JPH0444036B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a dyeing method for obtaining sharp and clear printed designs that are prevented from bleeding when printing designs on a base material such as a fibrous structure using an inkjet or spray method. (Prior Art) Conventionally, the screen printing method, roller printing method, rotary printing method, and transfer printing method are common as methods for printing on fibrous structures. All of these printing methods require a plate-making process, which requires a great deal of labor and preparation time before production.Furthermore, in today's world where fabric properties are diversifying, high-mix, low-volume production is desired. However, there is a problem in that there is a significant lack of instant printability. To improve this, inkjet recording, which can be printed without a plate, has recently been developed in the field of paper recording and printing, and has begun to attract attention. This method is mainly used for paper, and the main problems when applied to fiber structures are bleeding and dyeability. Fiber structures do not have as much water absorption as paper, and because they have a wide variety of fiber textures and yarns, they have the disadvantage that ink bleeds significantly and it is difficult to obtain clear designs. As a method to prevent bleeding in fiber structures, BP-1587930 incorporates carbohydrates (starch, etc.) into the ink components, and
A method of pre-treating the Coagulation Agent (aluminum sulfate, borax) has been proposed. Furthermore, USP 4330293 proposes a method in which a carboxylic acid-containing synthetic polymer is blended into the ink and the fibrous structure is pretreated with an alkali compound. However, according to studies conducted by the present inventors, when acrylic fibers, cationically dyeable polyester fibers, etc. are inkjet dyed with cationic dyes, the above method has the following drawbacks. (1) It is effective for thick fabrics such as carpets, but it is not sufficient for thin fabrics that bleed significantly. (2) Cationic dyes have drawbacks such as forming aggregates with polycarboxylic acids and clogging inkjet nozzles. Furthermore, Japanese Patent Laid-Open No. 59-106989 proposes a method in which a recording medium is pretreated with a metal salt and a cationic substance, and an ink made of a water-soluble dye is used to improve water resistance and light resistance. This method is effective for anionic dyes, but not for cationic dyes. (Problems to be Solved by the Invention) The present invention was achieved as a result of extensive research into means for preventing bleeding that does not have the above-mentioned drawbacks when performing inkjet or spray dyeing using cationic dyes. An object of the present invention is to provide a method that provides good ink ejection properties and satisfies both bleeding prevention and coloring properties at the same time. (Means for solving the problems) The present invention has the following configuration. When performing inkjet or spray dyeing using a cationic dye, a liquid containing at least one anionic substance selected from the following A, B, and C that can form a complex salt with the cationic dye is used as an ink component, and the fiber structure is An inkjet or spray dyeing method characterized in that the product is coated with a water-soluble metal salt or a cationic substance that coagulates the anionic substance. A Condensation product of naphthalene sulfonic acid and formalin B Sulfonated product of lignin and lignin derivatives C Polyoxyethylene aralkyl phenyl ether sulfates According to the present invention, for example, in the case of an inkjet method, the ink discharge properties are good, and the dye itself It does not insolubilize, does not change dyeability or hue, and can prevent bleeding. That is, the present invention aims to prevent bleeding by aggregating a cationic dye that forms an ionically complex salt of an anionic compound together with the anionic compound on the surface of a fiber structure, and the dye itself is not changed. Has characteristics. The present invention will be explained in more detail below. The inkjet method is a printing method that uses a computer to control ink ejected from a 30-500μ nozzle or slit for non-contact memorization and printing, and is applied to a method of forming designs on a base material. point to something Many inkjet methods have been devised, and these methods can be classified into three main types depending on the method of generating ink droplets. The present invention can be applied to any method including these. The first method is a pressure pulse type (on-demand type) in which ink droplets are ejected from an orifice on demand using only the force of a piezoelectric element. The second method is a pressurized vibration type in which pressurized ink is ejected from pores in the form of a jet, and vibration is applied to the ink to break it up into droplets, while at the same time applying an electric charge to control this. The third method is an electrostatic acceleration type in which ink is drawn out from a nozzle by electrostatic attraction, whereas the second method described above jets pressurized ink from pores. It can also be applied to methods such as bubble jets and slit jets. On the other hand, the spray method may be any method such as a one-fluid type, a two-fluid type, or an electrostatic spray method. Both inkjet and spray methods can be used for printing or plain dyeing. The most preferred method is the inkjet method, which can easily obtain uniformity of droplets. In the present invention, the water-soluble metal salt used to pre-treat the fiber structure is a water-soluble polyvalent metal salt having a monovalent or divalent or higher valence that coagulates an anionic substance, and the metals include Na, K, Zn, Mg, etc. , Ca, Ba, B, Al, etc. Salts include halides, nitrates,
Examples include acetate. Among these, metals that have a particularly strong bonding force with anionic compounds are Ba, Ca, and K, and halogen compounds of these, particularly chlorides, are preferably used. Further, the cationic substance is an organic nitrogen-containing cationic compound, and one that has the effect of coagulating an anionic substance is selected. Examples of such compounds include various amine salts, quaternary ammonium salt type cationic surfactants, quaternary ammonium salt polymers, polyamines, and the like. Examples of amine salts include higher alkyl amine salts and amide-type amine salts obtained from fatty acids and lower amines, and quaternary ammonium salts include higher alkyl amine salts obtained from higher alkyl amines such as alkyltrimethylammonium salts and alkyldimethylbenzylammonium salts. quaternary ammonium salt,
