JPS60156760A - Heterocyclic compound, dyeing and coloring using it - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I {R1 and R2 are H, (substituted)alkyl, cycloalkyl, alkenyl, alkynyl, or (substituted)phenyl; R3-R5 are H, or lower alkyl; X is H, halogen, lower alkyl, lower alkoxy, -NHCOR6, -NHSO2 R6 [R6 is H, lower alkyl, or (substituted)phenyl]}. EXAMPLE:A compound shown by the formula II. USE:A colorant for coloring a hydrophobic fibrous material or a synthetic resin in reddish blue - greenish blue, a dyestuff for a recording material. PREPARATION:A compound shown by the formula III is reacted with a compound shown by the formula IV at 0-100 deg.C in an inert solvent (e.g., DMF, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel heterocyclic compound useful for dyeing or coloring hydrophobic fiber materials, synthetic resins, etc.

More specifically, the present invention relates to the general formula (■) 2 [wherein R1 and Rg are a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, or an optionally substituted alkyl group] phenyl group,
Ra, R,,R.

each represents a hydrogen atom or a lower alkyl group.

X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, -NHCOR6 or -NH5O2R61゜However, R6 is a hydrogen atom, a lower alkyl group, a base alkyl group, a halogen atom or a lower □alkoxy group This invention relates to a heterocyclic compound represented by the following formula (representing an optionally substituted phenyl group), and a hydrophobic delicate dyeing method or synthetic resin coloring method using the same.

In the present invention, the optionally substituted alkyl group □ in +R1, R2 includes, for example, chlorine, bromine, chlorine, water/acid group, cyano group, -0R7゜-CO2
R7,-0COR7,-0CO,R7,-050,R,
.

-NH8O2R,, -NHR7, -0CONHR7, -
NHCOR7°(6) -NHCO2R, -5R8, alkenyl group, and substituents include lower alkyl group, lower alkoxy group, and halogen. However, R8 represents the above meaning, and R7
may be substituted on an arb4 group, a cycloalkyl group, an alkenyl group, an aralkyl group, a phenyl group (a lower alkyl group, a lower alkoxy group, a mihalogene atom, a lower alkanoylamino group, a cyano lower alkoxycarbonyl group) ).

R8 represents a lower alkyl group, an optionally substituted C)benzothiazolyl group or a benzoxacylyl group. R9 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, an i-class alkanoylamino group, a cyano/a group, or a lower alkoxycarbonyl group.

n represents an integer of 1 or more.

Specifically, R6 includes, for example, methyl, ethyl, propyl, butyl, phenyl, chlorphenyl,
Bromphenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, methoxyphenyl,
Examples include ethoxyphenyl, propoxyphenyl, and butoxyphenyl groups.

Examples of R7 include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, cyclohexyl, cyclopentyl, hinyl, -
CH=CHBr a, -CH=C(CHa) 2, -
CH=CHBr, -CH=CHBr, fxnyl, methylphenyl, ethylphenyl, flobyrphenyl, methoxyphenyl, ethoxyphenyl, chlorphenyl,
Bromphenyl, benzyl, methylbenzyl, ethylbenzyl, propylbenzyl, methoxybenzyl, ethoxybenzyl, chlorbenzyl, prombenozyl, phenethyl, methylphenethyl, ethylphenethyl, methoxyphenethyl, ethoxyphenethyl, chlorphenethyl,
Bromphenethyl, acetylaminophenyl, propionylaminophenyl, propylcarbonylaminophenyl, butylcarbonylaminophenyl, cyanophenyl 1
Examples include methoxycarbonylphenyl, ethoxycarbonylphenyl, propoxycarbonylphenyl, and butoxycarbonylphenyl groups.

Examples of R8 include methyl, ethyl, propyl,
Butyl, phenyl, methylphenyl, ethylphenyl,
propylphenyl, butylphenyl, methylphenyl,
Ethoxyphenyl, propoxyphenyl, xyphenyl, cyanophenyl, chlorphenyl, bromphenyl, acetylaminophenyl, propionylaminophenyl, propylcarbonylaminophenyl, butylcarbonylaminophenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, propoxycarbonylaminophenyl Examples of the group include butoxycarbonylphenyl group.

The compound represented by the general formula (I) is a compound represented by the general formula (n)1 (wherein, R1 represents the above-mentioned meaning), and a compound represented by the general formula (m)25 (wherein, X, R2, R8, R4, R5+, each having the above-mentioned meanings) can be synthesized by reacting the compound represented by the following in an inert solvent at a temperature of 0 to 100°C. Examples of the inert solvent include (9) dimethylformamide, dimethylsulfoxide, acetonitrile, ethyl acetate, sulfolano, tetrahydrofuran, toluene, and the like.

