JP2001089978A - Sizing agent for printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sizing agent for printing, having a very good de-sizing property, showing a good touch feeling of the printed cloth and exhibiting good basic performance required for the sizing agent for printing such as a uniform dyeing property, sharpness, etc. SOLUTION: This sizing agent for printing is obtained by including a poly(acidic amino acid) as an active ingredient and further a polymeric polysaccharide as necessary.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a printing paste, and more particularly to a printing paste containing an acidic polyamino acid as an active ingredient. More particularly, the present invention relates to a printing paste which can be easily washed and removed from a cloth to be dyed after dyeing, and which is excellent in so-called degreasing property.

2. Description of the Related Art Generally, sizing agents for fiber processing can be roughly classified into warp pastes, printing pastes and finish pastes. The printing paste is included in the fiber processing paste and imparts viscous properties to the dye in order to faithfully draw a pattern or pattern on a cloth to be dyed. At the time of fixing the dye, it does not cause uneven dyeing and enhances the surface coloring, and is removed by washing after dyeing. As printing pastes used for such purposes, high-molecular polysaccharides such as starches, natural gums, carboxymethylcellulose and sodium alginate have been known.

However, since starches and natural gums are extremely difficult to deglue after dyeing, a large amount of glue remains on the printed cloth and the texture is impaired. However, there was a problem that it decreased. Carboxymethylcellulose and sodium alginate also have improved desizing properties compared to starches and natural gums, but are still difficult to completely remove by washing with water, and are not necessarily satisfactory from the viewpoint of the texture of the cloth to be dyed. There has been a demand for a printing paste agent having a better degreasing property. An object of the present invention is to provide a sizing agent which solves the above-mentioned drawbacks observed in conventional sizing agents for printing, that is, an sizing agent having excellent de-sizing properties.

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a sizing agent which eliminates the disadvantages of conventional sizing agents for printing can be obtained by using polyacidic amino acids. This has led to the present invention. That is, [1] the present invention provides a printing paste containing a polyacidic amino acid as an active ingredient, and [2] the present invention provides:
The present invention also provides the paste for printing according to the above [1], which further comprises a high molecular polysaccharide. [3] The present invention provides a method for producing a paste according to the present invention, wherein the polyacid amino acid is polyaspartic acid, polyaspartate, polyaspartic acid, Glutamic acid, polyglutamate,
The present invention provides the paste for printing according to the above [1] or [2], which is one or more selected from these modified products and their soluble crosslinked products.

BEST MODE FOR CARRYING OUT THE INVENTION The polyacid amino acid used in the present invention is not particularly limited, but for example, polyglutamic acid, polyaspartic acid, polyglutamate, polyaspartate, modified products such as copolymers and derivatives thereof, And the like, a soluble cross-linked product. One or more of these polyacidic amino acids are appropriately selected and used. Non-limiting examples of the counter ion of the polyamino acid and the modified polyamino acid salt include metal salts such as sodium, potassium, lithium, calcium, zinc, barium, cobalt and iron; tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutyl Ammonium, tetrapentyl ammonium, tetrahexyl ammonium, ethyl trimethyl ammonium, trimethyl propyl ammonium, butyl trimethyl ammonium, pentyl trimethyl ammonium, hexyl trimethyl ammonium, cyclohexyl trimethyl ammonium, benzyl trimethyl ammonium, triethyl propyl ammonium, triethyl butyl ammonium, triethyl pentyl ammonium, Triethylhexylammonium, shik Ammonium salts such as hexyltriethylammonium and benzyltriethylammonium; trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triethanolamine, tripropanolamine, tributanolamine, tripentanolamine, trihexanol Amine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dicyclohexylamine, dibenzylamine, ethylmethylamine, methylpropylamine, butylmethylamine, methylpentylamine, methylhexylamine, methylamine, Ethylamine, propylamine, butylamine, pentylamine, hexylamine, octylamine , Decylamine, there dodecylamine, amine salt of hexadecyl amine and the like. Further, different ionic species, for example, an alkali metal salt and an alkaline earth metal salt may coexist in the same molecule. The method for producing the polyacidic amino acids is not particularly limited. Examples of the production method include the following method. That is, (a) a method for producing poly-γ-glutamic acid by culturing a poly-γ-glutamic acid-producing bacterium in a medium containing L-glutamic acid. (B) a method for producing polysuccinimide by subjecting D / L-aspartic acid to thermal dehydration condensation, and producing polyaspartic acid and polyaspartate by hydrolyzing the polysuccinimide;
(C) D / L-aspartic acid is heated and dehydrated and condensed in the presence of a catalyst such as phosphoric acid to produce a polysuccinimide, and by hydrolyzing the polysuccinimide, polyaspartic acid and polyaspartic acid are produced. (D) heating and dehydrating and condensing D / L-aspartic acid in a suitable solvent in the presence of a catalyst such as phosphoric acid to produce a polysuccinimide; Polyaspartic acid by hydrolysis,
And (e) maleic anhydride, fumaric acid, malic acid, etc., and heat-reacted ammonia to produce a maleimide, or maleamic acid, ammonium maleate, etc., to produce a polysuccinimide. A method for producing polyaspartic acid and polyaspartic acid salt by hydrolyzing polysuccinimide, (f) Maleimide anhydride, fumaric acid, malic acid and the like are reacted with ammonia to produce maleimide or maleamic acid, maleic acid After producing ammonium acid or the like, a polysuccinimide is produced in the presence of a suitable catalyst and optionally in a suitable solvent, and the polysuccinimide is hydrolyzed to obtain polyaspartic acid and polyaspartate. It is a method of manufacturing. These reactions are shown below for L-aspartic acid.

