JPH0714969B2 - 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 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.

The coloring method using a dye allows highly transparent coloring, 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 recommended diligent research, and as a result, a polymer coloring material obtained by dyeing a copolymer having a specific monomer structure with an acid dye was uniformly applied to oils and fats and waxes. The present invention has been accomplished by finding that it is compatible with and that highly transparent coloring can be obtained.

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

[Work]

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

The polymer 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 monomers having an acid dye dyeable disite. It can be produced by dyeing the copolymer consisting of the above with an acid dye.

More specific examples of the monomer represented by the general formula (I) include esters of acrylic acid and methacrylic acid with saturated and / or unsaturated aliphatic alcohols.

Further 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, Examples include methacrylic acid eicosane ester, acrylic acid docosane ester, and methacrylic acid docosane ester.

Esters of saturated and / or unsaturated aliphatic alcohols having 12 to 22 carbon atoms with acrylic acid and methacrylic acid are preferable, and those having less than 12 carbon atoms are not compatible with oils and fats and waxes.

In particular, when the number of carbon atoms is less than 14, the dyeing product of the obtained copolymer has a melting temperature of around room temperature and becomes sticky easily, and therefore, esters having 14 or more carbon atoms are particularly preferable for normal use.

Examples of the monomer having an acid dye dyeable disite which is copolymerized with one or more of these monomers include a monomer having an amine salt, and examples thereof include acryloyloxyethyltrimethylammonium chloride and methacryloyloxyethyltrimethylammonium. Monomers having a quaternary ammonium salt group such as chloride and methacrylamidopropyltrimethylammonium chloride, or dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl methacrylate, dimethylaminopropyl acrylate, diethylaminoethyl methacrylate, acrylic New diethylaminoethyl, tert-butylaminoethyl methacrylate, tert-butylaminoethyl acrylate, vinyl pyridine, etc. Salts of monomers having amino group, such as hydrochloride, sulfate, formate, acetate, may be mentioned lactic acid salt.

The copolymerization ratio of the monomer represented by the general formula (I) and the monomer having an acid dye dyeable disite is determined by the melting temperature of the obtained polymer coloring material, compatibility with fats and oils, waxes,
It can be selected depending on the color density and the like, but when the monomer unit represented by the general formula (I) in the copolymer is less than 60 mol%,
The compatibility with oils and fats and waxes tends to be insufficient, and the number of monomer units having acid dye-dystable disite is 1
If it is less than mol%, a sufficient color density cannot be obtained.

The monomer represented by the general formula (I) and the monomer having an acid 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, the amount of coagulation during the polymerization will increase, and it will be difficult to remove the heat of the polymerization reaction, which is not preferable, and too low a 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 such a polymerization temperature that is adopted in a normal polymerization reaction by using a polymerization initiator.
It may be carried out at 10 to 100 ° C, usually at 40 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 an acid dye. The acid dye used may be a dye having a group capable of binding to the die side of the copolymer, that is, a dye having a sulfonic acid group or a carboxylic acid group.
Acid mordant dyes and the like can also be preferably used.

The dyeing method is not particularly limited, but it is basically achieved by, for example, subjecting the water-soluble acid dye and the 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. As a separation method, for example, the solvent is removed by a method such as distillation, or the coloring matter precipitated by directly pouring in a large amount of water is used. There are methods such as separation.

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

By dyeing an acid dye on a copolymer composed of the above-mentioned specific monomer composition, a coloring material which can prevent dyeing property 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, for example, as a hot-melt coloring material.

Petroleum waxes such as paraffin wax, which have been conventionally useful as heat-melting substances, natural waxes such as carnauba wax and montan wax, polyethylene wax,
It is extremely compatible with ethylene vinyl acetate waxes or resins, and also with fats and oils such as linseed oil and soybean oil, so it is useful as a coloring material for starting materials using these, and has extremely high transparency. Is possible.

Further, the color tone has a feature that it is clear because the pickling 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.

The compatibility was evaluated by adding 1 g of colored polymer to 10 g of measured material.
It was determined that they were compatible with each other when they were heated and melted together, and were uniformly dissolved and dispersed in a molten state.

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 is such that the dyed product of the copolymer is sandwiched between two glass plates,
It was determined by measuring the temperature at which two heated glass plates adhere to each other.

