JPS61203107A - Production of oil-soluble colored polymer - Google Patents

Abstract

PURPOSE:To produce the titled colored polymer excellent in light resistance, by copolymerizing a complex of an ethylenically unsaturated sulfonic acid (salt) with a basic dye with another ethylenically unsaturated monomer in a solvent. CONSTITUTION:At least one insoluble complex (A) obtained by reacting an ethylenically unsaturated sulfonic acid (salt) (e.g., vinylsulfonic acid) (a) with a basic acid (b) at 5-50 deg.C and a pH of 2-8 is copolymerized with at least one ethylenically unsaturated monomer (B) other than component (a) (e.g., methyl methacrylate) at 40-100 deg.C in a solvent (e.g., N-methylpyrrolidone) in the presence of 0.001-10wt%, based on monomer, radical polymerization initiator (e.g., azobisisobutyronitrile).

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to various oil-based inks, papers, and fibers.

It relates to the production of non-aqueous colorants that can be used for leather, wood materials, etc.

[Conventional technology]

Conventionally, various oil-based inks, paper, #! Inorganic or organic pigments or oil-soluble dyes are used to color textiles, leather, wood materials, etc.

These colorants are used for coloring by being held in a suitable binder (vehicle) by dispersion or dissolution.

The present invention relates to a method for producing colorants that can replace conventional oil-soluble dyes. Conventionally, oil-soluble dyes have had the disadvantage of being inferior to water-soluble dyes in terms of richness and clarity of color.

[Problem that the invention seeks to solve]

Among the water-soluble dyes mentioned above, the present invention provides basic dyes with:
Taking advantage of the advantages of richness and clarity of colors, and
The purpose is to provide an oil-based colorant with excellent light resistance.

[Summary of the invention]

The present invention relates to a method for producing a colored polymer having an oil-soluble polymer skeleton and useful as an oil-based colorant.

The present inventors conducted research with the aim of providing an oil-based colorant with excellent performance, and found that the colored polymer obtained by polymerizing a complex formed from a specific monomer and a basic dye is The present invention was completed based on the discovery that it retains the characteristics of a coloring dye, has excellent light resistance, and can be used as a useful oil-based colorant.

[Means for solving problems]

The present invention can basically be achieved by polymerizing a complex having polymerization activity obtained by reacting an ethylenically unsaturated sulfonic acid or its salt with a basic dye and other copolymerizable monomers.

As the ethylenically unsaturated sulfonic acid or its salt,
For example vinylsulfonic acid, allylsulfonic acid, methallylsulfo/acid, styrenesulfonic acid.

Acryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, 2-acryloyloxypropylsulfonic acid 2-acryloyloxyethylsulfonic acid
-Methylpropanesulfonic acid, argyl (Oso~8.
) Unsaturated sulfonic acids such as allylsulfosuccinic acid or salts thereof, such as lithium salts, sodium salts, potassium salts, calcium salts, and ammonium salts.

Basic dyes to be reacted with these ethylenically unsaturated sulfonic acids or their salts are listed, for example, in the Dye Handbook (edited by the Organic Synthesis Association, published by Maruzen Co., Ltd.) or the British Society of Dyers (8ociet7ofDyers).
and Co1oriets) and American textile chemists,
American Dyers Association
of'rectile chemists and
Basic dyes are represented by the basic dyes listed in the Color Index (COXOR INDEX) co-edited by Co., Ltd., and the term "basic dyes" as used herein is broadly defined to include cationic dyes.

The reaction between the ethylenically unsaturated sulfonic acid or its salt and the basic dye can be carried out by a conventional method of forming a complex between an anionic substance and the basic dye. For example, this can be achieved by mixing the respective aqueous solutions. The conditions for producing such a complex having polymerization activity include pH 2-8, preferably pH 5-8.
Implemented within the scope of 5. Temperature conditions in complex production may generally be 5°C to 50°C.

If the pH at the time of complex production is outside of 2 to 8, it is not preferable because color fading, discoloration, or decomposition may occur.

If the temperature during production of the complex is too high, the dye or polymer may change in quality, and it is also undesirable for economic reasons.

Other ethylenically unsaturated monoprecious substances include methyl acrylate, ethyl acrylate, butyl acrylate, Acrylic acid esters such as 2-ethylhexyl acrylate, dodecyl acrylate, 2-and droxyethyl acrylate, 2-hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, 2- and methacrylic acid esters such as droxyethyl methacrylate and 2-hydroxypropyl methacrylate, styrene,
methylstyrene.

Examples include vinyltoluene, vinyl acetate, vinyl propionate, acrylonitrile, and methacrylonitrile.

The oil-soluble colored polymer of the present invention comprises one or more of the water-insoluble complexes produced by the reaction of the above monomer having a sulfonic acid group with a basic dye and one or more of the above monomers. It can be produced by copolymerizing the above in an organic solvent according to a conventional solution polymerization method.

