JPH0725813B2 - Polymer color material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention provides a novel polymer coloring material compatible with fats and oils and waxes.

[Conventional technology]

Conventionally, various pigments or dyes have been used as colorants for materials containing oils and fats and waxes. For example, a method of coloring by dispersing a pigment or a dye or coloring by a dye which can be dissolved in these pigments has been used.

[Problems to be solved by the invention]

The conventional method of coloring oils and waxes with pigments has difficulty in dispersing the pigments. In practice, even if an attempt is made to disperse using a disperser with various shearing forces, the dispersion is poor or the dispersion is unstable. However, there is a problem in that it is difficult to obtain highly transparent coloring.

The method of coloring with a dye enables coloring with high transparency, but has a problem such as contamination due to migration of the dye.

[Means for solving problems]

In order to solve such a problem, the inventors of the present invention have conducted extensive studies, and as a result, a polymer coloring material obtained by dyeing a copolymer having a specific monomer structure with a cationic dye
The present invention has been completed by finding that it is compatible with waxes uniformly and that coloring with high transparency can be obtained.

That is, the following general formula (I) (Wherein R ₁ is H or CH ₃ , and R ₂ is a C _{12 to} C ₂₂ saturated or unsaturated aliphatic hydrocarbon group.) 60% by mole or more of one or more of the monomers represented by The object was achieved by a polymeric coloring material obtained by dyeing a copolymer consisting of one or more kinds of monomers having a cationic dye-dysite with 1 mol% or more with a cationic dye.

[Work]

 Hereinafter, the present invention will be described in more detail.

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

Examples of the monomer represented by the general formula (I) include
More specifically, mention may be made of esters of acrylic acid and methacrylic acid with saturated and / or unsaturated aliphatic alcohols.

More specifically, acrylic acid dodecyl ester,
Methacrylic acid dodecyl ester, acrylic acid tetradecyl ester, methacrylic acid tetradecyl ester, acrylic acid hexadecyl ester, acrylic acid hexadecene ester, methacrylic acid hexadecyl ester, methacrylic acid hexadecene ester, acrylic acid octadecyl ester, acrylic acid octadecene ester, Methacrylic acid octadecyl ester, methacrylic acid octadecene ester, acrylic acid eicosane ester, methacrylic acid eicosane ester, acrylic acid docosane ester,
Examples thereof include methacrylic acid docosane ester.

Esters of saturated and / or unsaturated aliphatic alcohols having 12 to 22 carbon atoms and acrylic acid or methacrylic acid are preferable, and those having less than 12 carbon atoms are incompatible with fats and oils and waxes.

In particular, when the number of carbon atoms is less than 14, the dyeing product of the resulting copolymer tends to be sticky because the melting temperature is around room temperature. Therefore, in normal use, esters having 14 or more carbon atoms are particularly preferable.

Examples of the monomer having a cationic dye dyeable disite that is copolymerized with 60 mol% or more of one or more of these monomers include sulfonic acid groups other than styrenesulfonic acid, phosphoric acid groups, carboxylic acid groups or salts thereof. Examples of the monomer having a sulfonic acid group other than styrenesulfonic acid include vinyl sulfonic acid,
Monomers having a phosphoric acid group, such as allyl sulfonic acid, methacryl sulfonic acid, acryloyloxyethyl sulfonic acid, methacryloyloxypropyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, are
2-hydroxyethyl acryloyl phosphate, 2-hydroxyethyl methacryloyl phosphate, 3-chloro-2-acid phosphoxypropyl methacrylate, etc.,
Examples of the monomer having a carboxylic acid group include acrylic acid,
Methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.
Further, these salts, for example, lithium salt, sodium salt, potassium salt, ammonium salt and the like can be mentioned.

The copolymerization ratio of the monomer represented by the general formula (I) and the monomer having a dye capable of dyeing a cationic dye depends on the melting temperature of the obtained polymer coloring material, the compatibility with oils and fats, the wax, and the color density. Although it can be selected, if the monomer unit represented by the general formula (I) in the copolymer is less than 60 mol%, compatibility with oils and fats and waxes tends to be insufficient, and a cationic dye dyeable disite If the amount of the monomer unit having is less than 1 mol%, sufficient color density cannot be obtained.

The monomer represented by the general formula (I) and the monomer having a cationic dye dyeable disite are polymerized in a solvent using a polymerization initiator, but the solvent used for the polymerization is not particularly limited, and dimethylformamide, Diethylformamide, N-methylpyrrolidone, ethylene carbonate, propylene carbonate, etc. may be used.

Further, the polymerization can be carried out at a monomer concentration in the solvent of 1 to 30% by weight, preferably 5 to 20% by weight.

If the monomer concentration in the solvent is too high, it is not preferable because the amount of coagulation during the polymerization is increased and it becomes difficult to remove the heat of the polymerization reaction, and too low concentration is economically disadvantageous.

