JPH09176371A - Colored thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic composition, having a bright color and comprising a new coloring matter compound salt hydrochloride good in heat and migration resistances, etc., and excellent in migration resistance. SOLUTION: This colored thermoplastic resin composition comprises a coloring matter compound hydrochloride of the formula, D-An .(HCl)n [D-An is a coloring matter compound; D is a coloring matter residue; A is a residue of an aliphatic amine or a cycloaliphatic amine capable of forming a slat with HCl; (n) is 1-3] in an amount of usually 0.01-5wt.% based on the total amount of the resin. A coloring matter residue such as an anthraquinone-based or a quinophthalone-based residue is preferred as the coloring matter residue of D. 2,2,6,6-Tetramethylpiperidinyl is preferred as A. A polyolefin-based resin is preferred as a thermoplastic resin composition for the objective composition. Furthermore, e.g. a compound of the formula obtained by reacting 1- chloroanthraquinone with 4-amino-2,2,6,6-tetramethylpiperidine is cited as the coloring matter compound of the formula, D-An .

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a colored thermoplastic resin composition, and more particularly to a resin composition having a clear hue and excellent migration resistance.

[0002]

2. Description of the Related Art Conventionally, inorganic pigments, organic pigments and dyes have been used for coloring resins. However, thermoplastics,
Especially in the coloring of polyolefin resins, dyes contaminate the mold during coloring, migrate to the surface of colored products after coloring (blooming phenomenon), and migrate to those that come into contact with colored products and contaminate them. It cannot be used because it will bleed (bleeding phenomenon). Further, among the organic pigments, azo pigments have insufficient heat resistance, and therefore cannot be used in polypropylene which is colored at a high temperature. Currently, the most widely used colorants for polyolefins are inorganic pigments and
It is a high-grade organic pigment. However, inorganic pigments have low tinting strength and few have clear hues. Further, there are few types of high-grade organic pigments that can be used for polyolefins, and they have the drawbacks of promoting crystallization of the resin during molding and causing shrinkage of the molded product. In addition, when coloring with a pigment, it is necessary to disperse the pigment. If the dispersion is insufficient, not only color spots will occur on the colored product, but also the mechanical strength of the product will deteriorate. .

British Patent No. 2,279,078 describes anthraquinone dye compounds as excellent dyes for polyolefin resins, but they also have insufficient migration resistance to resins. (See Comparative Example 2 below)

[0004]

DISCLOSURE OF THE INVENTION The present invention uses a novel dye compound having a clear hue and having good heat resistance, migration resistance, dispersibility, etc., and is excellent in coloring resistance and has excellent migration resistance. A resin composition is provided.

[0005]

The present invention provides a compound represented by the following general formula (I):

[0006]

## STR00002 ## D-An. (HCl) n (I) (In the formula, D-An is a dye compound, D represents a residue of the dye, and A is an aliphatic amine or cyclic compound which forms a salt with HCl. Represents a group containing a residue of an aliphatic amine, n is 1
A thermoplastic resin composition colored by using a dye compound hydrochloride (representing an integer value of ˜3) is provided.

In the present invention, the dye residue represented by D includes anthraquinone type, quinophthalone type, perinone type, perylene type, phthalocyanine type, naphthalimide type, xanthene type, coumarin type, triphenylmethane type, Examples thereof include methine-based, azomethine-based, and azo-based dye residues. Among these, anthraquinone type, quinophthalone type and perinone type are particularly advantageous.

As the aliphatic amine residue contained in A,
Aliphatic amines having a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms are mentioned, and examples of this substituent include:
Hydroxy group, halogen atom, aryl group, cyano group,
Examples thereof include an alkoxy group and a carboxyl group. Specifically, N, N-dimethylpropylamino group, N, N-diethylpropylamino group, N, N-dimethylbutylamino group, N, N-diethylbutylamino group, N-ethyl-N
-Methylpropylamino group, N-ethyl-N-methylbutylamino group and the like.

Examples of the cyclic aliphatic amine residue contained in A include those having the following structures. Among them, preferred are 2,2,6,6, -tetramethylpiperidinyl group, 1, It is a 2,2,6,6-tetramethylpiperidinyl group, and most preferably a 2,2,6,6-tetramethylpiperidinyl group.