For example, in the above polymerization, a polymerization-active complex prepared from a monomer having a sulfonic acid group and a basic dye and other monomers are combined with a conventional radical polymerization initiator in a solvent such as N-methylpyrrolidone. Example T: Each component is combined in bulk or with an oil-soluble radical polymerization initiator such as azobisinobutyronitrile, t-butyl hydroperoxide, and t-butyl hydroperoxide. This can be more easily carried out by partial summation or by continuous introduction into the polymerization vessel under stirring.

There is no need to limit the range of solvents that can be used other than Oka, K-methylpyrrolidone, but it is desirable that they are good solvents for complex and colored polymers, such as pyrrolidone, r-butyrolactone, etc. ethyl, ethal,
Ethylene carbonate, DM80, etc. can be used.

Usually, the polymerization temperature may be 40°C to 100°C.

The molecular weight of the colored polymer obtained by this polymerization method depends on the concentration of each monomer present in the polymerization system.

Amount of chain transfer agent and radical polymerization initiator used.

It depends on the polymerization temperature, type of solvent, etc.

The monomer concentration can be freely selected, but is generally 3
-50 wt%, usually 5-20 wt%.

Polymerization at a high monomer concentration is not preferred because the viscosity of the polymerization system increases and it becomes difficult to remove the heat of the polymerization reaction. Furthermore, polymerization at too low a concentration is not preferred for economic reasons.

Furthermore, as the amount of radical polymerization initiator used in polymerization increases, the molecular weight of the colored polymer tends to decrease.
Furthermore, as the amount of radical polymerization initiator used decreases, the molecular weight of the colored polymer tends to increase.

Usually, the amount of radical polymerization initiator used is 11
[Function] The complex formed from the ethylenically unsaturated sulfonic acid or its salt and the basic dye in the present invention and other ethylenically unsaturated monomers. In colored polymers obtained by copolymerization, the reason why the light resistance of basic dyes, which originally have low light resistance, is improved is not clearly understood.

For example, in a copolymerization composition of the complex of the ethylenically unsaturated sulfonic acid or its salt and a basic dye of the present invention with another ethylenically unsaturated monomer, the light resistance decreases as the ratio of the complex increases. The light resistance is also affected by the type of other ethylenically unsaturated monomers copolymerized, with copolymers with methacrylate having better light resistance than copolymers with styrene. It shows the tendency to

〔Effect of the invention〕

Among the effects obtained by the present invention, 4? The light resistance of the colored polymer is remarkable.

As mentioned above, although basic dyes have excellent properties as dyes, they have the disadvantage of poor light resistance (discoloration and fading of color due to light).

The present invention provides a coloring material with excellent light resistance using a basic dye.

The colored polymer solution of the present invention also has the properties of a polymer solution, is extremely stable even during long-term storage, and does not suffer from problems such as color separation, phase separation, and sedimentation that are seen with conventional coloring materials. It will be resolved.

Furthermore, the colored polymer of the present invention is chemically stable and has the characteristic that it does not discolor or fade even when applied or written on acidic paper surfaces such as thermal paper and pressure-sensitive paper.

Since the colored polymer of the present invention is water-insoluble, for example, when the colored polymer is used as an ink, there is no smearing or running away of characters due to water.

The colored polymer of the present invention is a novel coloring material that can be used as a variety of oil-based colorants by taking advantage of its characteristics.

For example, the colored polymers of the present invention may be used in the form of a solvent solution or in conjunction with other oil-soluble polymers to impregnate or apply these colorants to wood-based materials such as paper, pulp, fibers, leather, etc. It can be used as or,
It can be used as a coloring agent for paints, inks, etc.

It is also possible to dry the colored polymer solution and use it as a colored film or as a powder.

[Example]

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

In the examples, parts and percentages are expressed on a weight basis. In addition, the light resistance test was conducted using a Sunshine Carbon Arc Fade Meter (black panel temperature 65℃±5”C9).
Tested at a relative humidity of 35 inches ± 5 inches.

The light resistance rating is 1. It was performed using the TIS L-0841 blue scale method.

Example-1 Spinomer Na5S (sodium p-styrene sulfonate/acid, purity 82. Owt%, manufactured by Toyo Soda Kogyo ■) 409
was dissolved in 200ml of water. Also, add 30g of Cachiron Prilliant Red 4GH (basic dye manufactured by Hodogaya Chemical) to 22g of water.
00fRt.

When the Canalon Brilliant Red 4GH aqueous solution was added dropwise to the Subinomer Na5B aqueous solution at 30° C. over 30 minutes while stirring, a red precipitate was formed. The precipitate precipitated by cooling to 22°C was heated with F, thoroughly washed with warm water, and then vacuum-dried at 40°C.

15 g of the obtained complex powder and 559 g of butyl methacrylate were charged into a polymerization flask together with 250 g of N-methylpyrrolidone, and the flask was purged with nitrogen gas in a conventional manner.

