JPH0570645B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to an aqueous ion, an aqueous colorant that can be used for paper, fibers, leather, wood materials, and the like. [Prior Art] Conventionally, inorganic or organic pigments or dyes such as acid dyes, direct dyes, and basic dyes have been used to color water-based inks, paper, fibers, leather, wood materials, and the like. The present invention relates to aqueous colorants that utilize basic dyes. Conventionally, basic dyes have been superior to other dyes in richness of color and clarity of color, but have had the disadvantage of poor light resistance. [Problems to be solved by the invention] The present invention takes advantage of the above-mentioned basic dyes, and
It is an object of the present invention to provide an aqueous colorant that also has excellent light resistance. [Means for solving the problems] The present invention uses a water-soluble polymer as a skeleton. This invention relates to colored polymer aqueous solutions useful as aqueous colorants. The present inventors conducted research with the aim of providing a water-based colorant with excellent performance, and found that a colored polymer obtained by dyeing a specific water-soluble copolymer with a basic dye has the characteristics of a basic dye. The present invention has been completed based on the discovery that the same properties can be maintained while also having excellent light resistance. The object of the present invention is to combine one or more ethylenically unsaturated sulfonic acids or salts thereof selected from styrene sulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, An aqueous coloring agent consisting of an aqueous solution of a dyed product using a basic dye of a water-soluble copolymer with one or more ethylenically unsaturated monomers having a hydroxyl group or an amide group selected from acrylamide and methacrylamide. It is achieved by doing so. As the ethylenically unsaturated sulfonic acid or its salt, styrene sulfonic acid or its salt is particularly preferred. Examples of the salt include lithium salt, sodium salt, potassium salt, calcium salt, and ammonium salt. The aqueous colored polymer of the present invention can be obtained by polymerizing the above monomer having a sulfonic acid group and a monomer having a hydroxyl group and/or an amide group in water to obtain an aqueous copolymer solution, to which a basic dye is added. It can be manufactured by doing. It can also be produced by carrying out the above polymerization in the presence of a basic dye. For example, the above polymerization can be carried out by adding these monomers in water to a conventional radical polymerization initiator, such as a persulfate such as potassium persulfate or ammonium persulfate,
Or organic peroxides such as kyumene hydroperoxide, t-butyl hydroperoxide,
The reaction can be easily carried out by introducing each component, together with 2,2'-azobis(2-amidinopropane) dihydrochloride, etc., all at once, partially or continuously into a polymerization vessel under stirring. For reasons such as removal of polymerization reaction heat, a method of continuous introduction is preferred. Polymerization temperature is 40℃~100℃
That's fine. The molecular weight of the water-soluble polymer obtained by such a polymerization method depends on the concentration of each monomer present in the polymerization system, the amount of radical polymerization initiator used, the polymerization temperature, and the like. Although the monomer concentration can be freely selected, it is generally 3 to 50 wt%, usually 10 to 30 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 water-soluble polymer tends to decrease, and as the amount of radical polymerization initiator used decreases, the molecular weight of the water-soluble polymer tends to increase. Normally, the amount of radical initiator used is
It is used in the range of 0.01wt% to 10wt%. The method for obtaining the water-soluble copolymer in the present invention is not limited to this method. Next, the water-soluble copolymer is dyed with a basic dye.As a basic dye, for example, Dye Handbook (edited by the Organic Synthesis Association, published by Maruzen Co., Ltd.)
