, a primary amine, an isocyanate ester, or the like. These polymers can be produced by bulk polymerization, suspension polymerization, bulk-suspension polymerization, emulsion polymerization, solution polymerization, and the like.

Furthermore, the imide group-containing resin used in the present invention may also be a polymer obtained by graft polymerizing the imide group-containing monomer component or other copolymer components thereof in the presence of an elastomer or its geothermal plastic resin. Can be used.

0 Other thermoplastic resins and elastomers (B) In the present invention, in addition to the resin (A) containing an imide group in the side chain, the resin (A) and other thermoplastic resins and/or elastomers (B) A resin composition consisting of the following can also be used.

Examples of these thermoplastic resins and elastomers include polystyrene, maleic anhydride-styrene copolymer, maleic anhydride-acrylonitrile-styrene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-d-methylstyrene copolymer, Methacrylonitrile-styrene copolymer, polymethyl methacrylate, methyl methacrylate-styrene copolymer.

Methyl methacrylate-acrylonitrile-styrene copolymer, methyl methacrylate-methacrylic acid copolymer, methyl methacrylate-maleic anhydride copolymer, methyl methacrylate-glutaric anhydride copolymer, methyl methacrylate-styrene-anhydride Glutaric acid copolymer, styrene
Acrylonitrile-methacrylic acid copolymer, ABS resin, AES resin, MBS resin, AC5 resin, AAS resin,
Polyethylene, polypropylene, polybutene-11 ethylene-butene-1 copolymer, propylene-butene-1 copolymer, propylene-ethylene block copolymer, ethylene-propylene rubber, maleic anhydride grafted polyolefin, chlorinated polyolefin, ethylene -vinyl acetate copolymer, ethylene-vinyl alcohol copolymer,
Ethylene-(meth)acrylic acid and its metal salt copolymers, ethylene-(meth)acrylic acid ester copolymers such as methyl (meth)acrylate, ethyl, propyl, butyl, glycidyl, dimethylaminoethyl, polytetrafluoro Ethylene, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, polyvinyl butyral, polyvinyl chloride, butadiene rubber, styrene -Butadiene random or block copolymer, hydrogenated styrene-butadiene random or block copolymer, acrylonitrile-
Butadiene rubber, isobutylene rubber, acrylic rubber, silicone resin, polycarbonate, polyester, polyamide, polyimide, polyamideimide, polyetherimide, polyetheretherketone, polyphenylene sulfide, polysulfone, polyethersulfone,
Examples include polyphenylene oxide, polyoxymethylene, etc., and one type or two or more types can be used.

Here, there is no particular restriction on the blending ratio of component (A) and component (B), but usually 99 to 1 part by weight of (B) to 1 to 99 parts by weight of (A) is suitable.

0 Colorant The colorant (C) essential in the present invention (first invention and second invention) is the above-mentioned Pigment Red 149.

In addition, the colorant (D) essential in the second invention is as follows:
Pigment Red 101. pigment red 10
2. Pigment Red 108, Pigment Red 122
, Solvent Red 111, Solvent Red 1511
Solvent Red 179, Pigment Orange 20. Pigment Orange 60, Pigment Iguro 37, Pigment Yellow 53, Pigment Yellow 183, Solvent Yellow 33, Pigment Brown 6, Pigment Brown 7, Pigment Brown 11, Pigment Brown 24, Pigment Green 14, Pigment Green 19, Pigment Green 36 , Pigment Blue 15, Pigment White 4, Pigment White 6,
Pigment White 7, Pigment White 21, Pigment Black 10, Disperse Violet 26 and 77500, and one or more of them can be used.

Among these colorants, combinations of Pigment Red 149 and especially Pigment White 4 and/or Pigment White 7, as well as combinations of these colorants in combination with other colorants, are even more stable against heat. This allows you to obtain products that are resistant to discoloration. Also,
By combining these, various colors can be obtained.

The particle size of the colorants (C and D) is not particularly limited, but fine particles of 0.5 μm or less are preferred.

