JPH02263868A - Organic polymer coloring material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to an organic polymer coloring material.

Specifically, the present invention relates to a dye used for coloring molded products such as fibers, thin films, plates, etc. made of organic polymeric materials, especially synthetic polymeric materials, in vivid and robust yellow to red tones. be.

[Conventional technology]

As a diarylthiadiazoloheterocyclic compound, Teha, “Dye and Drugs Vol. Jj, A/J, j j Ir~
The following compound is described in J 4cr(/rirr)'.

are each independently a hydrogen atom, a 01-C3° substituted or unsubstituted alkyl group, an aryl group, or, however, the above-mentioned known literature does not mention at all the possibility of using such a compound as an organic polymer 7 coloring material. Not listed.

On the other hand, various proposals have been made regarding dyes and methods for coloring organic polymer materials, such as those described in Japanese Patent Application Laid-open No. 4 (1973).
2-/Zayo No. 757 describes a thiadiazoloheterocyclic compound consisting of the following structure in which the hydrogen bonded to the 6th carbon of the thiadiazoloheterocycle is replaced with a specific group .

(In the formula, X is an optionally substituted phenyl group, alkyl dicarbonyl group, or cyano group
Rb, RC and URdIri hydrogen atoms, alkyl groups,
It represents an acylamino group, an alkoxy group, 7R6, and Rf...gen atom or N to Rf represents a hydrogen atom, an optionally substituted C5 to C2 alkyl group, an aryl group, or a cyclohexyl group.

) Normally, when applying organic polymer coloring materials to fibers, they are insoluble or poorly soluble in water, so they are dispersed in an aqueous medium using a dispersant using a conventional method. Or use it by printing. In addition, when coloring a synthetic resin, it is blended into the synthetic resin, heated and kneaded, and used for coloring by various molding methods.

[Problems to be Solved by the Invention] The object of the present invention is to provide a dye that has good light resistance and sublimation resistance and is capable of coloring a polymeric material with high concentration.

[Means to solve the problem]

The present invention relates to diarylthiadiazine represented by the general formula [I] acylamino group, alkoxy group, halogen atom and hydrogen atom, C□ to C2o substituted or unsubstituted alkyl group, aryl group ti represents a cyclohexyl group). The gist is an organic polymer coloring material made of a zoroheterocyclic compound.

The present invention will be explained in more detail below.

R', R2, R3 and R4 are hydrogen atoms; alkyl groups such as methyl group, ethyl group, propyl group, butyl group, octyl group; acetylamino group, propionylamino group, be/diylamine group, methylsulfonylamino group,
Acylamino groups such as methoxycarbonyloxyamino groups; alkoxy groups such as methoxy groups and ethoxy groups; halogens such as chlorine atoms, bromine atoms, fluorine atoms, and iodine atoms (wherein, Z represents CH or N, R', R2゜R3 and I
t' is each independently a hydrogen atom, an alkyl group, 01
Examples of substituents for the substituted or unsubstituted alkyl group, aryl group or cyclohexyl group of ~C1o include an alkoxy group, an allyloxy group, an aryl group, an aryloxy group, a cyano group, a hydroxy group, a tetrahydrofurfuryl group, etc. .

R1, R2, R3 and R4 are preferably hydrogen atoms: C
1 to C4 lower alkyl group; C□ to C4 lower alkylcarbonylamino group; C1 to C6 lower a (in the formula, R1
, R'', R3 and R4 are the same as defined above.) and the following structural formula [■] )(,NC)l, C00C,H.

・・・・・・・・・CIII"1 is reacted with glycine ethyl ester to form the following - Monna [■] R5 and R6 are unsubstituted C1 to C4 lower alkyl groups)
It is.

Among the compounds of the present invention represented by the above-mentioned -Momonana [I], those in which Z is CH can be produced, for example, as follows according to a known method.

In other words, the following - Monana [■] J (In the formula, R1, R'', R3 and R4 are the same as defined above.

) was obtained, and then hydrolyzed in an alkaline alcohol solution to obtain the following - Monena [
■] RI R2 (wherein, R1, R2+R3 and R4 are the same as defined above.

) The compound of the present invention can be produced by obtaining a carboxylic acid derivative represented by the following and then decarboxylating it.

On the other hand, among the compounds of the present invention represented by the above-mentioned -Momona [I], those in which Z is N, for example, the compound shown by the above-mentioned -Momona (II) and the following structural formula [■] NH, NH, j [-(,
O...... Can be produced by reacting with hydrazine hydrate represented by [■].

The organic polymer materials that can be applied in the present invention include synthetic polymer materials such as polyester, polyamide, polyurethane, polyacrylonitrile, polyolefin, polyvinyl chloride, polystyrene, and polyacrylate. Examples include fibers, thin films, plates, and other molded products, but fibers and other molded products made of cellulose acetate-based semi-synthetic polymer substances may also be used, as well as polyester fibers, polyamide fibers, and cellulose fibers. Various blended products, such as blends of semi-synthetic or synthetic fibers such as acetate fibers, or blends with natural fibers such as cellulose and wool, or molded products made of copolymers such as ABS. It's okay.

In order to color the organic polymeric material using the compound of the present invention, when applying it to fibers, the compound of the present invention represented by the above-mentioned pattern C1) is insoluble or sparingly soluble in water. Therefore, it is sufficient to prepare a dyeing bath or printing paste dispersed in an aqueous medium using a dispersing agent in a conventional manner, and perform dyeing or printing. For example, in the case of dyeing, it is possible to apply coloring with excellent fastness to ordinary dyeing, highly semi-synthetic or synthetic fibers or their blends. Maku, Said - Monana (
The compound of the present invention represented by 1) can also be applied to the so-called stock solution coloring method, in which it is added during polymerization or spinning during the manufacturing process of synthetic fibers such as polyester fibers.