Embedded image (Where n is an integer) The modified amino acid is an anhydrous polyacid amino acid represented by the general formula (1) at the time of production of the polyacid amino acid.

Embedded image Before or after partial hydrolysis of the compound of formula (1).

Embedded image (Wherein, R ₁ is a monovalent organic group, A is an organic group containing a reactive organic group such as a sulfonic acid group, an amino group, a carboxyl group, or an epoxy group, and m is an integer of 1 to 10.) In the methods for producing polyaspartic acid of b) to (d), the polyaspartic acid can be obtained by blending various monomers or oligomers with D / L-aspartic acid monomer, and polymerizing and hydrolyzing. In addition, the soluble crosslinked product in the present invention is not particularly limited as long as it is a soluble crosslinked product containing a water-soluble polyacidic amino acid crosslinked product. For example, (a) a crosslinked product of polyaspartic acid and / or polyaspartate, and (b) a crosslinked polyaspartate / protein obtained by reacting a protein with polysuccinimide and then hydrolyzing the protein. body,
(C) a crosslinked product of polyaspartate / protein obtained by reacting polyaspartic acid and / or polyaspartate with a protein and a crosslinking agent, and (d) reacting a polysuccinimide with a polysaccharide and a crosslinking agent. And a polyaspartate / polysaccharide crosslinked product obtained by hydrolysis and (e) polyaspartic acid and / or polyasparagine obtained by reacting polyaspartate with a polysaccharide and a crosslinking agent (F) radiation of poly-γ-glutamic acid obtained by culturing poly-γ-glutamic acid-producing bacteria in a medium containing L-glutamic acid,
A crosslinked product obtained by crosslinking with an electron beam or a crosslinking agent, and (g) poly-γ-glutamic acid and L-glutamic acid obtained by culturing a poly-γ-glutamic acid-producing bacterium in a medium containing L-glutamic acid. Poly-γ- obtained by mixing poly-ε-lysine obtained by culturing lysine-producing bacteria in a lysine-containing medium
And a soluble crosslinked product comprising at least one selected from the group consisting of glutamic acid polyglutamic acid / poly-ε-lysine crosslinked product. Among them, (a) a crosslinked product of polyaspartic acid and / or polyaspartate,
(B) a polyaspartate / protein crosslinked product obtained by reacting a polysuccinimide with a protein followed by hydrolysis; (c) a polyaspartic acid and / or a polyaspartate, a protein and a crosslinker A crosslinked product of polyaspartate / protein obtained by the reaction, and (d) cross-linking of polyaspartate / polysaccharide obtained by reacting polysuccinimide with a polysaccharide and a cross-linking agent, followed by hydrolysis. And (e) a soluble crosslinked product selected from the group consisting of a polyaspartic acid / polysaccharide crosslinked product obtained by reacting polyaspartic acid and / or polyaspartate with a polysaccharide and a crosslinking agent. It is particularly preferable because it can be obtained industrially at low cost. The molecular weight of the polyacid amino acid in the present invention is not particularly limited, but is preferably 3,000 to 5,000,000, more preferably 5,000 to 3,000,000 in weight average molecular weight, More preferably, it is 10,000 to 1,000,000. When the molecular weight is less than 3,000, performance as a sizing agent cannot be obtained, and 5,000,
When it exceeds 000, the degreasing property is significantly impaired.
In the present invention, the polyacid amino acid, when used alone as a paste for printing, has extremely good de-sizing properties, and thus not only significantly improves the texture of the printed cloth, but also has a uniform workability, Regarding other basic properties required for printing pastes such as leveling property and sharpness, a printed paste having the same performance as the conventional paste can be obtained. When used as a printing paste, the viscosity may not be sufficient. In such a case, it is preferable to use the paste together with an existing paste for fiber processing. The existing sizing agent for fiber processing is not particularly limited, but high molecular polysaccharides are preferred in that when used in combination with a polyacid amino acid, the performance as a sizing agent can be increased additively.
Examples of the high molecular polysaccharide in the present invention include starch (corn starch, rice starch, wheat starch, etc.), starch derivatives (dextrin, British gum, etherified starch, esterified starch, dialdehyde starch, etc.), and cellulose derivatives (carboxymethyl cellulose). , Methylcellulose, hydroxyethylcellulose, etc.), natural gums (such as gum arabic, tragacanth, karaya gum, crystal gum, locust bean gum, guar gum, etc.), sodium alginate, carrageenan, seaweed and mixtures of two or more of these. Of these, it is particularly preferable to mix carboxymethylcellulose and sodium alginate. In addition, a synthetic paste can be added. Examples of the synthetic sizing agent include vinyl alcohols such as polyvinyl alcohol and polyvinyl methyl ether, acrylics such as poly (meth) acrylic acid, poly (meth) acrylate, and polyacrylamide, maleic acid and styrene, vinyl acetate, and the like. Examples thereof include a copolymer with ethylene, other polyvinylpyrrolidone, and polyethylene oxide. In the present invention, the acid groups in the above-mentioned polymer polysaccharides and synthetic pastes are partially or wholly in the form of salts, for example, Na, K, Mg, Li, Ca, Z
It may be in the form of n, Ba, Co, Fe, and ammonium salts. Further, different ionic species, for example, an alkali metal salt and an alkaline earth metal salt may coexist in the same molecule. The effect of the polyacid amino acid in the present invention is further improved when used in combination with one or more of the various pastes described above. The mixing ratio of these existing fiber sizing agents is usually 5 to 900 parts by weight based on 100 parts by weight of the polyacidic amino acid.
Parts by weight, preferably 10 to 100 parts by weight. If the amount is less than 5 parts by weight, the characteristics of the existing sizing agent for fibers will not be sufficiently obtained, and if it exceeds 900 parts by weight, the function of the polyacid amino acid will not be sufficiently exhibited. The dye for which the paste of the present invention is used is not particularly limited, and various dyes such as a direct dye, an acid dye, a disperse dye, and a reactive dye are used.
When preparing a color paste using these dyes, various known additives can be used in combination, if necessary. Examples of these additives include acids (such as citric acid, tartaric acid, malic acid, and acetic acid), alkalis (such as sodium bicarbonate, soda ash, and caustic soda), salts (such as ammonium sulfate and ammonium tartrate), and reduction inhibitors (sodium chlorate, m -Sodium nitrobenzenesulfonate), dye dissolving agents (glycerin, acetin, diethylene glycol, cellosolves,
Resorcinol, urea, etc., antifoaming agent, penetrant, leveling agent, dyeing agent, hygroscopic agent, humectant, preservative, surfactant (anionic surfactant, nonionic surfactant, and amphoteric surfactant) Agents) and the like. Further, a UV absorber and a dispersant thereof may be blended for the purpose of photochemical stabilization. An example of the method of using the paste in the present invention is as follows. That is, after dissolving the paste of the present invention in water to obtain an original paste, a dye and the above-mentioned additives are added thereto to prepare a color paste. The obtained color paste is hand-printed or hand-printed using a paper pattern, roller printing,
The printed cloth is printed on the cloth to be printed by a mechanical method such as screen printing or transfer printing, or by ink jet, and then heated and steamed in a steamer, followed by rinsing with water and drying.