In addition, there is no limit to the amount of colorant (C) or colorants (C) and (D) added, but usually resin (A) alone or (
A) (B) 0.0001 per 100 parts by weight of the composition
A range of 30 parts by weight is preferred. These can be colored in various tones.

Furthermore, the colorants (C) and (I)) can be in various forms such as powder, paste, masterbatch, dry color, and moisturizing colorant.

0 Resin Composition The colorant-containing resin composition of the present invention can be produced by any method. For example, a coloring agent can be added during the synthesis process or post-treatment process of the imide group-containing resin, thermoplastic resin, and/or elastomer. In general, the colorant mentioned above is added to the resin and mixed, and the mixture is kneaded in a melt mixer such as a Banbury mixer or a single- or twin-screw presser to obtain a uniform colorant-containing resin composition. .

For the resin composition of the present invention, an antioxidant, if necessary,
Heat stabilizers, light stabilizers, lubricants, plasticizers, antistatic agents, blowing agents, inorganic and organic fillers, flame retardants, surface gloss improvers, matting agents, etc. can be added.

These various additives can be added during the manufacturing process of the resin composition or in subsequent processing steps.

Glass fiber, metal fiber, carbon fiber or their powder, calcium carbonate, talc,
Composite materials such as gypsum, alumina, silica, mica, boron nitride, zirconia, silicon carbide, potassium titanate, and low melting point alloys are used for vehicle parts, ship parts, aircraft parts,
It can be widely used in many fields such as building materials, electrical parts, furniture, and office supplies.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

All parts and percentages given in the examples are by weight.

Reference Example: Resin (A) Synthetic Resins A-J: A maleimide-based copolymer was synthesized by directly copolymerizing a maleimide-based monomer and another monomer using a known emulsion polymerization method.

To the resin: Methyl methacrylate was added using a known suspension polymerization method.
After synthesizing the styrene copolymer, it is heated to 290℃ using an extruder.
A copolymer containing glutarimide groups was synthesized by reacting with ammonia.

Resin L: After synthesizing methyl methacrylate-methacrylic acid copolymer by all known suspension polymerization methods, 2
A copolymer having an N-phenylglutarimide group was synthesized by reacting with aniline at 90°C.

Resin M: A graft polymer containing N-phenylmaleimide was synthesized by graft polymerizing N-phenylmaleimide, styrene, and acrylonitrile to polybutadiene (weight average particle diameter 0.37 μm) using a known emulsion polymerization method.

(Grafting rate 55%, intrinsic viscosity of ungrafted copolymer 0
．． 67) Resin N: Acrylonitrile-
A styrene copolymer was synthesized.

Resin 0: Polybutadiene (weight average particle diameter 0.45 μm) is graft-polymerized with styrene and acrylonitrile by a known emulsion polymerization method, resulting in a rubber content of 60%, a graft ratio of 43%, and an intrinsic viscosity of the ungrafted copolymer of 0. .5
A graft copolymer of No. 5 was obtained.

Table 1 shows the resins synthesized by the above method.

Note that the intrinsic viscosity ([η], unit: cl//F) of the resin is a value measured in a dimethylformamide solution at 30°C.

Examples 1 to 29 Pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4
30.2 parts of -hydroxyphenyl)propionate, 0.1 part of trisnonylphenyl phosphite, and 0.1 part of distearyl-a,a'-thiodipropionate were added. To this were added 0.3 part of magnesium stearate, 0.02 part of ethylene bisstearamide, and the coloring agents shown in Tables 2 to 4, and mixed in a Henschel mixer. Add this mixture to a 40-diaphragm vent.
The mixture was melt-kneaded using a shaft extruder and then pelletized. This pellet was molded at 280°C using an injection molding machine to prepare a test piece.

Here, the degree of discoloration is determined by the color difference (△E) between the test piece that has not been retained in the injection molding machine and the test piece that has been retained for 10 minutes.
The color difference formula (CIE1976L*a) by the International Commission on Illumination
*b*). (Unit: NBS) These results are shown in Tables 2 to 4. In both results, it is recognized that the change in color tone is smaller than that of the colorant used in the comparative example shown below.