When coloring a synthetic resin, the required amount of the compound of the present invention represented by the above-mentioned -Momona CI) is blended with the synthetic resin, heated and kneaded to perform compression molding, injection molding, calendar molding,
By applying ordinary molding methods such as extrusion molding, it is possible to apply robust coloring to films, sheets, pipes, and other molded products. Furthermore, a molded article with a strong color can be obtained by a cast molding method in which the compound of the present invention represented by the above-mentioned formula [I] is blended into a liquid monomer prepolymer, and then polymerized and cured.

EXAMPLES Next, the present invention will be explained in more detail by examples.
The present invention is not limited to these examples unless it goes beyond the gist thereof.

Example 1 A dyeing bath was prepared by dispersing the compound O1!2 represented by the following structural formula in 3 tons of water containing a condensate of naphthalene sulfonic acid and formaldehyde/2 and a higher alcohol sulfate co2.

Polyester fiber 1002 is immersed in this dyeing bath, /3
After dyeing at 0'C for 60 minutes, the fibers were noped, washed with water, and dried to obtain polyester fibers dyed in a highly concentrated yellow color with good light fastness and sublimation fastness.

The compounds used in this example were synthesized as follows.

A compound represented by the following structural formula % formula % 0. /μ2 for 30 minutes at -00°C in an open glass tube, the reaction product was subjected to column chromatography (silica gel, Wako Gel C-300), and the product obtained from the dichloromethane fraction was purified using a mixed solvent of methyl ethyl ketone and ethanol ( /:J) The compound of this example (0.09F, yield: 7 units) was obtained by recrystallization.

Physical properties Melting point: /Tako/Li≠°C1 Yellow needle crystals (recrystallized from ethanol) Mass spectrum: m/eJ77 (M+)
IR spectrum: λλri♂2°/1,07. /j10
．． /4L! l,, /3 riyo, /2 evening/.

/17ri, ///l, 10≠6. ri23. ♂♂7゜Ir
Hiro 05-1 'H-NMR spectrum (CDC1m): δha≠≠
(6H2t,cHs),g,t,2 (2H,q,
CHJ,≠,/Hiroshi (JH, q, CHI), 7.
o a (<48.m, Ar!-() +7゜ta 2
(-2H, m, ArH), r, lr O(2H, m
.

ArH), L70 (/H,s, ArH) Elemental analysis (C22[(uN*so4) Implementation flJ2 The compounds used in the following structural formula examples were synthesized as follows.

Compounds o and sy represented by the following structural formulas are converted into condensates of naphthalene sulfonic acid and formaldehyde l? and 3 tons of water containing 22% higher alcohol sulfate ester, and a methylnaphthalene carrier isy was added thereto to prepare a dye bath.

100 y of polyester fibers were immersed in this dyeing bath,
After dyeing at 0° C. for 20 minutes, the fibers were soaped, washed with water, and dried to obtain polyester fibers dyed in a highly concentrated yellow color with good light fastness and sublimation fastness.

0 C48e The compound represented by 0.32 and 0, l? Acetic acid solution/Jml with 2 After cooling, the precipitated crystals are removed by P. Then, the compound of this example was 0.23 Physical property value melting point isz~/! Hiro ℃, orange needles Crystal (recrystallized from ethanol) drazine hydrate A memorial service for Kojiki.

Ethanol cleaning ? I got it.

Elemental Analysis Table 1 Example 3 Polyester fibers were dyed using the compounds shown in Tables 1 and 2 below to obtain dyed products having the colors shown in the same table.

In addition, the compound used in this example was manufactured according to the method described in Example 1 or Example-.

Table 2 Example ψ Compound O8 used in Example 2! ? Is the condensate of naphthalene sulfonic acid and formaldehyde l? Prepare a dyeing bath by dispersing it in 3 tons of water containing sodium chloride and higher alkylbenzenesulfonate, immerse 100 y of polyamide fibers in this dyeing bath, dye at 100°C for 20 minutes, and then unwind, wash with water, and dry. Polyamide fibers dyed in a highly concentrated yellow color were obtained.

Example! 0.29% of the compound used in Example was mixed with polystyrene resin, and the heating cylinder temperature was 200-200℃.
When the mixture was melted and kneaded and injection molded using a conventional method, a robust polystyrene resin colored in yellow with a high concentration and a thickness of 100 ml was obtained.

Example 6 Prepolymerization was carried out by adding a polymerization initiator to methyl methacrylate (monomer) 9, and the resulting silica was treated with the compound used in Example 1. ．． After adding and dissolving l f, this colored sill was poured into a glass cell and polymerized at 50-70°C for 6 hours, then at ioo~/, 20'C for 3 hours, and then cooled. Polymethyl methacrylate resin plate colored in concentrated yellow (plate thickness! rf
aR) was obtained.

〔Effect of the invention〕

The coloring material of the present invention has excellent light resistance and sublimation resistance, and can color a polymer material with high concentration.

Claims (1)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Z represents CH or N, R^1, R^2,
R^3 and R^4 each independently represent a hydrogen atom, an alkyl group,
Acylamino group, alkoxy group, halogen atom or ▲
There are mathematical formulas, chemical formulas, tables, etc. Diaryl represented by ▼, R^5 and R^6 each independently represent a hydrogen atom, C_1 to C_2_0 substituted or unsubstituted alkyl group, aryl group or cyclohexyl group) An organic polymer coloring material consisting of a thiadiazolo heterocyclic compound.