Further, the polymerization initiator used may be a usual radical polymerization initiator such as AIBN, t-butyl hydroperoxide and cumene hydroperoxide.

Polymerization is carried out at a polymerization temperature which is adopted in a usual polymerization reaction using such a polymerization initiator.
It may be carried out at -100 ° C, usually 40-90 ° C.

The copolymer obtained below is dyed with a cationic dye. The cationic dye used includes ordinary basic dyes and cationic dyes.

The dyeing method is not particularly limited, but is basically achieved by, for example, subjecting an aqueous solution of a cationic dye and a specific copolymer solution of the present invention to contact treatment.

The dyeing treatment conditions are not particularly limited, but may range from room temperature to 10
It may be 0 ° C, usually 30 to 80 ° C. After such a dyeing treatment, the polymeric coloring material of the present invention is separated from the dyeing solution, and as a separation method, for example, a solvent is removed by a method such as distillation, or a coloring matter which is directly poured into a large amount of water to be precipitated. There is a method of over-separating.

The present invention is not limited by such dyeing conditions, separation and purification methods.

By dyeing a cationic dye onto a copolymer composed of the above-mentioned specific monomer composition, a coloring material which can prevent staining due to migration of a dye, which is unprecedented, and gives highly transparent coloring can be obtained.

The reason for this is not clear, but it is considered 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.

〔The invention's effect〕

The polymer coloring material of the present invention can be used, for example, as a hot-melt coloring material.

Petroleum waxes such as paraffin wax, natural waxes such as carnauba wax and montan wax, polyethylene wax, ethylene-vinyl acetate waxes or resins, which have been conventionally useful as heat-melting substances,
Furthermore, since it is very easily compatible with oils and fats such as linseed oil and soybean oil, it is useful as a coloring material for various materials using these and enables extremely highly transparent coloring.

Further, the color tone has a feature that it is clear because a cationic dye is used.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to Examples, but the scope of the present invention is not limited to these Examples.

For compatibility evaluation, 1 g of the colored polymer was heated and melted together with 10 g of the material to be measured, and what was uniformly melt-dispersed in a molten state was determined to be compatible.

The monomer composition ratio in the obtained copolymer was determined by performing elemental analysis by a combustion method on the dyed product of the copolymer.

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

Example 1 A 500 ml polymerization flask purged with nitrogen was charged with 360 g of N-methylpyrrolidone, 34 g of stearyl metal acrylate, and 6 g of acrylamido-2-methylpropanesulfonic acid, and the temperature was raised to 90 ° C. with stirring to obtain 2 g of azobisisobutyronitrile. Was added to initiate polymerization. Then, stirring was continued and polymerization was carried out at 90 ° C. for 15 hours.

To the obtained polymer solution, 30 g of Eisencatilone Brilliant Red 4GH (cationic dye CI Basic Red 14, manufactured by Hodogaya Chemical Factory Co., Ltd.) was added and stirred at 70 ° C. for 60 minutes.

Next, this solution is poured into a large amount of water to precipitate a colored polymer, which is separated and dried to obtain the polymer coloring material 3 of the present invention.
Obtained 5.3 g.

The monomer composition ratio in the obtained copolymer was 75 mol% of stearyl methacrylate and 25 mol% of acrylamido-2-methylpropanesulfonic acid, and the melting temperature of the dyed product was 48%.
It was ~ 53 ° C.

This colored polymer is well compatible with liquid paraffin, paraffin wax, linseed oil, ethylene-vinyl acetate copolymer resin (Ultrasen 722, MI400, vinyl acetate content 28% by weight, manufactured by Toyo Soda Industry Co., Ltd.), It was possible to color these.

Example 2 Polymerization and dyeing were performed in the same manner as in Example 1 except that 34 g of stearyl methacrylate was changed to 34 g of tridecyl methacrylate, and the mixture was put into water to obtain 30.5 g of the polymeric coloring material of the present invention. The monomer composition ratio in the obtained copolymer was 80 mol% tridecyl methacrylate and 20 mol% acrylamido-2-methylpropanesulfonic acid, and the melting temperature of the dyed product was 30 to 35 ° C. When this colored polymer was 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 performed in the same manner as in Example 1 except that 34 g of stearyl methacrylate was changed to 34 g of 2-ethylhexyl methacrylate, and the mixture was put into water to obtain 28.6 g of a colored polymer. The monomer composition ratio in the obtained co-aggregate was 85% by weight of 2-ethylhexyl methacrylate and acrylamide-2.
-Methyl propane sulfonic acid 15 mol%. When this colored polymer was evaluated for compatibility in the same manner as in Example 1, it was found not compatible.

