JPS63309503A - Polymeric coloring material - Google Patents

Abstract

PURPOSE:To obtain a polymeric coloring material useful as a heat-meltable coloring material which can perform coloration excellent in transparency, by dyeing a copolymer comprising a specified monomer such as a (meth)acrylate and a monomer having a cationic dye-dyeable dye site with a cationic dye. CONSTITUTION:A copolymer (A) is obtained by polymerizing at least 60mol% at least one monomer (a), such as a (meth)acrylate, of the formula [wherein R1 is H or CH3 and R2 is a 12-22C (un)saturated aliphatic hydrocarbon group], e.g., dodecyl (meth)acrylate, with at least 1mol% monomer (b) having a dye site dyeable with a cationic dye, such as a monomer having a sulfonic group, a phosphoric group, a carboxyl group or a salt thereof, except styrenesulfonic acid, e.g., acrylsulfonic acid (sodium salt), in a solvent (c) such as N- methylpyrrolidone in the presence of a polymerization initiator (d). Component A is dyed with a cationic dye (B) at room temperature to 100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides a novel polymeric coloring material that is compatible with oils and fats and waxes.

[Conventional technology]

Conventionally, various pigments or dyes have been used as colorants for materials containing oils, fats, and waxes. For example, methods of coloring by dispersing pigments or dyes, or coloring with dyes that can be dissolved in these have been used.

[Problem that the invention seeks to solve]

Conventional methods for coloring oils, fats, and waxes with pigments have difficulty dispersing the pigments, and in practice, even when attempts are made to disperse them using various types of shearing force dispersion machines, dispersion is poor or unstable. However, there are problems in that coloring often occurs and highly transparent coloring is difficult to obtain.

Although highly transparent coloring is possible with dye-based coloring methods, there are problems such as staining due to dye migration.

(Means for Solving the Problems) In order to solve these problems, the present inventors have conducted intensive research and have developed a polymer made by dyeing a copolymer with a specific heptamer structure with a cationic dye. The coloring material is oils and fats,
The present invention was achieved by discovering that it is uniformly compatible with waxes and can provide highly transparent coloring.

That is, the following general formula (I> ■ CH2 = C 1 (■) C = 0 - R2 (However, in the formula, R1 is H or CH3, R2 is C12 to C2
2, a saturated or unsaturated aliphatic hydrocarbon group. ) by dyeing with a cationic dye a copolymer consisting of 60 mol% or more of one or more monomers and 1 mol% or more of one or more monomers having cationic dye dyeable dainite. The goal was achieved with the resulting polymeric coloring material.

(For production) The present invention will be explained in more detail below.

The polymer coloring material of the present invention comprises 60 mol% or more of one or more monomers represented by the general formula (I>) and 1 mol% of one or more monomers having cationic dye dyeable dicite. It can be produced by dyeing a copolymer consisting of the above with a cationic dye.

Examples of the monomer represented by the general formula (I>) are:
More specifically, esters of acrylic acid and methacrylic acid with saturated and/or unsaturated aliphatic alcohols can be mentioned.

To be more specific, acrylic acid dodecyl ester,
Methacrylic acid dodecyl ester, acrylic acid tetradecyl ester, methacrylic acid tetradecyl ester, acrylic acid hexadecyl ester, acrylic acid hexadecene ester.

Hexadecyl methacrylate, hexadecene methacrylate, octadecyl acrylate,
Acrylic acid octadecene ester, methacrylic acid octadecyl ester, methacrylic acid octadecene ester,
Examples include eicosane acrylate ester, eicosane methacrylate ester, tocosane acrylate ester, and tocosane methacrylate ester.

Esters of saturated and/or unsaturated aliphatic alcohols having 12 to 22 carbon atoms and acrylic acid or methacrylic acid are preferred; if the number of carbon atoms is less than 12, they are not compatible with oils, fats, and waxes.

Further, especially when the number of carbon atoms is less than 14, the melting temperature of the dyed product of the obtained copolymer will be around room temperature and it will become sticky, so esters having 14 or more carbon atoms are particularly preferred for normal use.

