JPH11189729A - Coloring matter-cum-ultraviolet stabilizer and polymer composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject stabilizer having heat resistance while retaining clear hue inherent in organic pigment/dyes. SOLUTION: This stabilizer is represented by formula I (R<1> is H, a halogen, a 1-12C alkyl or the like; R<2> and R<3> are each H, a halogen, a 1-4C alkoxy or the like; D is a coloring matter residue; (n) is 1-2). This stabilizer is obtained by the following procedure: A 2-hydroxyphenylbenzotriazole of formula II is nitrated to obtain a 2-hydroxy-3-nitro-phenylbenzotriazole of formula III and the nitro group of the resultant compound is converted to an amino group to obtain a 2-hydroxy-3-aminophenylbenzotriazole-based compound of formula IV, an ultraviolet-absorbing component. The nitration is performed preferably using 5-40 wt.% nitric acid as a nitration agent, in an inert solvent (e.g. chlorobenzene, dichlorobenzene) and at 30-60 deg.C. The reduction of the compound of formula IV to the corresponding compound of formula I is preferably performed by catalytic hydrogenation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel dye / ultraviolet stabilizer and a colored polymer composition using the same, which is excellent in light resistance.

[0002]

2. Description of the Related Art In the past, inorganic pigments and organic facial dyes have been used for coloring resins. Of these, inorganic pigments containing heavy metals are hardly used at present because they cause environmental pollution.

[0003] On the other hand, organic facial dyes have poor heat resistance and light resistance as compared with inorganic pigments. In particular, in order to blend pigments with resins, discoloration occurs due to high temperature and light stability after coloring. Is also bad.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a dye / ultraviolet absorber having heat resistance while maintaining the vivid hue of an organic facial dye. A second object of the present invention is to provide a colored polymer composition having light resistance using the dye and the ultraviolet absorber.

[0005]

Means for Solving the Problems A first aspect of the present invention is the following general formula (1):

Embedded image (In the formula, R ¹ is hydrogen, halogen, a linear or branched alkyl group having 1 to 12 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, and 1 to 8 carbon atoms.
A phenyl group substituted with an alkyl group, a phenoxy group and a phenylalkyl group having 1 to 4 carbon atoms in the alkyl portion, wherein R ² and R ³ are hydrogen,
Halogen is a group independently selected from the group consisting of halogen, a linear or branched alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, a carboxyl group and a sulfonic acid group; And n is an integer of 1-2. The present invention relates to a dye / ultraviolet stabilizer characterized by the following.

A second aspect of the present invention relates to a colored polymer composition containing the above-mentioned dye and ultraviolet stabilizer.

In order to produce the above-mentioned dye / ultraviolet stabilizer, first, it is necessary to produce a 3-aminophenylbenzotriazole compound which is an ultraviolet absorbent component. The production method of this compound is as follows.

The following general formula (2)

Embedded image (In the formula, R ¹ is hydrogen, halogen, a linear or branched alkyl group having 1 to 12 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, and 1 to 8 carbon atoms.
A phenyl group substituted with an alkyl group, a phenoxy group and a phenylalkyl group having 1 to 4 carbon atoms in the alkyl portion, wherein R ² and R ³ are hydrogen,
It is a group independently selected from the group consisting of halogen, a linear or branched alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, a carboxyl group and a sulfonic acid group. ) Is nitrated to give the following general formula (3)

Embedded image (In the formula, R ¹ is hydrogen, halogen, a linear or branched alkyl group having 1 to 12 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, and 1 to 8 carbon atoms.
A phenyl group substituted with an alkyl group, a phenoxy group and a phenylalkyl group having 1 to 4 carbon atoms in the alkyl portion, wherein R ² and R ³ are hydrogen,
It is a group independently selected from the group consisting of halogen, a linear or branched alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, a carboxyl group and a sulfonic acid group. 2-hydroxy-3-)
Nitro-phenylbenzotriazole was obtained, and the nitro group of this compound was converted to an amino group to obtain a compound represented by the following general formula (4).