In this specification, the term basic dye described in ``Basic dye'' is broadly defined to include cationic dye, and dyeing can be carried out by a conventional method. The industrially simplest method for dyeing such water-soluble polymers is to dye an aqueous solution of the polymer with an organic acid such as formic acid, acetic acid, or butyric acid, or an inorganic acid such as hydrochloric acid or sulfuric acid to a pH of 2 to 7, preferably 3 to 5. This is achieved by stirring and reacting with a basic dye within a certain range. The dyeing temperature may be 30°C to 100°C. during dyeing
If the pH is outside the range of 2 to 7, the dye may fade, discolor, or decompose, which is undesirable. If the dyeing temperature is too low, dyeing takes too long, and if the dyeing temperature is too high, the dye or polymer may deteriorate, which is also undesirable for economic reasons. In the production of the colored polymer of the present invention, the dyeing of this water-soluble copolymer with a basic dye is not limited to such dyeing conditions. [Function] The reason why the light resistance is improved by dyeing the above-mentioned water-soluble copolymer with a basic dye which originally has low light resistance is not clear. For example, a homopolymer of a monomer having a sulfonic acid group or a copolymer of a monomer having a sulfonic acid group and a monomer having a carboxyl group (for example, acrylic acid, methacrylic acid, etc.) has low light resistance. is not improved. [Effects of the Invention] Among the effects obtained by the present invention, a particularly remarkable one is the improvement in the light resistance of the colored polymer. 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). ADVANTAGE OF THE INVENTION The present invention provides a coloring material with excellent light resistance using a basic dye. The aqueous solution of the water-based colored polymer of the present invention also has the properties of a polymer and is extremely stable even during long-term storage, causing color separation, phase separation, and sedimentation, which are common to conventional coloring materials. The problem is resolved. Furthermore, the colored polymer in the aqueous colored polymer of the present invention is chemically stable, such as thermal paper,
It has the characteristic that it does not change color or fade even when applied or written on acidic paper surfaces such as pressure-sensitive paper. Since the colored polymer in the water-based colored polymer of the present invention is water-soluble, for example, when the water-based colored polymer is used as ink, it is extremely easy to erase characters and remove ink stains on skin, clothes, etc. . The water-based coloring polymer of the present invention is a novel coloring material that can be used as various water-based coloring materials by taking advantage of its characteristics. For example, the aqueous colored polymers of the present invention can be used in the form of an aqueous solution or together with other water-soluble polymers, aqueous polymer emulsions, etc. to
By adding to, impregnating, or coating paper, pulp, fibers, leather, etc., it can be used as a coloring agent for these materials, and also as a coloring agent for paints, various water-based inks, etc. It is also possible to dry an aqueous solution of an aqueous colored polymer and use it as a colored film, or use it as a powder by spray drying. [Example] The present invention will be explained in more detail by referring to Examples below, but the scope of the present invention is not limited in any way by the descriptions of these examples. In the examples, parts and percentages are expressed on a weight basis. The light resistance test was carried out using a sunshine carbon arc fade meter (black panel temperature: 65°C ± 3°C, relative humidity: 35% ± 5%). Light resistance was evaluated by comparing the degree of discoloration on the JIS L-0841 blue scale or by the color difference (ΔE) in L, a, and b displays. Example 1 25g of water was charged into a polymerization flask purged with nitrogen,
The temperature was raised to 90°C while stirring under a nitrogen stream. To this polymerization flask were added 12.2 g of spinomer NaSS (sodium p-styrene sulfonate, purity 82.0%, manufactured by Toyo Soda Kogyo Co., Ltd.), a monomer aqueous solution prepared by dissolving 91.0 g of 2-hydroxyethyl methacrylate in 300 g of water, and 7.5 g of ammonium persulfate. 75g
An aqueous solution of a polymerization initiator dissolved in the solution was added over 3 hours, and polymerization was carried out at 90°C. After the addition of the monomer aqueous solution and the polymerization initiator aqueous solution was completed, stirring was continued at 90° C. for 2 hours, and then the mixture was cooled to room temperature. Solution viscosity 27 cps (25
A clear aqueous polymer solution was obtained. The evaporation residue of this aqueous solution at 110°C was 21.1%. The polymerization rate of the monomers was 99% or more based on the analysis results of unreacted monomers and sulfur in the purified polymer. 50 parts of the polymer aqueous solution obtained in this way
An aqueous dye solution containing 0.5 part of aqueous solution of % acetic acid, 10 parts of water, and 0.5 part of Cachilon Marine Blue GRLH (basic dye, manufactured by Hodogaya Chemical Co., Ltd.) was added and dyed by stirring at 60° C. for 1 hour. A portion of the dyed aqueous polymer solution was passed through a commercially available ultrafiltration membrane, but almost no elution of the dye was observed. Ethylene glycol in 80 parts of colored polymer aqueous solution
After adding 20 parts, I filled it into a felt pen and was able to write clearly. In addition, when a light fastness test was conducted on a colored polymer aqueous solution applied to Kent paper and dried, and a dye aqueous solution with the same dye concentration applied on Kent paper and dried, ΔE was as follows, and the colored polymer of the present invention It showed excellent light resistance. ΔE Light resistance of colored polymer of the present invention 2.9 Light resistance of dye 14.3 Comparative examples 1 to 2 In Example 1, a water-soluble polymer (polymer A) using acrylic acid instead of 2-hydroxyethyl methacrylate and methacrylic acid were used. A water-soluble polymer (Polymer B) was produced. In all polymerizations, the monomer conversion rate was 99% or more. The solution viscosity is 125 cps (25℃) when using acrylic acid and 70 cps when using methacrylic acid.