Furthermore, in Examples 4 to 6 in Table 2, the degree of discoloration was very small in the systems in which Pigment White 4 and/or Pigment White 7 were used in combination with Pigment Red 149 as the colorant. Among these, the effect is particularly remarkable in the system in which Pigment White 7 is used in combination.

Comparative Examples 1 to 20 Test specimens were created by the method of Examples, except that the colorants shown in Comparative Examples 1 to 20 in Tables 5 to 7 were used instead of the colorants used in Examples. , color difference (ΔE) was measured. These results are shown in Tables 5 to 7.

From these results, it can be seen that the colorants shown in the comparative examples all have a large degree of discoloration. Here, in particular, the products to which Pigment Red 178 and Solvent Red 135 shown in Comparative Examples 3 and 4 were added not only showed significant discoloration but also deteriorated the resin itself. were extremely brittle, and the intrinsic viscosities of these resins were reduced to 0.21 and 0.17, respectively.

It should be noted that the example shown in Comparative Example 3 shows that Pigment Red has very poor thermal stability.

Reference Examples 1 to 4 Test pieces were prepared by the method of the example except that the colorants shown in the comparative examples in Table 5 were added to resins that do not contain imide groups (acrylonitrile-styrene copolymer). Then, the color difference (ΔE) was measured. These results are shown in Figure 8.

This result shows that the degree of discoloration is very small in resins that do not contain imide groups. These results indicate that discoloration or deterioration occurs due to the interaction between the imide group-containing resin and the colorant.

Table 4 Example 1) Polycarbonate (Kijin Kasei, Panramito L-1
225) 2) Polyamide (Mitsubishi Kasei, Tsubamitsudo 10
15G80) 3) Ethylene-glycidyl methacrylate copolymer (Sumitomo Chemical, Bond First 2B) Table 5 Comparative Examples Table 7 Comparative Examples 1), 2), 3): Same as Table 4.

Table 8 Reference Examples (Effects of the Invention) The imide group-containing resin composition containing the colorant specified in the present invention has a very small degree of thermal discoloration at high temperatures and has excellent thermal stability. have

Claims (3)

[Claims] (1) Color index [The Society of Dyers] a
ndColourists (UK) and The Am
erican Ass-organization of Te
xtile Chemists and Colori
A colorant-containing heat-resistant resin composition having excellent heat stability, characterized in that it contains a colorant (C) whose name is Pigment Red 149, which is listed in the United States of America. (2) Color index [The Society of Dyers an
d Colourists (UK) and TheAme
rican Association of Text
ile Chemists and Colorists
Pigment Red 149 is the coloring agent (C) whose name is Pigment Red 149 (according to the US label), and Pigment Red 101, Pigment Red 102, Pigment Red 108, and Pigment Red are the names or numbers listed in the color index. 122, Solvent Red 1
11, Solvent Red 151, Solvent Red 17
9. Pigment Orange 20, Solvent Orange 60
, Pigment Yellow 37, Pigment Yellow 53,
Pigment Yellow 183, Solvent Yellow 33,
Pigment Brown 6, Pigment Brown 7, Pigment Brown 11, Pigment Brown 24, Pigment Green 14, Pigment Green 19, Pigment Green 36, Pigment Blue 15, Pigment White 4, Pigment White 6, Pigment White 7
, Pigment White 21, Pigment Black 10,
One or more colorants selected from the colorants Disperse Violet 26 and 77500 (
D) A heat-resistant resin composition containing a colorant and having excellent thermal stability. (3) The amount of the colorant (C) or colorants (C) and (D) added is the same as the amount of the imide group-containing resin (A) or the resin (A) and other thermoplastic resins and/or elastomers (B). ) per 100 parts by weight of a resin composition consisting of 0.
0001 to 30 parts by weight of a heat-resistant resin composition containing a colorant having excellent thermal stability as claimed in claims 1 and 2.