Embedded image (In the formula, R ¹ is hydrogen, halogen, a linear or branched alkyl group having 1 to 12 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, and 1 to 8 carbon atoms.
A phenyl group substituted with an alkyl group, a phenoxy group and a phenylalkyl group having 1 to 4 carbon atoms in the alkyl portion, wherein R ² and R ³ are hydrogen,
It is a group independently selected from the group consisting of halogen, a linear or branched alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, a carboxyl group and a sulfonic acid group. )) Can be produced.

Specific examples of R ¹ include methyl, ethyl, propyl, n-butyl, sec-butyl, t-butyl, n-amyl, t-amyl, n-
Hexyl group, t-hexyl group, n-heptyl group, t-heptyl group, n-octyl group, t-octyl group, n-nonyl group, t-nonyl group, n-decyl group, t-decyl group, n
-Undecyl group, t-undecyl group, n-dodecyl group,
and a t-dodecyl group. Examples of the halogen include fluorine, chlorine, bromine, and iodine. Examples of the lower alkoxyl group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the cycloalkyl group include cyclopentyl and cyclohexyl groups, and examples of the phenyl group substituted with an alkyl group having 1 to 8 carbon atoms include a tolyl group and an ethylphenyl group. Examples of the phenylalkyl group having 1 to 4 carbon atoms include a benzyl group and a cumyl group.

Examples of the halogen atom for R ² or R ³ include chlorine, bromine, fluorine and iodine, but chlorine is relatively preferred. Examples of the alkyl group having 1 to 4 carbon atoms for R ² or R ³ include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-
Butyl group, t-butyl group and the like. Examples of the lower alkoxyl group having 1 to 4 carbon atoms include a methoxy group,
An ethoxy group, a propoxy group, a butoxy group and the like can be mentioned.

The nitration in the present invention can employ any conventional nitration means. Examples of the nitrating agent include nitric acid, sulfuric acid, a mixed acid composed of sulfuric acid-nitric acid, a mixed acid composed of nitric acid-acetic acid, nitrate-sulfuric acid, nitrous oxide, and an organic nitrate ester, with nitric acid being particularly preferred.
The concentration of nitric acid used is 5 to 70% by weight, preferably 5 to 70% by weight.
４０40% by weight, and the amount used is 1 equivalent or more based on 2-hydroxyphenylbenzotriazole represented by the general formula (2). In some cases, nitric acid may also serve as the solvent.

Usually, in the nitration, a solvent which is inert under the reaction conditions can be used. As the inert solvent, chlorobenzene, dichlorobenzene,
There are trichlorobenzene, nitrobenzene, etc., preferably, chlorobenzene, dichlorobenzene,
The amount used is 3 to 10 times, preferably 5 to 7 times the amount of the compound of the general formula (2).

The reaction temperature for the nitration is from 10 to 80 ° C., preferably from 30 to 60 ° C.

The method of reducing the compound of the general formula (3) to the compound of the general formula (1) includes catalytic hydrogenation, reduction with a strong acid or a metal in caustic alkali, reduction with an alkali sulfide or hydrazine. Although a typical reduction method is employed, a catalytic hydrogenation method is preferred.

In the above reduction reaction, Raney nickel, palladium, rhodium, platinum and the like can be usually used as a catalyst.

The following general formula (5) having an active group capable of reacting with an amino group of the 3-aminophenylbenzotriazole compound

Embedded image (Wherein D is a dye residue, X is a group bonded to the dye compound, and is an active group capable of reacting with an amino group to form a derivative, for example, a group such as halogen, acid chloride, acid bromide, and sulfonyl chloride) Can be used as a dye / ultraviolet stabilizer. This reaction is represented by the following reaction formula.

[0017]

Embedded image

Examples of the dye for forming the dye residue include anthraquinone, quinophthalone, phthalocyanine, triphenylmethane, coumarin, and azo dyes. Of these, anthraquinone-based and quinophthalone-based ones are preferred.

Examples of anthraquinone dyes and pigments include Alizarin (CI. 1027; 58000, Mord.
RedI), Alizarin Blue Black B (C.I.
I. 1085; 63615, Mord. Black1
3), Alizarin Direct Blue AGG; and the like.

Examples of phthalocyanine dyes and pigments include phthalocyanine green (C.I.7; 74260, pi
gment Green 7), copper phthalocyanine (C.I.
I. pigment Blue 15).