(25℃). An aqueous solution of a colored polymer dyed in the same manner as in Example 1 was applied to Kent paper, dried, and subjected to a light fastness test. The ΔE was as follows. Comparative Example ΔE 1 Light resistance of colored polymer A 24.3 2 Light resistance of colored polymer B 21.5 Example 2 25 g of water was charged into a polymerization flask purged with nitrogen, and the temperature was raised to 90° C. while stirring under a nitrogen stream. Spinomer NaSS (sodium p-styrene sulfonate, purity 82.0%, Toyo Soda Kogyo Co., Ltd.) was added to this polymerization flask.
) 24.4g, 2-hydroxyethyl methacrylate 52g, 2-hydroxyethyl acrylate 28g
An aqueous monomer solution prepared by dissolving 7.5 g of ammonium persulfate in 75 g of water were added over 3 hours, and polymerization was carried out at 90°C. After the addition of the monomer aqueous solution and the polymerization initiator aqueous solution was completed, stirring was further continued at 90°C for 2 hours, and then the mixture was cooled to room temperature. A transparent polymer aqueous solution with a solution viscosity of 32 cps was obtained. The evaporation residue of this aqueous solution at 110℃ is 21.0
It was %. The polymerization rate of the monomers was 99% or more based on the analysis values of unreacted monomers and sulfur in the purified polymer. 50 parts of the polymer aqueous solution obtained in this way
% acetic acid aqueous solution, 10 parts of water, and a dye aqueous solution containing 0.5 part of Cachilon Brilliant Flavin 10GFH 300% (basic dye, manufactured by Hodogaya Chemical) were added.
The mixture was stirred at 60°C for 1 hour and dyed. Ethylene glycol in 80 parts of colored polymer aqueous solution
After adding 20 parts, I filled it into a felt pen and wrote a clear yellow marker line. In addition, when a colored polymer aqueous solution and a dye aqueous solution of the same concentration were applied to Kent paper and dried, a light fastness test was conducted, and the light fastness of the dye was below blue scale grade 1. The colored polymer of the present invention was coated with blue scale grade 3-4 and showed excellent light resistance. Example 3 25g of water was charged into a polymerization flask purged with nitrogen,
The mixture was stirred and heated to 90°C while passing nitrogen gas through it. Spinomer NaSS (p-
Sodium styrene sulfonate, purity 82.0%, manufactured by Toyo Soda Kogyo Co., Ltd.) 45.7 g, a monomer aqueous solution of 87.5 g of 2-hydroxyethyl methacrylate dissolved in 300 g of water, and 1.25 g of ammonium persulfate were added to the
An aqueous solution of a polymerization initiator dissolved in g was added over 3 hours, and polymerization was carried out at 90°C. After the addition of the monomer aqueous solution and the polymerization initiator aqueous solution was completed, stirring was continued at 90° C. for 2 hours and then cooled to room temperature. A transparent aqueous polymer solution with a solution viscosity of 345 cps was obtained. The residue of this aqueous solution after evaporation at 110°C was 25.1%. The polymerization rate of the monomers was calculated to be over 99% from the analysis values of unreacted monomers and sulfur in the purified polymer. To 50 parts of the obtained polymer aqueous solution
0.5 part of 50% acetic acid aqueous solution, Kayacryl Blue GRL300
An aqueous dye solution containing 0.2 part of a basic dye (made by Nippon Kagaku Co., Ltd.) dissolved therein was added, and the mixture was stirred at 60° C. for 1 hour for dyeing. A portion of the dyed polymer aqueous solution was dialyzed in a cellulose transparent tube, but hardly any dialysis of the dye was observed. A colored polymer aqueous solution was added to a commercially available acrylic emulsion "Primal AC-64" (Sanyo Boeki) to color the emulsion. The colored polymer aqueous solution and the colored acrylic emulsion could be stably maintained for more than one month. When a colored polymer aqueous solution was applied to Kent paper and dried, a light resistance test was performed and the result was blue scale 4.