[0010]

Embedded image (In the formula, R represents a hydrogen atom or an alkyl group)

Further, the dye residue D and the group A containing a (cyclic) aliphatic amine residue are linked to each other via a direct bond or a methylene group, an amino group, an ether bond, an amide bond or the like. The number (n) of groups containing an amine residue bonded to the dye residue D is 1 to 3. Examples of the dye compound represented by D-An include those shown in Table 1. These dye compounds are used in the form of the hydrochloride.

The thermoplastic resin used in the present invention includes: polyethylene, polypropylene, ethylene-butene 1
Random copolymer, polyolefin resin such as maleic anhydride modified polypropylene, polystyrene, styrene resin such as acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), Polyvinyl chloride, -polymethylmethacrylate-polyester-polycarbonate-polyphenylene oxide-polyamide and the like can be mentioned, but it is particularly advantageous to use a polyolefin resin.

The resin can be colored by a known method. For example, a dye compound is mixed with resin pellets and a dispersant, and then kneaded and extruded to produce a masterbatch, which is blended with a thermoplastic resin by a tumbler or a Henschel mixer, and then molded, or in a suitable mixer. , A thermoplastic resin pellet or powder and a crushed pigment compound, and various additives are mixed if necessary, and then a processing machine such as an extruder, an injection molding machine, or a roll mill,
A method of coloring and molding may be mentioned. It is also possible to add a coloring compound to a monomer containing an appropriate polymerization catalyst to form a desired thermoplastic resin by polymerization and mold it by an appropriate method. The pigment compound is usually 0.01 to 5 with respect to the total amount of resin.
It can be used in weight percent.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

[0015]

【Example】

(Synthesis Example 1) 1-chloroanthraquinone 4.9 g, 4-
Amino-2,2,6,6-tetramethylpiperidine 7.
8 g and triethanolamine 7.5 g were charged in 50 ml of N-methylpyrrolidone, reacted at 160 to 165 ° C. for 10 hours, cooled to room temperature, 100 ml of water was added, and the precipitated crystals were filtered. The obtained crystals are methanol 30
Charge 0 ml, add 5% caustic soda aqueous solution 100 ml, treat under reflux for 1 hour, cool, and then crystallize.
After washing with water and drying, 7 g of red crystals were obtained. The parent ion peak of the mass spectrum of this product was 362, and the elemental analysis results were as follows, which were in agreement with the calculated values of the following structural formula compound (A ′).

C (%) H (%) N (%) Analytical value 75.9 7.2 7.5 Calculated value 76.2 7.2 7.7 C23H26N2O2

[0017]

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2 g of the above compound (A ') was added to methanol 1
The mixture was charged in 00 ml, 10 ml of concentrated hydrochloric acid was added, and the mixture was stirred at room temperature for 2 hours, filtered, washed with water and dried to obtain 2.1 g of red crystals. The maximum absorption wavelength (λmax) of this product in N, N-dimethylformamide was 511 nm, and the parent ion peak of the mass spectrum was 362.
It was the same as the above compound (A ′), but the elemental analysis results were as follows, and were consistent with the calculated values of the following structural formula compound (A).

C (%) H (%) N (%) Analytical value 69.1 6.7 7.0 Calculated value 69.3 6.8 7.0 C23H27N2O2Cl1

[0020]

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Example 1 0.1 g of the dye compound represented by the above structural formula (A) was added to a polyethylene resin (HF310).
(F: manufactured by Mitsubishi Chemical Co., Ltd.) 100 g, and processed at 200 ° C. using an extruder to prepare colored pellets. The pellets are molded by an injection molding machine at 200 ° C for 2 minutes,
A colored molded plate was obtained. The colored plate obtained was uniform and had a vivid red color and exhibited excellent migration resistance. In the migration resistance test, the bleeding resistance and the blooming resistance were tested under the following conditions, but neither bleeding nor blooming was observed, and a gray scale for contamination (JIS L080) was used.
The grade was 5 according to the judgment in 5).