Monomers having cationic dye-dyeable dicite that copolymerize with 60 mol% or more of one or more of these monomers include sulfonic acid groups other than styrene sulfonic acid, phosphoric acid groups, carboxylic acid groups, or salts thereof. Examples of monomers having sulfonic acid groups other than styrene sulfonic acid include vinyl sulfonic acid, allyl sulfonic acid, methacryl sulfonic acid, and acryloyloxyethyl sulfonic acid.

Examples of monomers having a phosphoric acid group such as methacryloyloxypropylsulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid include 2-hydroxyethyl acryloyl phosphate and 2-hydroxyethyl methacryloyl phosphate.

Examples of heptanomers having a carboxylic acid group such as 3-chloro-2-acid phosphoxypropyl methacrylate include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and salts thereof, such as lithium salts and sodium salts. , potassium salt.

Examples include ammonium salts.

The copolymerization ratio of the monomer represented by the general formula (I>) and the monomer having dicite that can be dyed with a cationic dye depends on the melting temperature of the resulting polymer colorant, compatibility with oils and fats, waxes, color density, etc. It can be selected, but if the content of seven units represented by the general formula (1) in the copolymer is less than 60 mol%, the compatibility with fats and oils and waxes tends to be insufficient, and cationic dyes are not dyeable. If the monomer unit containing dicite is less than 1 mol %, sufficient color density cannot be obtained.

These monomers represented by general formula (I>) and monomers having cationic dye-dyeable dicite are polymerized in a solvent using a polymerization initiator, but the solvent used for polymerization is not particularly limited, and includes dimethylformamide, diethylformamide, N-methylpyrrolidone, ethylene carbonate,
Propylene carbonate etc. are good.

Further, during polymerization, the monomer concentration in the solvent can be within the range of 1 to 30% by weight, preferably 5 to 20% by weight.

If the concentration of heptamer in the solvent is too high, the amount of coagulated substances during polymerization will increase, and it will be difficult to remove the heat of the polymerization reaction, which is undesirable, and if the concentration is too low, it will be economically disadvantageous.

Examples of polymerization initiators used in Zara include AIBN, t-
Butyl hydroperoxide.

A conventional radical polymerization initiator such as cumene hydroperoxide may be used.

Using such a polymerization initiator, polymerization is carried out at the polymerization temperature used in ordinary polymerization reactions, but the polymerization temperature is 1.
What is necessary is just to carry out at 0-100 degreeC, usually 40-90 degreeC.

Next, the copolymer obtained is dyed with a cationic dye. The cationic dyes used include common basic dyes and cationic dyes.

The dyeing method is not particularly limited, but is basically achieved by, for example, contacting an aqueous solution of a cationic dye with a solution of the specific copolymer of the present invention.

The dyeing treatment conditions are not particularly limited, but from room temperature to 1
00°C, usually 30 to 80°C. After such dyeing treatment, the polymer coloring material of the present invention is separated from the dyeing solution,
Examples of separation methods include removing the solvent by distillation or other methods, or directly adding the solution to a large amount of water and filtering and separating the precipitated colored material.

The present invention is not limited by such staining conditions 2 separation, purification methods, etc.

By dyeing the copolymer having the above-mentioned specific seven-mer structure with a cationic dye, it is possible to prevent staining caused by migration of the dye, which was not possible in the past, and to obtain a coloring material that provides highly transparent coloring.1. .

Although the reason for this is not clear, it is thought that the size of the dyeing molecule in the specific polymer skeleton of the present invention and the specific aliphatic group in the copolymer are involved.

[Effects of the Invention] The polymer coloring material of the present invention can be used, for example, as a heat-melting coloring material.

Petroleum waxes such as paraffin wax, which have traditionally been useful as heat-melting substances, natural waxes such as carnauba wax and montan wax, polyethylene wax, ethylene-vinyl acetate waxes or resins, colander, linseed oil, Since it is extremely easily compatible with oils and fats such as soybean oil, it is useful as a coloring material for various materials that use these oils, making it possible to color with extremely high transparency.

Also, the color tone is bright because cationic dyes are used.

]Examples] The present invention will be explained in more detail below with reference to Examples, but the scope of the present invention is not limited in any way by these Examples.

In addition, for evaluation of compatibility, 1 g of colored polymer was mixed with 10 g of the window material to be measured.
A product that was heated and melted together with No. 9 and uniformly dissolved and dispersed in the molten state was judged to be compatible.