-It was grade 5. Apply a dye aqueous solution of the same concentration,
The dried product was grade 1 on the blue scale. Example 4 In Example 1, spinomer NaSS67.1g,
Polymerization was carried out in the same manner as in Example 1, except that an aqueous monomer solution prepared by dissolving 45.5 g of acrylamide in 300 g of water was used to obtain a transparent aqueous polymer solution with a solution viscosity of 58 cps (25° C.). The evaporation residue of this aqueous solution at 110°C was 21.0%. Analysis of sulfur in the purified polymer showed that the polymerization rate of the monomer was over 99%. 50% acetic acid aqueous solution to 50 parts of the obtained polymer aqueous solution
0.3 parts, 10 parts of water, Cachiron Brilliant Retz
An aqueous dye solution containing 0.5 part of 4GH (basic dye, manufactured by Hodogaya Chemical) was added and dyed at 70°C for 1 hour. Ethylene glycol in 80 parts of colored polymer aqueous solution
When 20 parts were added and filled into a felt pen, the writing was clear. A light fastness test was conducted on Kent paper coated with a colored polymer aqueous solution and dried, and on Kent paper coated with a dye aqueous solution with the same dye concentration and dried.
The ΔE was as follows, indicating that the colored polymer of the present invention exhibited excellent light resistance. ΔE Light resistance of colored polymer of the present invention 7.8 Light resistance of dye 22.2 Comparative example 3 An aqueous polymer solution with a solution viscosity of 27 cps was obtained by carrying out the same procedure as in Example 4 except that 45.5 g of acrylonitrile was used instead of acrylamide. . The evaporation residue of this aqueous solution at 110℃ is 21.2%
It was hot. Analysis of sulfur in the purified polymer showed that the polymerization rate of the monomer was over 99%. A colored polymer aqueous solution obtained by dyeing using the dye shown in Example 4 under the same conditions was applied to Kent paper and dried, and a light resistance test was conducted.
ΔE was 31.7. Comparative Example 4 25g of water was charged into a polymerization flask purged with nitrogen.
The temperature was raised to 90°C while stirring under a nitrogen stream. In this polymerization flask, a monomer aqueous solution prepared by dissolving 122 g of spinomer NaSS (sodium p-styrene sulfonate, purity 82.0%, manufactured by Toyo Soda Kogyo Co., Ltd.) in 300 g of water and 7.5 g of ammonium persulfate were added to 75 g of water.
An aqueous solution of a polymerization initiator dissolved in g was added over 3 hours, and polymerization was carried out at 90°C. After the addition of the monomer aqueous solution and the polymerization initiator aqueous solution was completed, stirring was continued at 90° C. for 2 hours and then cooled to room temperature. A transparent polymer aqueous solution with a solution viscosity of 18 cps (25°C) was obtained. The evaporation residue of this aqueous solution at 110℃ is 21.1
It was %. The polymerization rate of sodium p-styrene sulfonate was calculated to be 99% or more from the analytical values of unreacted monomers. Similarly to Example 4, the obtained polymer aqueous solution 50
A dye aqueous solution prepared by dissolving 0.3 parts of a 50% acetic acid aqueous solution, 10 parts of water, and 0.5 parts of Cachilon Prilianthread 4GH (basic dye, manufactured by Hodogaya Chemical) was added to 70°C.