Bleeding resistance: The above colored plate was replaced with a colorless polyethylene resin plate and a soft vinyl chloride resin plate (DOP20).
% Content), and 24 hours at 70 ° C, 100 g / cm2
Then, the degree of contamination of each resin by the dye is evaluated. Blooming resistance: After the above colored plate was treated at 70 ° C. for 24 hours, the surface of the colored plate was wiped with a white cloth to evaluate the degree of staining of the white cloth with the dye.

In addition, the color tone of the colored plate molded by allowing it to stay at 250 ° C. for 10 minutes during injection molding has the same color tone as that of the colored plate molded at 200 ° C. × 2 minutes, and there is no discoloration due to thermal decomposition of the dye. It showed excellent heat resistance. (Comparative Example 1) The following structural formula

[0024]

[Chemical 6]

The dye represented by (CI Solvent
Using 0.1 g of Red 111), a colored molded plate was prepared and a migration resistance test of the colored molded plate was carried out in the same manner as in Example 1. As a result, the bleeding resistance to the polyethylene resin was grade 2, the bleeding resistance to the soft vinyl chloride resin was grade 1, and the blooming resistance was grade 2. (Comparative Example 2) The following structural formula

[0026]

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A dye represented by (GB2279078,
Using 0.1 g of the pigment described in P14), a colored molded plate was prepared and a migration resistance test of the colored molded plate was carried out in the same manner as in Example 1. As a result, the bleeding resistance to the polyethylene resin was grade 4, the bleeding resistance to the soft vinyl chloride resin was grade 3, and the blooming resistance was grade 4. (Synthesis example 2)

[0028]

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A quinophthalone compound 8.2 represented by
g into o-dichlorobenzene 70 ml, N, N-
After adding 0.5 g of dimethylformamide and heating to 70 ° C. and dropwise adding thiol chloride (4,8 g), 90-
The reaction was carried out at 100 ° C for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, 70 ml of hexane was added, the precipitated crystals were filtered,
Washing with hexane gave acid chloride.

The acid chloride obtained above was charged into 100 ml of o-dichlorobenzene, and 4-amino-2,2,6,6 was added.
-Tetramethylpiperidine 4.7 g and pyridine 10 ml
Was added, and the mixture was reacted at 150 to 155 ° C. for 5 hours, cooled to room temperature, and the precipitated crystals were filtered and washed with methanol.
The obtained crystals were charged in 300 ml of methanol, 5 g of sodium acetate was added, the mixture was treated under reflux for 1 hour, cooled to room temperature, filtered, washed with water and dried to give yellow crystals 7.1.
g was obtained. The parent ion peaks of the mass spectrum of this product were 549 and 551, and the elemental analysis results were as follows, which were in agreement with the calculated values of the following structural formula compound (B ′).

C (%) H (%) N (%) Analytical value 61.0 5.1 7.5 Calculated value 61.1 5.1 7.6 C28H28N3O4Br1

[0032]

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3 g of the above compound (B ') was charged in 50 ml of N-methylpyrrolidone, 5 ml of concentrated hydrochloric acid was added, the mixture was stirred at room temperature for 3 hours, 50 ml of water was added, and the crystals were filtered and washed with water. After drying, 2.8 g of yellow crystals were obtained.
The maximum absorption wavelength (λmax) in N, N-dimethylformamide of this product was 400 nm, and the parent ion peaks of the mass spectrum of this product were 549 and 551, which were the same as those of the above compound (B ′). However, the elemental analysis results are as follows and were in agreement with the calculated values of the following structural formula compound (B).

C (%) H (%) N (%) Analytical value 57.0 5.0 7.2 Calculated value 57.3 4.9 7.2 7.2 C28H29N3O4Br1Cl1

[0035]

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Example 2 0.05 g of the dye compound represented by the above structural formula (B) was added to polypropylene resin (BC-3).
G: manufactured by Mitsubishi Chemical Co., Ltd.) and mixed at 100 ° C. using an extruder to prepare colored pellets. The pellets are molded by an injection molding machine at 220 ° C for 2 minutes,
A colored molded plate was obtained. The colored plate obtained was uniform and had a clear yellow color, and showed excellent migration resistance. The migration resistance test was carried out in the same manner as in Example 1 except that a polypropylene resin was used in place of the polyethylene resin used in Example 1, but there was no bleeding or blooming, and a grayscale stain (JISL0805) was used. It was the 5th grade by the judgment in ().