The heptamer composition ratio in the obtained copolymer was determined by elemental analysis using the combustion method of a dyed product of the copolymer.

The melting temperature was determined by heating the dyed copolymer between two glass plates and measuring the temperature at which the two glass plates stick together.

Example 1 In a 500 mi polymerization flask purged with nitrogen, 360 g of N-methylpyrrolidone, 34 g of stearyl methacrylate,
6 g of acrylamide-2-methylpropanesulfonic acid was charged, the temperature was raised to 90° C. with stirring, and 2 g of azobisisobutyronitrile was added to initiate polymerization. Subsequently, stirring was continued, and polymerization was carried out at 90° C. for 15 hours.

Add 1q of Eisenryoku Chiron Brilliant Red 4GH (cationic dyes C and I) to the polymer solution.

Basic Red 14 (manufactured by Hodogaya Chemical Industry ■) 307 was added and stirred at 70°C for 60 minutes.

Next, this solution is poured into a large amount of water to precipitate the colored polymer, which is then separated and dried.
5.39 was obtained.

The copolymer 1q had a composition ratio of 75 mol% stearyl methacrylate and 15 mol% acrylamide-2-methylpropanesulfonic acid, and the melt humidity of the dyed product was 48 to 53°C.

This colored polymer is liquid paraffin, paraffin wax, necessarily oil, or ethylene-vinyl acetate copolymer resin (Ultracene 722, MI400).

It was well compatible with vinyl acetate (28% by weight, manufactured by Toyo Soda Kogyo Co., Ltd.), etc., and could be colored.

Example 2 Polymerization and dyeing were carried out in the same manner as in Example 1, except that 34 g of stearyl methacrylate was replaced with 34 g of tridecyl methacrylate, and the polymer coloring material of the present invention was poured into water.
I got q. The heptamer composition ratio in the obtained copolymer was 80 mol% of tridecyl methacrylate and acrylamide.
The content of 2-methylpropanesulfonic acid was 15 mol %, and the melting temperature of the dyed product was 30-35°C. When this colored polymer was also evaluated for compatibility in the same manner as in Example 1, it was found to be completely compatible.

Comparative Example 1 Polymerization and dyeing were carried out in the same manner as in Example 1 except that 34 g of stearyl methacrylate was changed to 349 g of 2-ethylhexyl methacrylate, and the colored polymer was poured into water to give a colored polymer of 28.6 g.
I got g. The heptamer composition ratio in the obtained copolymer was 2-
The contents were 85 mol% ethylhexyl methacrylate and 15 mol% acrylamide-2-methylpropanesulfonic acid. When this colored polymer was evaluated for compatibility in the same manner as in Example 1, it was found that the colored polymers were not compatible.

Comparative Example 2 Stearyl methacrylate and acrylamide-2-
Polymerization was carried out in the same manner as in Example 1 except that the amount of methylpropanesulfonic acid was changed to 24 g and 12 g, respectively, and then the amount of Catilon Brilliant Yellow 5GLH200% was changed to 5
Dyeing was carried out in the same manner as in Example 1 except that the amount was changed to 2 g, and the dye was poured into water to obtain 30.7 g of colored polymer. The monomer composition ratio in the copolymer 1q was 55 mol% stearyl methacrylate and 45 mol% acrylamide-2-methylpropanesulfonic acid. When this colored polymer was evaluated for compatibility in the same manner as in Example 1, it was found that the colored polymers were not completely compatible and particles of the colored polymer remained partially.

Example 3 N-methylpyrrolidone 209 was charged into a 500 mI polymerization flask purged with nitrogen, and the temperature was raised to 90'C. Next, into this flask with stirring, 11.99% of stearyl methacrylate and 2.1% of sodium allylsulfonate were added.
g, a heptamer solution consisting of 200 g of N-methylpyrrolidone and 1.39 g of azobisin butyronitrile.
A catalyst solution consisting of 23.79 kg of N-methylpyrrolidone was
Polymerization was carried out while dropping over a period of time, and the reaction was continued for 15 hours.