As triphenylmethane dyes and pigments, diaminotriphenylmethane dyes (malachite green dyes)
, Triaminotriphenylmethane type (magenta type), and hydroxytriphenylmethane type (rosoleic acid type).

The polymers used in the present invention include polyolefins such as polyethylene and polypropylene,
Polystyrene, acrylonitrile-styrene copolymer,
Thermoplastic resins such as acrylonitrile-butadiene-styrene copolymer, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polymethyl methacrylate, polyester polycarbonate, polyphenylene oxide, polyamide, urea resin, melamine resin, unsaturated polyester resin, etc. Thermosetting resin, natural resin, semi-synthetic resin, natural or synthetic rubber, cellulose, polypeptide and the like.

The resin is colored by a known method.
For example, after mixing a dye / stabilizer with resin pellets and a dispersing agent, kneading and extruding to produce a masterbatch, blending it with a thermoplastic resin using a Henschel mixer or the like, and then molding or a thermoplastic resin in a suitable mixer. Examples thereof include a method in which resin pellets or powder, a powdery dye-stabilizer, and various additives are mixed as required, and then colored by a processing machine such as an extruder or a roll mill.
As another method, there is a method in which a dye / stabilizer is added to a monomer, the mixture is polymerized with a suitable polymerization catalyst to form a thermoplastic resin composition, and then the composition is molded.

The dye / stabilizer of the present invention can be used usually in an amount of 0.01 to 5% by weight based on the whole resin.

[0025]

The present invention will be described below with reference to examples.
The present invention is not limited thereby.

Example 1 4.9 g of 1-chloroanthraquinone, 8.5 g of 2- (2-hydroxy-3-amino-5-t-octylphenyl) benzotriazole and 14.8 g of tributylamine in 50 ml of N-methylpyrrolidone. After reacting at 160 to 165 ° C. for 20 hours under a nitrogen stream, the mixture was cooled to room temperature, 100 ml of water was added, and the precipitated crystals were separated by filtration.
The obtained crystals were sufficiently washed with water, washed with a mixed solution of 30 ml of toluene and 30 ml of methanol, and dried to obtain 8.2 g of red crystals.

The results of elemental analysis and structure confirmation of this product are as follows. C (%) H (%) N (%) Analyzed value 74.8 5.75 10.00 Calculated value 75.0 5.88 12.29

Embedded image

0.2 g of the dye stabilizer obtained in the above step represented by the above structural formula and 100 g of polyethylene resin were uniformly mixed and extruded at 200 ° C. using an extruder to produce colored pellets. The pellets were kneaded with a roll mill at 200 ° C. and press-molded to obtain a colored resin plate having a thickness of 2 mm. This resin plate was bright red. This red resin plate was subjected to a light resistance test using a fade meter. It took about 70 hours until the discoloration was clearly recognized with the naked eye. The standard of the apparent fading was defined as the difference between grade 5 and grade 4 in the lightfast gray scale.

Comparative Example 1 The following structural formula

Embedded image In the same manner as in Example 1, a colored resin plate was prepared using 0.2 g of the anthraquinone dye represented by the formula (1), and a light resistance test was performed.
The time until the fading was clearly recognized by the naked eye was about 30 hours.

Example 2 5.5 g of 1,5-dichloroanthraquinone, 2- (2-
(Hydroxy-3-amino-5-methylphenyl) benzotriazole 18.4 g, triethanolamine 15.
After 0 g was charged in 50 ml of N-methylpyrrolidone and reacted at 160 to 165 ° C. for 10 hours under a nitrogen stream, the mixture was cooled to room temperature, 100 ml of water was added, and the precipitated crystals were separated by filtration. After sufficiently washing the obtained crystals with water, toluene 30
After washing with a mixed solution of 30 ml of methanol and 30 ml of methanol, drying was performed to obtain 11.6 g of red crystals.

The results of elemental analysis and structure confirmation of this product are as follows. C (%) H (%) N (%) Analytical value 70.12 4.10 16.29 Calculated value 70.18 4.09 16.37

Embedded image

A colored resin plate was molded in the same manner as in Example 1 except that 0.2 g of the dye stabilizer obtained in the above step represented by the above structural formula was used. The resin plate was bright red, and its light resistance was measured in the same manner as in Example 1. As a result, it showed a light resistance time of about 60 hours.

