JPH0629368B2 - 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 that can be dissolved in them 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.

Highly transparent coloring is possible with the dyeing method,
There are problems such as contamination due to migration of dye.

[Means for solving problems]

In order to solve such problems, as a result of intensive research, as a result, a polymer coloring material obtained by dyeing a copolymer composed of a specific monomer composition with a cationic dye is uniformly compatible with fats and waxes, and It was found that highly transparent coloring was obtained, and the present invention was reached.

That is, the general formula (1) (Wherein R ₁ is H or CH ₃ , C ₂ H ₅ , and R ₂ is a C _{12 to} C ₂₂ saturated or unsaturated aliphatic hydrocarbon group), and 60 mol% of one or more of the monomers represented by The object was achieved by a polymer coloring material obtained by dyeing a copolymer consisting of the above and 1 mol% or more of styrenesulfonic acid or a salt thereof with a cationic dye.

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

The polymer coloring material of the present invention comprises a copolymer composed of 60 mol% or more of one or more of the monomers represented by the general formula (1) and 1 mol% or more of styrenesulfonic acid or a salt thereof. It can be produced by dyeing with a cationic dye.

More specifically, examples of the monomer represented by the general formula (1) will be described. Saturation of acrylic acid and methacrylic acid and / or
Alternatively, esters with unsaturated aliphatic alcohols can be mentioned.

More specifically, acrylic acid dodecyl ester,
Methacrylic acid dodecyl ester, acrylic acid tetradecyl ester, methacrylic acid tetradecyl ester, acrylic acid hexadecyl ester, acrylic acid hexadecane 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,
Methacrylic acid docosane ester etc. can be mentioned.

When the carbon number is less than 12, it becomes incompatible with fats and oils and waxes. In particular, in normal use, in terms of compatibility, melting temperature, manufacturing method, etc., saturation of 14 to 18 carbon atoms and / or
Alternatively, esters of unsaturated aliphatic alcohol with acrylic acid or methacrylic acid are preferable.

Examples of the styrene sulfonic acid salt copolymerizable with 60 mol% or more of one or more of these monomers include lithium salt, sodium salt, potassium salt and ammonium salt.

The copolymerization ratio of the monomer represented by the general formula (1) and styrene sulfonic acid or a salt thereof can be selected depending on the softening temperature of the obtained polymer coloring material, the compatibility with fats and oils and waxes, the color density and the like. When the amount of the monomer unit represented by the general formula (1) in the copolymer is less than 60 mol%, the compatibility with oils and fats and waxes tends to be insufficient, and 1 mol of styrene sulfonic acid or a salt thereof is present. If it is less than%, a sufficient color density cannot be obtained.

The monomer represented by the general formula (1) and styrenesulfonic acid or a salt thereof 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.

In addition, the polymerization may 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, cumene hydroperoxide.

Polymerization is carried out at a polymerization temperature which is adopted in a usual polymerization reaction by using such a polymerization initiator.
It may be carried out at 0 ° C to 100 ° C, usually at 40 ° C to 90 ° C.

The polymer coloring material of the present invention is not limited by the method for producing such a copolymer.

The copolymer obtained below is dyed with a cationic dye, and 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 are from room temperature to 1
The temperature may be 00 ° C, usually 30 to 80 ° C. After such dyeing treatment, the polymeric coloring material of the present invention is separated from the dyeing solution,
Examples of the separation method include a method of removing the solvent by a method such as distillation, or a method of directly adding the solvent to a large amount of water to excessively separate the precipitated colored substance.

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

[Action]

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.

Although the reason for this is not clear, it is considered that the size of the dye 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 as a coloring material for, for example, a hot-melt adhesive or a hot-melt ink.

Petroleum waxes such as paraffin wax, natural waxes such as carnauba wax and montan wax, polyethylene wax, ethylene diacetate-based wax 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 coloring with extremely high transparency.

In addition, the color tone is also clear because it uses a cationic dye.

〔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.

In addition, the compatibility was evaluated by adding 1 g of the colored polymer to the measured material 1
Those which were heated and melted together with 0 g and uniformly dissolved and dispersed in a molten state were judged to be compatible.

The melting temperature was determined by narrowing 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.

Examples -1 to 450 N-methylpyrrolidone 450 g, spinomer NaSS (sodium p-styrene sulfonate, purity 82.0%, Toyo Soda Kogyo Co., Ltd.) was placed in a 500 ml polymerization flask substituted with nitrogen.
(Manufactured by K.K.) 9.15 g, stearyl methacrylate (reagent, purity 95.0%) 44.7 g, and azobisisobutyronitrile 4.5 g were charged, and the temperature was raised to 90 ° C. with stirring.

Further, stirring was continued and polymerization was carried out at 90 ° C. for 20 hours.

A gas chromatographic analysis and an analysis of the amount of sulfur in the polymer showed that the polymerization rate of the monomer was 95% or more, and the monomer composition ratio in the obtained copolymer was stearyl methacrylate 7.
It was 7 mol% and sodium p-styrenesulfonate was 23 mol%.