Add Eisencatylone Brilliant Yellow 5GLH 200% (cationic dye C, 1, Basic Yellow 13, Hodogaya Chemical Industry Co., Ltd. (Tai-made) 109 to the obtained polymer solution.
was added and stirred at 70°C for 60 minutes.

Next, it was poured into water in the same manner as in Example 1 to obtain 8.0 g of the polymer coloring material of the present invention. The resulting copolymer contained 80 mol% of stearyl methacrylate and 20 mol% of sodium allylsulfonate, and the melting temperature of the dyed product was 40 to 45°C. This colored polymer was also used in Example 1.
When the compatibility was evaluated in the same manner as above, it was found that they were completely compatible.

Example 4 Polymerization and dyeing were carried out in the same manner as in Example 3 except that 9 g of stearyl methacrylate ii was changed to 11.9 g of tridecyl methacrylate, and the resultant was poured into water to obtain a polymer coloring material 5.09 of the present invention. . The monomer composition ratio in the obtained copolymer was 80 mol% of tridecyl methacrylate and 20 mol% of sodium allylsulfonate, and the melting temperature of the dyed product was 20 to 25°C. This colored polymer was also used in Example 1.
When the compatibility was evaluated in the same manner as above, it was found that they were completely compatible.

Comparative Example 3 Polymerization and dyeing were carried out in the same manner as in Example 3 except that 11.99 g of stearyl methacrylate was changed to 9 g of octyl methacrylate II, and 4.7 g of colored polymer was poured into water.
I got it. The seven-mer composition ratio in the copolymer was determined to be 80 mol% of octyl methacrylate and 20 mol% of sodium allylsulfonate. When this colored polymer was evaluated for compatibility in the same manner as in Example 1, it was found that the colored polymers were not compatible.

Example 5 The monomer solution in Example 3 was converted to stearyl methacrylate 21.3!7. Light ester P-A (2-hydroxyethyl acryloyl phosphate, Kyoeisha Yushi Kagaku Kogyo ■Iu> 3.7 g, N-methylpyrrolidone 2
Polymerization was carried out in the same manner as in Example 3, except that the solution was changed to a 7-mer solution consisting of 0.00 g.

Add Eisen Chiron Blue GLH to the obtained polymer solution.
(Cationic dye C,1, Basic Blue 65, manufactured by Hodogaya Chemical Industry ■) was added thereto, and the mixture was stirred at 70'C for 60 minutes.

Next, it was poured into water in the same manner as in Example 1 to obtain 11.4 g of the polymer coloring material of the present invention. The monomer composition ratio in the obtained copolymer was 80 mol% of stearyl methacrylate and 20 mol% of light ester PA, and the melting temperature of the dyed product was 55 mol%.
The temperature was ~60°C. When this colored polymer was also evaluated for compatibility in the same manner as in Example 1, it was found to be completely compatible.

Example 6 The monomer solution in Example 3 was mixed with stearyl methacrylate 23.09. Acrylic acid 2.5! ? Polymerization was carried out in the same manner as in Example 3 except that the monomer solution was changed to N-methylpyrrolidone 2009.

Eisen force Chiron Blue GL in the polymer solution
Added 26 g of H and stirred at 70'C for 60 minutes.

Next, it was poured into water in the same manner as in Example 1 to obtain 17.0 g of the polymer coloring material of the present invention. The copolymer composition ratio of 1q is 75 mol% stearyl methacrylate and 25 mol% acrylic acid, and the melting temperature of the dyed product is 50-55 mol%.
It was ℃. When this colored polymer was also evaluated for compatibility in the same manner as in Example 1, it was found to be completely compatible.

Claims (2)

[Claims] (1) One type of monomer having 60 mol% or more of one or more monomers represented by the following general formula (I) and cationic dye-dyeable dicite (excluding styrene sulfonic acid or its salts) A polymer colorant obtained by dyeing a copolymer comprising 1 mol% or more of 1 mol% or more with a cationic dye. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, in the formula, R_1 is H or CH_3, R_2 is C_1
_2 to C_2_2 represents a saturated or unsaturated aliphatic hydrocarbon group. ) (2) The polymer according to claim (1), wherein the monomer having cationic dye-dyeable dicite is a monomer having a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, or a salt thereof other than styrene sulfonic acid. Molecular colorants.