Example 3 The following structural formula

Embedded image 4.1 g of a quinophthalone-based dye represented by
ml, N, N-dimethylformamide 0.5g
And heated to 70 ° C. to give thionyl chloride 1.8.
After dropping g, the reaction was carried out at 90 to 100 ° C. for 4 hours. After the reaction, the temperature was gradually raised, and the mixture was heated to a boiling point of 110 ° C., and 20 ml of toluene containing excess thionyl chloride was distilled off to obtain a toluene solution of the acid chloride of the dye represented by the above formula.

The toluene solution containing the acid chloride of the dye obtained in the above step was mixed with 4.4 g of 2- (2-hydroxy-3-amino-5-t-octylphenyl) benzotriazole, 2.4 g of pyridine and 30 ml of toluene. The resulting solution was dropped at 30 to 40 ° C. over 1 hour, and then reacted at the boiling point (110 ° C.) for 10 hours. After the reaction, most of the toluene is recovered first at normal pressure and finally under a vacuum of 20 to 30 mmHg, cooled to room temperature,
Then, the dye stabilizer was precipitated. The precipitated crystals were filtered, washed with 100 ml of methanol, sufficiently washed with water and dried to obtain 5.8 g of yellow crystals.

The results of elemental analysis and structure confirmation of this product are as follows.

Embedded image

A colored resin plate was molded in the same manner as in Example 1 except that 0.1 g of the dye stabilizer obtained in the above step represented by the above structural formula was used. The resin plate was bright yellow and its light resistance was measured in the same manner as in Example 1.
The light fastness time was 0 hours.

Comparative Example 2 The following structural formula

Embedded image In the same manner as in Example 1, a colored resin plate was prepared using 0.1 g of the quinophthalone-based dye represented by the formula (1), and a light resistance test was performed.
The light fastness time was about 20 hours.

Example 4 In the same manner as in Example 1, the following structural formula

Embedded image Was obtained as a yellow stabilizer. 0.1 g of this yellow stabilizer
The resin plate obtained in the same manner as in Example 1 showed a clear yellow color, and the light resistance was extremely good.

Example 5 The following structural formula was obtained in the same manner as in Example 1.

Embedded image Was obtained as a yellow stabilizer. 0.1 g of this yellow stabilizer
The resin plate obtained in the same manner as in Example 1 showed a clear yellow color, and the light resistance was extremely good.

Example 6 The following structural formula was obtained in the same manner as in Example 1.

Embedded image Was obtained as a yellow stabilizer. 0.1 g of this yellow stabilizer
The resin plate obtained in the same manner as in Example 1 showed a clear orange color, and the light resistance was extremely good.

Example 7 The following structural formula was obtained in the same manner as in Example 1.

Embedded image Was obtained as a yellow stabilizer. 0.1 g of this yellow stabilizer
The resin plate obtained in the same manner as in Example 1 showed a clear yellow color, and the light resistance was extremely good.

[0042]

According to the present invention, a novel dye / ultraviolet absorber having heat resistance while maintaining the vivid hue of an organic facial dye can be provided. Further, according to the present invention, a colored polymer composition having light resistance can be provided by using the novel dye / ultraviolet absorber.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // C07D 249/20 501 C07D 249/20 501

Claims (3)

[Claims] [Claim 1] The following general formula (1) (In the formula, R ¹ is hydrogen, halogen, a linear or branched alkyl group having 1 to 12 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, and 1 to 8 carbon atoms.
A phenyl group substituted with an alkyl group, a phenoxy group and a phenylalkyl group having 1 to 4 carbon atoms in the alkyl portion, wherein R ² and R ³ are hydrogen,
Halogen is a group independently selected from the group consisting of halogen, a linear or branched alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, a carboxyl group and a sulfonic acid group; And n is an integer of 1-2. A) a dye / ultraviolet stabilizer. 2. The dye and ultraviolet stabilizer according to claim 1, wherein the dye residue is an anthraquinone dye residue or a quinophthalone dye residue. 3. A polymer composition containing the dye and ultraviolet stabilizer according to claim 1.