The obtained polymer solution was fractionated every 100 g, and ¹⁾ Catilon Brilliant Yellow 5GLH 200% (Cation Basic Yellow 13) 6.5 g, ²⁾ Catilon Brilliant Red 4GH (Cation Basic Red 14)
7.5 g and ³⁾ CATILON BLUE GLE (cationic basic blue 65) 8.5 g- (both are cationic dyes manufactured by Hodogaya Chemical Co., Ltd.-) were added respectively as 2% aqueous solution, and 4
The mixture was stirred at a temperature of 5 ° C to 50 ° C for 60 minutes.

Each solution was poured into a large amount of water to precipitate a colored polymer, and the polymer was dried and dried to obtain a polymer coloring material of the present invention.

The melting temperatures of the obtained polymeric coloring materials are 58 to 63 ° C. and 6 respectively.
It was 0-65 degreeC and 52-57 degreeC.

These colored polymers are liquid paraffin, paraffin wax, linseed oil or ethylene vinyl acetate copolymer resin (Ultrasen 722, MI400, vinyl acetate content 2
8%, which was well compatible with Toyo Soda Kogyo Co., Ltd., etc., and was able to give clear coloring to these.

Example 4 In a 500 ml polymerization flask purged with nitrogen, 450 g of N-methylpyrrolidone, 6.1 g of spinomer NaSS, 35.4 g of methacrylic acid stearate (reagent, purity 95%), hexadecyl acrylate (sample, purity 96%) 10 ．
Charge 4g and AIBN 5.0g, 90 ℃ with stirring
The temperature was raised to. Further, stirring was continued and polymerization was carried out at 90 ° C. for 23 hours.

By gas chromatographic analysis and analysis of the amount of sulfur in the polymer in the same manner as in Examples-1 to 3, the polymerization rate of each monomer was 97% or more, and the monomer composition ratio in the obtained copolymer was 64% methacrylic acid stearate. It was 20 mol% of acrylic acid hexadecyl ester and 16 mol% of sodium p-styrenesulfonate.

Catylon 5GLH20 was added to 100 g of the obtained polymer solution.
8.0 g of 0% (Cation Blue 45, Hodogaya Chemical Co., Ltd.) was added, and the mixture was stirred and dissolved, then heated to 50 ° C. and stirred for 60 minutes.

Then, the mixture was poured into a large amount of water to obtain a colored precipitate.

This was washed with water and dried.

The melting temperature of the obtained polymer coloring material was 50 to 55 ° C.

When the compatibility was evaluated in the same manner as in Examples 1 to 3, they were completely compatible.

Comparative Examples 1-3 N-methylpyrrolidone 450 g, spinomer NaSS (sodium p-styrenesulfonate, purity 82%, manufactured by Toyo Soda Kogyo Co., Ltd.) 1 in a 500 ml polymerization flask substituted with nitrogen.
2.2 g, methacrylic acid octyl ester 40.8 g and AIBN 5.0 g were charged and the temperature was raised to 90 ° C.

Polymerization was further carried out at 90 ° C. for 20 hours while stirring.

As a result of gas chromatographic analysis and analysis of sulfur in the polymer, the polymerization rate of the monomer was 98% or more, and the monomer composition ratio in the obtained copolymer was octyl methacrylate 8
It was 1 mol% and sodium p-styrenesulfonate 19 mol%.

The same amount of the cationic dye used in Examples -1 to 3 was added to 100 g of each of the obtained polymer solutions in the same manner, and the same treatment as in Examples 1 to 3 was performed to obtain colored polymers.

The compatibility of these colored polymers with liquid paraffin, paraffin wax, linseed oil and ethylene vinyl acetate copolymer resin (Ultrasen 722, manufactured by Toyo Soda Kogyo Co., Ltd.) was examined in the same manner as in Examples 1 to 3. But they didn't agree.

Comparative Examples-4 to 7 In Examples-1 to 3, spinomer NaSS 18.3 g,
Copolymers were obtained in the same manner as in Examples -1 to 3 except that 36.8 g of stearyl methacrylate was used.

The polymerization rate of the monomers was 97% or more, and the monomer composition ratio in the obtained copolymer was 58 mol% stearyl methacrylate and 42 mol% sodium p-styrenesulfonate.

The obtained polymer solution was dyed in the same manner as in Examples-1 to 3 to obtain colored polymers.

The compatibility of the colored polymers obtained in the same manner as in Examples-1 to 3 was evaluated, but they were not completely compatible, and the colored particles remained partially.

Claims (1)

[Claims] 1. An oil or fat obtained by dyeing a copolymer of 60 mol% or more of one or more of the monomers represented by the general formula (1) and styrenesulfonic acid or a salt thereof with a cationic dye, A heat-melting polymer color material that is compatible with waxes. General formula (1) 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.