stained for 1 hour. The resulting colored polymer aqueous solution was applied to Kent paper, dried, and subjected to a light fastness test. ΔE was
It was 20.8. Further, a colored polymer aqueous solution dyed in the same manner using Cachilon Marine Blue GRLH used in Example 1 as a basic dye was applied and dried on Kent paper, and as a result of a light fastness test, ΔE was 15.3. Examples 5 to 8 25 g of water was charged into a polymerization flask purged with nitrogen,
The mixture was stirred and heated to 90°C while passing nitrogen gas through it. Into this polymerization flask, 12.2 g of spinomer NaSS (sodium p-styrene sulfonate, purity 82.0%, manufactured by Toyo Soda Kogyo Co., Ltd.) and 90 g of acrylamide were added to water.
A monomer aqueous solution dissolved in 300 g and a polymerization initiator aqueous solution prepared by dissolving 2.0 g of ammonium persulfate in 75 g of water were added over 3 hours for polymerization. After the addition of the monomer aqueous solution and the polymerization initiator aqueous solution was completed, stirring was further continued at 90°C for 2 hours, and then the mixture was cooled to room temperature. A transparent polymer aqueous solution with a solution viscosity of 115 cps (25°C) was obtained. The residual content of this aqueous solution at 110℃ is 20.1%.
It was hot. The polymerization rate of the monomers was calculated to be over 99% based on the analysis values of unreacted monomers and sulfur in the polymer. Add 0.5 parts each of Cachilon Yellow 7GLH, Cachilon Red SGLH, Cachilon Blue-GLH and Proxy FF (all manufactured by Hodogaya Chemical) as basic dyes to 50 parts of each polymer aqueous solution to an aqueous solution of 10 parts of water and 0.3 parts of 50% acetic acid aqueous solution. Dissolve and add at 80℃
Stir for hours and dye. Each of the colored polymer aqueous solutions obtained was applied to Kent paper and dried, and a light resistance test was conducted, showing excellent light resistance, with grades 3 to 6 on the blue scale. Those coated with each dye aqueous solution having the same dye concentration and dried were grade 1 or below grade 1.

[Table] Examples 9 to 11 25 g of water was charged into a polymerization flask purged with nitrogen, and the flask was stirred and heated to 90°C while nitrogen gas was passed through it. In this polymerization flask, 30 g of 2-acrylamido-2-methylpropanesulfonic acid and 70 g of 2-hydroxyethyl methacrylate were dissolved in 300 g of water, and the pH of this monomer aqueous solution was adjusted to 8.3 with a 5% aqueous sodium hydroxide solution. An aqueous polymerization initiator solution prepared by dissolving 8.0 g of ammonium persulfate in 75 g of water was added over 3 hours to carry out polymerization. After the addition of the monomer aqueous solution and the polymerization initiator aqueous solution was completed, stirring was continued at 90° C. for 2 hours, and then cooled to room temperature. A transparent aqueous polymer solution with a solution viscosity of 8.0 cps (25°C) was obtained. The evaporation residue of this aqueous solution was 20.9%. The polymerization rate of the monomers was 99% or more based on the analysis values of unreacted monomers and sulfur in the polymer. Add Cachilon Yellow GLH and Cachilon Red CD- as basic dyes to each 50 parts of the polymer aqueous solution.
0.5 parts each of FBLH and Cachilon Blue 5GH (both manufactured by Hodogaya Chemical), 10 parts of water, and 0.3 parts of 50% acetic acid aqueous solution.
The mixture was dissolved in an aqueous solution of 50% and added, and the mixture was stirred at 70°C for 1 hour to dye. The resulting colored polymer aqueous solutions were each applied to Kent paper, dried, and subjected to a light fastness test, which showed excellent light fastness as blue scale grade 4-5. The light resistance of each dye aqueous solution having the same dye concentration applied and dried was 1st class or below 1st class.