In addition, the color tone of the colored plate molded by allowing it to stay at 280 ° C. for 10 minutes during injection molding has the same color tone as that of the colored plate molded at 220 ° C. × 2 minutes, and there is no discoloration due to thermal decomposition of the dye. It showed excellent heat resistance. (Comparative Example 3) The following structural formula

[0038]

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The dye represented by (CI Solvent
Example 2 using 0.05 g of Yellow 114)
A colored molded plate was prepared and a migration resistance test of the colored molded plate was carried out in the same manner as in. As a result, the bleeding resistance to the polypropylene resin was grade 2, the bleeding resistance to the soft vinyl chloride resin was grade 1, and the blooming resistance was grade 2. (Synthesis example 3) 1,5-dichloroanthraquinone 5.5
g, 4-amino-2,2,6,6-tetramethylpiperidine 7.8 g and triethanolamine 7.5 g were charged in N-methylpyrrolidone 50 ml, and the temperature was 160 to 165 ° C.
After reacting for 10 hours at room temperature, the mixture was cooled to room temperature, 100 ml of water was added, and the precipitated crystals were filtered. The obtained crystals were charged in 300 ml of methanol and 100% 5% aqueous sodium hydroxide solution was added.
ml was added, and the mixture was treated under reflux for 1 hour, cooled, filtered, washed with water, and dried to obtain 7.5 g of red crystals. The parent ion peak of the mass spectrum of this product was 516, and the elemental analysis results were as follows, which were in agreement with the calculated values of the following structural formula compound (C ′).

C (%) H (%) N (%) Analytical value 74.3 8.3 10.7 Calculated value 74.4 8.5 10.9 C32H44N4O2

[0041]

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2 g of the above compound (C ') was added to methanol 1
The mixture was charged in 00 ml, 10 ml of concentrated hydrochloric acid was added, and the mixture was stirred at room temperature for 2 hours, filtered, washed with water and dried to obtain 1.8 g of red crystals. The maximum absorption wavelength (λmax) of this product in N, N-dimethylformamide was 527 nm, and the parent ion peak of the mass spectrum was 516.
It was the same as the above compound (C ′), but the elemental analysis results were as follows, and were consistent with the calculated values of the following structural formula compound (C).

C (%) H (%) N (%) Analytical value 64.9 7.8 9.3 Calculated value 65.2 7.8 9.5 C32H46N4O2Cl2

[0044]

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Example 3 A colored molded plate was prepared in the same manner as in Example 2 using 0.05 g of the dye represented by the above structural formula (C), and a migration resistance test of the colored molded plate was carried out. . The colored plate obtained was uniform, had a vivid red color, showed excellent migration resistance, had no bleeding or blooming, and had a gray scale for contamination (JIS L0805).
It was the 5th grade by the judgment in.

Further, the color tone of the colored plate molded by allowing it to stay at 280 ° C. for 10 minutes during injection molding has the same color tone as that of the colored plate molded at 220 ° C. × 2 minutes, and there is no discoloration due to thermal decomposition of the dye. It showed excellent heat resistance.

[0047]

According to the method of the present invention, excellent migration resistance,
It is possible to obtain a polyolefin resin colored product having a uniform and clear color tone.

[0048]

[Table 1]

[0049]

[Table 2]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Osamu Kawashima 1-1 Kurosaki Shiroishi, Hachimannishi-ku, Kitakyushu City Mitsubishi Chemical Corporation Kurosaki Development Laboratory

Claims (5)

[Claims] 1. A compound represented by the following general formula (I): ## STR1 ## wherein D-An is a dye compound, D is a dye residue, and A is a dye compound. Represents a group containing a residue of an aliphatic amine or a cycloaliphatic amine which forms a salt with HCl, and n is 1
A thermoplastic resin composition, which comprises a dye compound hydrochloride (representing an integer value of 3). 2. The resin composition according to claim 1, wherein D is an anthraquinone dye residue. 3. The resin composition according to claim 1, wherein D is a quinophthalone dye residue. 4. The method according to claim 1, wherein A is 2, 2, 6, 6
-A resin composition which is a group having a tetramethylpiperidinyl group. 5. The resin composition according to claim 1, wherein the thermoplastic resin is a polyolefin resin.