Example 1 N-methylpyrrolidone (420 g), stearyl methacrylate (21.3 g), methacrylate DMC-80 (methacryloyloxyethyl trimethylene ammonium carolide, purity 80%, Sanyo Kasei Co., Ltd.) was placed in a nitrogen-substituted 500 ml polymerization flask.
(Manufactured by K.K.) was charged and the temperature was raised to 90 ° C. with stirring. Then, stirring was continued and polymerization was carried out at 90 ° C. for 15 hours.

Sumilan black WA (acid dye
CI Acid Black 52, Sumitomo Chemical Co., Ltd.) 25.6
g was added, and the mixture was 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 then over-dried to obtain the polymer coloring material 1 of the present invention.
I got 2.0g. The monomer composition ratio in the obtained copolymer was stearyl methacrylate 80 mol%, methacrylate DMC.
-80 20 mol% and the melting temperature of the dyeing was 57-62 ° C.

This colored polymer is well compatible with liquid paraffin, paraffin wax, linseed oil, ethylene-vinyl acetate copolymer resin (Uritracene 722, MI400, vinyl acetate content 28% by weight, manufactured by Toyo Soren Kogyo Co., Ltd.). However, they could be colored.

Example 2 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 stearyl methacrylate 21.3 g, dimethylaminoethyl methacrylate 3.8 g, and N-methylpyrrolidone 160 g, and a catalyst consisting of ozobisisobutyronitrile 1.3 g and N-methylpyrrolidone 23.7 g. The solution was added dropwise over 2 hours to carry out polymerization, and then continued.
The reaction was continued for 15 hours.

After hydrochloric acid was added to the obtained polymer solution for neutralization, 17.0 g of Sumilan Black WA was added, and the mixture was stirred at 70 ° C. for 60 minutes.

Then, the mixture was put into water in the same manner as in Example 1, and the monomer composition ratio in the obtained copolymer was stearyl methacrylate 70.
Mol%, dimethylaminoethylmethacrylate 30 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 3 Polymerization and dyeing were performed in the same manner as in Example 2 except that 21.3 g of stearyl methacrylate was changed to 21.3 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 75 mol% tridecyl methacrylate and 25 mol% dimethylaminoethyl methacrylate, and the melting temperature of the dyed product was 30 to 35%.
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 In Example 2, 17.0 g of Sumilan Black WA was added to KAYARAS SPLABLE-FF2GL (direct dye CI Direct Blue 1
06, manufactured by Nippon Kyaku Co., Ltd., except that the amount was changed to 17.7 g to obtain 20.9 g of a polymeric coloring material of the present invention (melting temperature 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.

Comparative Examples 1,2 Stearyl methacrylate 21.3 g was polymerized and dyed in the same manner as in Example 2 except that 2-ethylhexyl methacrylate (Comparative Example 1) or butyl methacrylate (Comparative Example 2) 21.3 g was used, and the mixture was put into water. , Colored polymer 23.5
g (Comparative Example 1) and 25.0 g (Comparative Example 2) were obtained. The monomer composition ratio in the obtained copolymer was 80 mol% of 2-ethylmexyl methacrylate, 20 mol% of dimethylaminoethyl methacrylate (Comparative Example 1), 90 mol% of butyl methacrylate, 10 mol% of dimethylaminoethyl methacrylate (comparative). Example 2). When this colored polymer was evaluated for compatibility in the same manner as in Example 1, it was found not compatible.

Comparative Example 3 Polymerization was carried out in the same manner as in Example 2 except that the amounts of stearyl methacrylate and methylaminoethyl methacrylate were changed to 14.7 g and 6.8 g, respectively, and then Sumilan Black.
Dyeing was carried out in the same manner as in Example 2 except that the amount of WA was changed to 30.4 g, and the dye was placed in water to obtain 30.2 g of a colored polymer. The monomer composition ratio in the obtained copolymer was 55 mol% of stearyl methacrylate and dimethylaminoethyl methacrylate.
It was 45 mol%. 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.

Claims (2)

[Claims] 1. A copolymer comprising at least 60 mol% of one or more monomers represented by the following general formula (I) and at least one mol% of one or more monomers having an acid dye-dystable disite. A polymeric coloring material made by dyeing a polymer with an acid 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. The polymer coloring material according to claim 1, wherein the monomer having an acid dye-dystable disite is a monomer having an amine salt.