The embodiments of the present invention will be described below with reference to examples, but these are exemplifications, and the present invention is not limited by these exemplifications. In addition, in an example, all parts and% mean a weight basis. [Reference Example 1] Preparation of polyaspartic acid 100 g of L-aspartic acid and 50 g of 85% phosphoric acid were charged into a 1 L metal separable flask, and the reaction temperature was 1
The reaction was carried out at 80 ° C. under a reduced pressure of 600 Pa for 3.5 hours with stirring. After completion of the reaction, 400 ml of N, N-dimethylformamide (hereinafter referred to as DMF) was added to the flask to uniformly dissolve the reaction product. The resulting solution was dropped into 1.5 L of ion-exchanged water to reprecipitate the formed resin, and then the slurry was pulverized by a mixer and filtered under reduced pressure. After filtration,
Washing was performed until the pH of the ion-exchanged water became neutral, and the obtained cake was dried with hot air at 150 ° C. for 24 hours.
5 g of a white powder of polysuccinimide was obtained. As a result of measuring the obtained resin by GPC, the weight average molecular weight was 12
It was 5,000. 20 g of 30 g of polysuccinimide
A solution obtained by dissolving 12.3 g of sodium hydroxide in 0 g of ion-exchanged water was added, and the mixture was stirred at room temperature for 3 hours to be hydrolyzed.
A viscous liquid was obtained. 1000 ml of methanol was added to this liquid, and the resulting precipitate was filtered under reduced pressure, washed with methanol, and dried under reduced pressure at 60 ° C. for 12 hours to obtain 26.4 g of a white powdery sodium salt of polyaspartic acid. [Reference Example 2] Preparation of polyaspartic acid-soluble crosslinked product 100 g of L-aspartic acid was charged into a 1-L metal separable flask, the reaction temperature was 260 ° C, and the pressure was 600 P.
The mixture was reacted for 6.0 hours with stirring at a. After completion of the reaction, 400 ml of DMF was added to the flask to uniformly dissolve the reaction product. Then, 15 g of m-xylylenediamine (MXDA) was added with stirring over about 5 minutes and the temperature was heated to 50 ° C. After heating for 3 hours and returning to room temperature, the reaction mixture was diluted with 1000 ml of methanol.
poured into the l. The formed precipitate was filtered and dried to obtain 101.3 g of a yellow soluble crosslinked product. As a result of measuring the obtained crosslinked resin by GPC, the weight average molecular weight was 143,000, and the average molecular weight was 13,000.
A solution in which 12.3 g of sodium hydroxide was dissolved in 200 g of ion-exchanged water was added to 30 g of the obtained crosslinked resin, and the mixture was stirred at room temperature for 3 hours to hydrolyze, thereby obtaining a viscous liquid. 1000 ml of methanol was again added to this solution, and the resulting precipitate was filtrated under reduced pressure, washed with methanol, and heated at 60 ° C for 1 hour.
After drying under reduced pressure for 2 hours, 28.1 g of a white powdery sodium salt of a crosslinked polyaspartic acid was obtained. [Examples 1 to 5, Comparative Examples 1 to 3] According to Table 1, a 6% aqueous solution (original paste) of the paste in the present invention and the comparative paste was prepared. 60 parts of each glue, "SumifixBlack
B ", 6 parts of baking soda, 5 parts of urea, and 27 parts of hot water to prepare a color paste. Apply this color paste at the bottom 1cm, height 10cm
After printing on a cotton cloth with a screen (180 mesh) having a wedge-shaped pattern of
C. for 10 minutes. Further, the printed fabric obtained by washing with water, soaping, and drying was subjected to surface coloration, leveling, sharpness, and desizing properties according to the following test methods. Table 2 shows the results.