[Table] Examples 12 to 14 25g of water was charged into a polymerization flask purged with nitrogen,
The temperature was raised to 90°C while stirring while passing nitrogen gas. In this polymerization flask, 36.6 g of spinomer NaSS (sodium p-styrene sulfonate, purity 82.0%, manufactured by Toyo Soda Kogyo Co., Ltd.), 42.0 g of 2-hydroxyethyl acrylate, and 28.0 g of methacrylamide were added to water.
A monomer aqueous solution dissolved in 300 g and a polymerization initiator aqueous solution prepared by dissolving 8.2 g of ammonium persulfate in 75 g of water were added over 3 hours and polymerized at 90°C. After the addition of the monomer aqueous solution and the polymerization initiator aqueous solution was completed, stirring was continued at 90° C. for 2 hours and then cooled to room temperature. A transparent aqueous polymer solution with a solution viscosity of 21 cps (25°C) was obtained. The evaporation residue of this aqueous solution is 21.0%
It was hot. The polymerization rate of the monomers was 99% or more based on the analysis values of unreacted monomers and sulfur in the polymer. Add 0.5 parts each of Cachilon Brilliant Yellow 5GLH 200%, Cachilon Red T-BLH, and Cachilon Blue SGLH (all manufactured by Hodogaya Chemical) as basic dyes to 50 parts of each polymer aqueous solution, and 10 parts of water.
% acetic acid aqueous solution and added by dissolving it in an aqueous solution of 0.3 parts,
The mixture was stirred at 60°C for 1 hour and dyed. The resulting colored polymer aqueous solutions were applied to Kent paper, dried, and subjected to a light resistance test, which showed excellent light resistance at blue scale grades 4 to 5. When an aqueous dye solution with the same dye concentration was applied to Kent paper and dried, the light resistance was approximately 1st grade on the blue scale.

[Table] Examples 15-16 15 g of water, 20 g of 2-hydroxyethyl methacrylate, 0.3 NaHSO ₃ in a nitrogen-substituted polymerization flask
g was charged and the temperature was raised to 60°C while stirring under a nitrogen stream. Spinomer NaSS (sodium p-styrene sulfonate, purity 82.0%, manufactured by Toyo Soda Kogyo Co., Ltd.)
220g was dissolved in 700g of water to prepare an aqueous sodium p-styrenesulfonate solution. potassium persulfate
A polymerization initiator aqueous solution was prepared by dissolving 0.3 g in 30 g of water. An aqueous solution of sodium p-styrenesulfonate and an aqueous polymerization initiator solution were added over a period of 3 hours, and polymerization was carried out at 60°C. After the addition was completed, the temperature was maintained at 60°C for an additional 2 hours and then cooled to room temperature. A transparent aqueous polymer solution with a solution viscosity of 24 cps was obtained. The evaporation residue at 110°C was 20.1%. As a basic dye, Cachilon Yellow 3GLH,
Cachiron Red GLH, (both manufactured by Hodogaya Chemical)
0.5 parts of each were dissolved in an aqueous solution of 10 parts of water and 0.3 parts of a 50% acetic acid aqueous solution, and added to each of 50 parts of each polymer aqueous solution, and the mixture was stirred at 70° C. for 1 hour to dye. The dyed polymer aqueous solution was dropped into a large amount of isopropanol to precipitate a colored polymer, which was filtered, washed, and dried to obtain a colored polymer. A 15% aqueous solution of the colored polymer was applied to Kent paper and dried. A light resistance test showed that it was grade 3-4 on the blue scale, showing excellent light resistance. When aqueous dye solutions with the same dye concentration were tested in the same way,
It was grade 1 or below grade 1 on the blue scale.

【table】

Claims (1)

[Claims] 1 Styrene sulfonic acid, 2-acrylamide-
one or more ethylenically unsaturated sulfonic acids or salts thereof selected from 2-methylpropanesulfonic acid, hydroxyethyl acrylate,
Consists of an aqueous solution of a dyed product using a basic dye of a water-soluble copolymer with one or more ethylenically unsaturated monomers having a hydroxyl group or an amide group selected from hydroxyethyl methacrylate, acrylamide, and methacrylamide. Water-based colorant.