-411 The compound of formula (If) is prepared by treating the reaction product of a lonnitrile dimer with a compound of the following formula (Rr represents the above meaning) using a chlorinating agent such as thionyl chloride, phosgene, benzene, etc. sulfonyl chloride,
The thus obtained general formula (I) can be obtained by treatment with pensitrichloride, phosphorus oxychloride, etc.
The compound has excellent dyeing properties on hydrophobic fibers, and also has good dye bath stability and build-up properties. Furthermore, it provides a dyed product having a clear color tone ranging from reddish-blue to greenish-blue, with excellent properties such as water fastness, sublimation fastness, light fastness, and washing fastness.

When the obtained compound is used as a dye, it is first dispersed according to a conventional method. For example, in a sand mill, anionic dispersants such as naphthalene sulfonic acid formalin condensate, lignin sulfonic acid, cresol, Scheffer's acid formalin condensate, or nonionic dispersants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, etc. The treatment may be carried out together with an appropriate amount of water and a dispersing agent selected from various dispersants such as a powder, and it may be processed as a liquid or as a powder or granules by drying.

Synthetic fibers to which the dyeing method of the present invention can be applied include synthetic polyamide fibers, polyester fibers, and other so-called hydrophobic synthetic fibers, and semi-synthetic fibers such as g- or triacetate, which can be used alone or in combination. refers to various forms of fibrous materials mixed with other natural fibers. Among these, it is particularly suitable for polyester fibers and mixed products of polyester fibers and natural or regenerated cellulose fibers.

Dyeing methods in the present invention include dip dyeing, continuous dyeing, textile printing, and transfer printing. In particular, the compound of the present invention is an extremely suitable dye for dyeing and continuous dyeing of mixed products of polyester fibers and cellulose fibers because stains on cellulose fibers can be easily removed.

Furthermore, in textile printing, it is particularly suitable as a t-C collecting dye for alkali resist discharge printing in addition to ordinary direct textile printing.

The compound of the present invention is also useful as a coloring agent for synthetic resins, and is useful for coloring various synthetic resins with clear color tones ranging from reddish-blue to greenish-blue, which is durable in terms of light, heat and migration properties. can be obtained.

Synthetic resins suitable for coloring with the compound of the present invention include polystyrene-based, polyolefin-based, polyacrylate-based, polyvinyl acetate-based, polyvinyl chloride-based, polyamide-based, polycarbonate-based, polyacetal-based, polyester-based resins, and Examples include acrylonitrile-styrene copolymer (ASfllt resin) and acrylonitrile-butadiene-styrene copolymer (ABS resin).

In order to color a synthetic resin using the compound of the present invention, for example, 1. The required amount of the compound of the present invention shown is blended into the synthetic resin, kneaded, and then subjected to compression molding, injection molding, or calendar molding.

By using any molding method such as the extraction molding method, it is possible to obtain solid molded products such as films, plates, pipes, etc. colored in a color tone ranging from reddish-blue to greenish-blue. It is preferable to use one or more of known colorants and additives such as colorants, antioxidants, etc., to obtain good results. , .

Moreover, the compounds of the present invention can be used as various dyes for recording materials,
It can also be used, used,, done. ,
.

The following is a more detailed explanation of the present invention according to Embodiment 15.
In the examples, unless otherwise specified, "part" means "part by weight," and "color tone" means "texture" on the polyester fiber.

Example 1 20.5 parts of a compound represented by the following formula (I[a)] was added to 150 parts of acetonitrile, and N-
Phenethyl-2,2,4-trimethyl-1,2,8,4
- Add 60.9 parts of tetrahydroquinoline at room temperature. 8
After 0 minutes, add 200 parts of water, filter the precipitate, wash with water, ・□
dry. 88 parts of a compound of the following formula (1) is obtained.

λmax: 642 parts m (7 setsones) Color tone: greenish blue Example 2 15 parts of the compound (na) shown in Example 1 was treated with acetic acid% I
In addition to 200 parts of LI, N-ethyl-2,2,4-trimethyl-1,2 dissolved in 100 parts of ethyl acetate was added to 200 parts of LI.
, a, 29.7 parts of 4-tetrahydroquinoline are added at room temperature, and after 1 hour, the precipitated solid is filtered, washed, and dried. 20 parts of a compound of the following formula (2) is obtained.

λmaX: 648 parts m (acetone) Color tone: greenish blue Example 8 21.8 parts of a compound represented by the following formula (ub) was mixed with 20 (l
In addition to this, N dissolved in 200 parts of acetonitrile was added.
-phenoxyethyl-2゜2.4-trimethyl-1,2
, 59 parts of 8,4-tetrahydroquinolino are added at room temperature. After 1 hour, add 200 parts of water and filter and wash the precipitated solid.
dry. 88 parts of a compound of the following formula (8) is obtained.

Ha λmax: 5g9nm (acetone) Color tone: greenish blue Example 4 Using the compound (1) obtained in Example 1, staining was performed by the following operation.

a) Preparation of dispersion Total: 100 parts (Note 1) Naphthalene sulfonic acid formalin condensate The above mixture was treated in a sand mill for 4 hours to obtain a dispersion.

b) Dyeing 8 parts of the dispersion obtained in a) are placed in a dyeing pot together with 8000 parts of water and adjusted to pH 5 using acetic acid. Next, 100 parts of polyester fabric was added to this and heated at 180°C for 6 hours.
Perform staining for 0 minutes. After finishing dyeing, wash and rinse using the usual method. A dyed product with an excellent bright greenish blue color is obtained.