Comparative Example 2 Stearyl methacrylate and acrylamide-2-
24g and 12g of methyl propane sulfonic acid, respectively
Polymerization was performed in the same manner as in Example 1 except that the amount of Catillon Brilliant Yellow 5GLH 200% was changed to 52 g, and dyeing was performed in the same manner as in Example 1, and the mixture was put into water to give 30.7 g of a colored polymer. Got The monomer composition ratio in the obtained copolymer was 55 mol% stearyl methacrylate and 45 mol% acrylamido-2-methylpropanesulfonic acid. When the compatibility of this colored polymer was evaluated in the same manner as in Example 1, it was found that the colored polymer was not completely compatible and particles of the colored polymer remained partially.

Example 3 20 g of N-methylpyrrolidone was charged into a 500 ml polymerization flask whose atmosphere was replaced with nitrogen, and the temperature was raised to 90 ° C. Next, while stirring into this flask, a monomer solution consisting of 11.9 g of stearyl methacrylate, 2.1 g of sodium allyl sulfonate and 200 g of N-methylpyrrolidone and azobisisobutyronitrile.
2 g of a catalyst solution consisting of 1.3 g and 23.7 g of N-methylpyrrolidone
Polymerization was carried out while dropping dropwise over a period of time, and then the reaction was continued for 15 hours.

To the obtained polymer solution, 10 g of Eisencatilone Brilliant Yellow 5GLH200% (cationic dye CI Basic Yellow 13, Hodogaya Chemical Co., Ltd.) was added, and the temperature was 70 ° C.
And stirred for 60 minutes.

Then, the mixture was put into water in the same manner as in Example 1 to obtain 6.0 g of the polymer color material of the present invention. The monomer composition ratio in the obtained copolymer was 80 mol% of stearyl methacrylate and 20 mol% of sodium allylsulfonate, and the melting temperature of the dyed product was 40 to 45%.
It was ℃. When this colored polymer was evaluated for compatibility in the same manner as in Example 1, it was found to be completely compatible.

Example 4 Polymerization and dyeing were carried out in the same manner as in Example 3 except that 11.9 g of stearyl methacrylate was changed to 11.9 g of tridecyl methacrylate, and the mixture was put into water to obtain 5.0 g of the polymer color material of the present invention. The monomer composition ratio in the obtained copolymer was 80 mol% tridecyl methacrylate and sodium allylsulfonate.
20 mol% and the melting temperature of the dyed product was 20-25 ° C. When this colored polymer was evaluated for compatibility in the same manner as in Example 1, it was found to be completely compatible.

Comparative Example 3 Polymerization and dyeing were performed in the same manner as in Example 3 except that 11.9 g of stearyl methacrylate was changed to 11.9 g of octyl methacrylate, and the mixture was put into water to obtain 4.7 g of a colored polymer. The monomer composition ratio in the obtained copolymer was 80 mol% octyl methacrylate and 20 mol% sodium allylsulfonate. When this colored polymer was evaluated for compatibility in the same manner as in Example 1, it was found not compatible.

Example 5 A monomer solution containing stearyl methacrylate 21.3 g, light ester PA (2-hydroxyethyl acryloyl phosphate, manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) 3.7 g, and N-methylpyrrolidone 200 g was used as the monomer solution in Example 3. Polymerization was carried out in the same manner as in Example 3 except that it was changed.

To the obtained polymer solution, 15 g of Aizen Katyro Blue GLH (cationic dye CI Basic Blue 65, Hodogaya Chemical Co., Ltd.) was added and stirred at 70 ° C. for 60 minutes.

Then, 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 stearyl methacrylate 80 mol%, light ester
PA was 20 mol% and the melting temperature of the dyed product was 55 to 60 ° C. When this colored polymer was evaluated for compatibility in the same manner as in Example 1, it was found to be completely compatible.

Example 6 Polymerization was performed in the same manner as in Example 3 except that the monomer solution in Example 3 was changed to a monomer solution containing stearyl methacrylate 23.0 g, acrylic acid 2.5 g, and N-methylpyrrolidone 200 g.

26 g of Eisencatilon Blue GLH was added to the obtained polymer solution.
Was added and stirred at 70 ° C. for 60 minutes.

Then, 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 monomer composition ratio in the obtained copolymer was 75 mol% stearyl methacrylate and 25 mol% acrylic acid, and the melting temperature of the dyed product was 50 to 55 ° C. When this colored polymer was evaluated for compatibility in the same manner as in Example 1, it was found to be completely compatible.

Claims (2)

[Claims] 1. A monomer having 60% by mole or more of one or more of the monomers represented by the following general formula (I) and a cationic dye-dyeable disite (excluding styrenesulfonic acid or a salt thereof). A polymeric coloring material obtained by dyeing a copolymer consisting of one or more kinds of 1 mol% or more with a cationic dye. (However, in the formula, R ₁ represents H or CH ₃ , and R ₂ represents a C _{12 to} C ₂₂ saturated or unsaturated aliphatic hydrocarbon group.) 2. A method according to claim 1, wherein the monomer having a cationic dye-dyable disite is a monomer having a sulfonic acid group other than styrenesulfonic acid, a phosphoric acid group, a carboxylic acid group or salts thereof. High polymer color material.