[Table 1]

[Table 2] <Test method> (1) Surface color development: The surface concentration of the dye on the printing cloth was measured using a reflection type color difference meter. The relative values are shown with the surface concentration as 100 when no polyacid amino acid is used (Comparative Example). (2) Leveling property: The degree of irritability of the printed surface was visually judged according to the following evaluation criteria. ：: Very uniform without any irritation, ○: Almost level without irritation, Δ: Slight irritation, ×: Irregularity with irritation, ××: Extremely uneven irritation (3) Sharpness: The height of the wedge-shaped pattern was measured and evaluated according to the following criteria. ◎: 9.9 cm or more, ：: 9.6 to 9.8 cm, 〜 to
Δ: 9.3 to 9.5 cm, Δ: 9.0 to 9.2 cm, Δ
X: 8.4 to 8.6 cm, x: 8.4 to 8.6 c
m, xx: 8.3 cm or less (4) Degleasing property: The texture of the printed cloth was evaluated according to the following criteria. ◎: very soft, ○: soft,
△: somewhat soft, △ to ×: slightly hard, ×: hard, ×
×: very hard

EFFECT OF THE INVENTION The printing paste of the present invention, by using a polyacidic amino acid for printing and dyeing, has a much better degreasing property than conventional pastes, so that the feeling of the printed cloth is greatly improved. In addition to the conventional pastes, other properties required for printing paste, such as leveling and sharpness, are equal to or better than those of conventional pastes, and greatly enhance the commercial value of printed cloth. It is.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shigeki Ideguchi 4-17 Jonanmachi, Izumiotsu-shi, Osaka (72) Inventor Yaya Kato 3-3-4-610, Kamotanidai, Sakai-shi, Osaka F-term (reference) 4H057 AA01 CA34 CA35 CB03 CB04 CC02 GA04

Claims (3)

[Claims] 1. A printing paste comprising a polyacidic amino acid as an active ingredient. 2. The printing paste according to claim 1, further comprising a high molecular polysaccharide. 3. The polyacid amino acid is one or more selected from polyaspartic acid, polyaspartate, polyglutamic acid, polyglutamate, modified products thereof, and soluble cross-linked products thereof. The paste for printing according to claim 1 or 2.