(17) Example 5 Using the compound (2) obtained in Example 2, a dispersion liquid is prepared according to a) of Example 4. Using this dispersion, a printing paste having the following composition is prepared.

(Printing paste composition) Above dispersion liquid 8 parts 7, -7 x v +L/') B A base paste (Note 2)
68 parts Liquor Tartaric acid 0.8 parts Sodium chlorate 02 parts Water Remaining total 100 parts (Note 2) Hafe Marjono original paste composition Kerosene 7 parts Water 25 parts Total 100 parts (Note 8) Shin-Nakamura Chemical Co., Ltd. : Emulsifier t 1 Q) 80 parts of an emulsion obtained by mixing the above in a high-speed mixer and 70 parts of Mapro Gum NpB% paste (Grinara product)
Make a half emulsion by mixing part III.

Using the dyeing paste thus obtained, hand printing is performed on polyester cloth. The cloth is then dried and subjected to superheated steam treatment at 175° C. for 7 minutes.

Thereafter, washing and drying are performed using a conventional method. A strong and vivid greenish-blue printed fabric is obtained.

Example 6 Using a dispersion of the compound of Example 8 prepared according to the method of Example 4, 100 parts of the polyester cloth of Example 4 is dyed using 100 parts of Kaebori ester and 100 parts of cotton cloth.

After dyeing is completed, the temperature of the dye bath is cooled to 60°C, 6 parts of sodium carbonate is added to the dye bath, and the temperature is kept at 60°C for 1 hour. Next, the cloth to be dyed is taken out and washed with hot water and water. Polyester fabrics are dyed in a vivid and strong greenish blue color, while cotton fabrics are dyed with virtually no staining.

Example 7 After heating and mixing 0.2 parts of the compound (14) described below in the form of fine powder and 100 parts of powdered ABS resin at 120°C, the mixture is passed through an extruder to create pelletite.

This is then molded using an injection molding machine at 280'C. A bright blue molding that is robust to heat, light and migration should be obtained.

Implementation, Example 8 80 parts of Sumikalon Brilliant Pink 5E-RL (Sumitomo Chemical Disperse Dye) was dispersed in 170 parts of hot water, and then 1350 parts of carbonic acid and 1 part of glycose 1. 150 parts of tf polyethylene glycol (MW800) and Kiprogum P-
670 parts of paste with a concentration of 12 parts of 2ON (Nippon Chemical Co., Ltd.) was added to prepare a total of 1000 parts of uniform printing paste, and this polyester fiber cloth was printed.

Separately, 100 parts of the dispersion obtained in Example 4 was dispersed in 8 GG parts of warm water, and then 665 parts of paste with a concentration of 12 parts of Kiprogum P-2ON and 4 parts of metanitrobenzenesulfonic acid salt were added.
F-611 is added to prepare a total of 1000 parts of uniform printing paste.

This printing paste is overprinted on the previously printed cloth,
It was dried at 175°C and subjected to HT steam treatment for 8 minutes. Then washed with water and diluted with caustic soda (40°B'e)
2 ml/l, hydrosulfide 2 f/L
, at 76°C with a cleaning solution containing 11/L of non-ionic cleaning agent.
Process for a minute and finish by washing with water.

In this way, a clear pink pattern was obtained on a greenish background.

Example 9 The compounds shown in the table below are obtained by the same method as in Examples 1 to 8.

(21)

Claims (1)

[Claims] (1) In the general formula (I) 2 R+ C, R1 and Rg are a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, or a substituted The optional phenyl group, R11, R4, and R5 each represent a hydrogen atom or a lower alkyl group. X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, -NHCOR6 or -NH302R6. Here, R6 represents a hydrogen atom, a lower alkyl group, a phenyl group optionally substituted with a halogen atom or a lower alkoxy group.] A heterocyclic compound represented by the following. (2) General formula (1) In formula C, R1 and R2 are a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, or an optionally substituted hnyl group,
R8. R4 and R5 each represent a hydrogen atom or a lower alkyl group. X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, -NHCOR6 or -NH502R6. However, R6 is Mu*+Laaa, Jre□t:
,! aaa□,. a phenyl group optionally substituted with a kill group, a halogen atom, or a lower alkoxy group. (8) General formula (I) 2 t [wherein Ih and R1 are a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, or an optionally substituted phenyl group, Ra, R4 and Rs each represent a hydrogen atom or a lower alkyl group. X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, -NHCOR6 or -NH8O2R. However, R6 represents a phenyl group, even if substituted with a hydrogen atom, a lower alkyl group, a lower alkyl group, a halogen atom, or a lower alkoxy group. A method of coloring synthetic resins.