After raising the temperature to 60"C, A, ■, B, N 1.59
-Methylpyrrolidone 209 was dissolved and added, polymerized for 20 hours, and cooled to room temperature. The polymerization rate of butyl methacrylate was measured by gas chromatography and was found to be 99.0 or higher.

The colored solution after the polymerization reaction was poured into a large amount of water to precipitate colored polymers, which were then washed with water and dried under vacuum.

When 5 g of the dried powder colored polymer [L0] was dissolved in THF (tetrahydrofuran) and fractionated using GPC, two clear peaks were observed, one of which was the peak of an unreacted complex. The other peak was in the high molecular weight region. Since clear coloring was observed in the eluents of both cases, it was confirmed that the complex was copolymerized with butyl methacrylate, and the polymerization rate of the complex was 95% or more based on the color density of these fractionated solutions. It was calculated that

Furthermore, 1 powder colored polymer was dissolved in 5 ethanol,
I was able to fill a felt-tip pen and draw lines on a piece of paper on a glass plate. The water resistance of the image was good.

When an ethanol solution of a colored polymer was applied to Kent paper using a knife coater and the light resistance was examined using a fade meter, the light resistance of the dye at the same solution concentration was about blue scale grade 1, compared to blue scale grade 4. It showed light resistance.

Examples 2 to 5 Subinomer-NaBB 409 was dissolved in water at 200 dK in the same manner as in Example-1. Further, Cachiron Brilliant Yellow 5GLI (200 pieces (manufactured by Hodogaya Chemical Co., Ltd.) 509 was dissolved in 2 tons of water.

Spinomer NaBB at 40"C while stirring the dye aqueous solution.
When an aqueous solution of was added dropwise over 30 minutes, a yellow precipitate was formed.

The precipitate precipitated by cooling to 15° C. was separated from each other, thoroughly washed with hot water under pressure, and then dried in vacuum.

159 of each of the obtained complex powders, the monomer ssy shown in Table 1, and NMP2509 were placed in a polymerization flask and polymerized by the method shown in Example 1.

Table 1 At the beginning of the polymerization, the yellow complex that existed as particles in the polymerization system disappeared as the polymerization progressed, and at the end of the polymerization, a completely transparent IMF solution of yellow colored polymer was obtained.

The IMF solution was poured into a large amount of inproper tool to precipitate the colored polymer, which was distributed from door to door. It was thoroughly washed with warm water and dried under vacuum.

The sulfur in the dried colored polymer was quantified, and the copolymerization composition of the complex and each monomer was calculated from the analytical values and was as shown in Table 1.The colored polymer was prepared in the same manner as in Example 1. G
When fractionated using the PC method, the initial eluate in the high molecular weight region was colored.

Each colored polymer (Examples 2-5) was dissolved in ethyl acetate.
The Q4 solution was filled into a feltben and was used to print on drawing paper, aluminum plates, and soft PVC sheets.

Furthermore, when we coated Kent paper with an ethyl acetate solution of the colored polymer using a knife coater and examined its light resistance using a fade meter, we found that the light resistance of the dye was about 2nd grade, but the light resistance of the colored polymers was as low as 1. It was as shown in -1.

Examples-6 to 7 In Example-1, instead of the basic dye used, Cachilon Red cD-tBLa (Example-6) and Cachilon Blue GR'rJTi (Example-7) (both dyes were manufactured by Hodogaya Chemical Co., Ltd.) ) except that a powder colored polymer was obtained in the same manner as in Example-1.

Analysis of each colored polymer and polymerization solution showed that the polymerization rate of butyl methacrylate was over 99%, and the polymerization rate of the complex was also over 90% based on the sulfur analysis value and the color analysis results by GPC preparative separation. there were.

In addition, a 10% butyl acetate solution of each colored polymer was coated on Kent paper to examine the light resistance, and the results were as shown in Table 2.

Table 2 Example 8 In Example 1, instead of using Subinomer WasB, 53 g of acrylamide-2-methylpropanesulfonic acid (Nitto Kagaku Department) was dissolved in 200+d of water and 5%
A colored polymer was obtained in the same manner as in Example 1, except that the pH was neutralized to 5.5 using an aqueous NaOH solution.

The polymerization rate of butyl methacrylate is 99% or more, while the polymerization rate of the complex depends on the amount of sulfur in the polymer,
It was calculated to be over 90 cm due to the GPO preparative method.

Further, when the light resistance was examined in the same way as in Example 1, it was found that the light resistance was about 4th grade on the blue scale.

Also, when a felt-tip pen was filled with a 10% solution of ethanol and ethyl acetate and a line was drawn, it was possible to write on paper, glass, aluminum plate, etc.

Claims (1)

[Claims] (1) Copolymerizing one or more complexes of ethylenically unsaturated sulfonic acid or its salt and basic dye with one or more other ethylenically unsaturated monomers in a solvent. A method for producing an oil-soluble colored polymer.