Examples include quaternary ammonium salts obtained from fatty acids and lower amines. The quaternary ammonium salt type polymer has the following formula:
Examples include polymers of quaternary ammonium salt-containing vinyl monomers shown in (1) and (2) or copolymers with multiple monomers. R ₁ : H or C ₁ to C ₆ lower alkyl group R ₂ to _{R 4} : C ₁ to _{C 6} lower alkyl group Q: Divalent substituent X ^- : Shadow ion n: Integer from 0 to 2 Next Examples of the polyamines include polyethyleneimine, a reaction product of a low molecular weight polyfunctional amine and a polyfunctional compound for an amine group such as epihalohydrin, and polyamide polyamines. Effective pretreatment agents for cationic compounds include polyamines or polyammonium salts. The cationic compound of the present invention is preferably water-soluble. In the present invention, the fiber structure may be pretreated with at least one of these metal salts or cationic substances. As the pretreatment substance, metal salts are more effective and are more preferably used. The concentration of the pretreatment varies depending on the substrate used and the degree of bleeding, but is 0.1 to 30%, preferably 0.5 to 10%, based on the object to be treated. The application method may be any method such as a dipping method, a pad method, a coating method, a spray method, or an inkjet method. Further, the pretreated object may be in a dry state or in a wet state. The anionic substance capable of forming a complex salt with the cationic dye referred to in the present invention is already known, and
81669 includes complex salts of cationic dyes, condensates of naphthalene sulfonic acid and formalin, or sulfonated products of rhiznin and lignin derivatives, and
57-94053 includes, but is not limited to, polyoxyethylene aralkyl phenyl ter sulfates, which form complex salts of cationic dyes and anionic compounds and are finely dispersed or dissolved in water. Everything contains something. In the present invention, when an ink consisting of a cationic dye forming a water-soluble or water-dispersible complex salt is applied to a fiber structure pretreated with a water-soluble metal salt or a cationic substance, the anion forming the complex salt The system compound causes an ionic reaction with, for example, a metal salt on the structure, and aggregates on the fiber surface together with the cationic dye. On the other hand, with general cationic dyes to which no anionic substance is added, there is no aggregation effect of the dye as described above even on fabrics pretreated with metal salts, and there is no bleeding prevention effect at all. Dispersed cationic dyes that form complex salts are unique in that they exhibit a dye aggregation effect on fabrics pretreated with metal salts and can impart a bleeding prevention effect. The main component of the present invention is a cationic dye forming a water-soluble or water-dispersible complex salt as described above.
Other anti-drying agents include ethylene glycol, diethylene glycol, thiodiethylene glycol, triethylene glycol, glycerin,
polyhydric alcohols such as propylene glycol,
It preferably contains 5 to 60% of polyhydric alcohol monoethers such as ethylene glycol monomethyl ether and diethylene glycol monoethyl ether, and high boiling point water-soluble solvents such as dimethylformamide and N-methyl 2-pyrrolidone. In addition, the ink composition may be appropriately added with a physical property adjuster (adjustment of viscosity, surface tension, conductivity, PH, etc.), preservative, bactericide, oxygen absorber, chelating agent, etc. Further, for the purpose of increasing the cohesive force of the ink, a compound that reacts and coagulates with a water-soluble metal salt or a cationic substance, such as an anionic water-soluble polymer, may be added. Examples of this type include water-soluble polymers such as starch, sodium alginate, CMC, PVA, and water-soluble or water-dispersible polyesters. More preferably, sodium alginate is preferred, and water-soluble or water-dispersible polyester is particularly preferred in terms of dischargeability. As for the ink composition of the present invention, the lower the viscosity of the ink is, the more preferable it is from the viewpoint of ejectability, and the viscosity is preferably 30 cp or less, more preferably 10 cp or less. Surface tension is 40~
60 dyne/cm is preferably used. Further, the viscosity is preferably 1μ or less, preferably 0.5μ or less. After inkjet or spray dyeing, a conventional fixing method using dry heat or moist heat may be used. Furthermore, the fiber structure referred to in the present invention is a type of fiber that can be dyed with cationic dyes, and is generally mainly acrylonitrile fiber and polyester fiber copolymerized with acidic groups, but it can also be used for silk, nylon, and wool. . The material may be in any form such as thread, cotton, knitted fabric, felt, or nonwoven fabric. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 Using a fabric (structure: Decine) made of cationic dye-dyeable polyester fibers copolymerized with 5 mol% of sodium 5-sulfonisophthalate,
It was pretreated with the following drugs. (1) Pretreatment (a) Calcium chloride (CaCl ₂ 2H ₂ O) 20g/
l (b) Barium chloride (BaCl ₂ 2H ₂ O) 20g/l (c) Potassium chloride (KCl) 20g/l Pad (squeezing ratio 50%) - Drying (100℃ x 10
) Next, the following ink composition was adjusted. (2) Ink composition Add 20 parts of CI Basie Red 14 and 420 parts of water, mix well, and add 2 parts of soda carbonate to make it neutral. Next, 60 parts of a sodium salt of a condensate of formaldehyde and 2-naphthalenesulfonic acid as an anionic compound was gradually added to the mixture to form a dye complex salt. This was dried and finely dispersed using a jet mill. An ink was prepared by adding 30 parts of propylene glycol and 50 parts of ion-exchanged water as anti-drying agents to 20 parts of this dye. Next, pass through a 5μ cut filter,
It was then degassed under a vacuum of 20 mmHg. Next, dyeing was carried out under the inkjet conditions (3) shown below. (3) Inkjet conditions Inkjet method: On-demand type Nozzle diameter: 60μ Distance between nozzle and fabric: 1mm Applied voltage: 50V Resolution: 8 lines/mm After applying ink with the inkjet, ink is applied with saturated steam (110℃). Fixation treatment was performed for 20 minutes, and then soaping was performed at 60°C. The diameter of the dots of the dyed product was determined by microscopic observation, and the major axis was determined, and the L value was determined for color development, which is shown in Table 1. Comparative Example 1 The same method as in Example 1 was carried out except that the dye and concentration were different. A regular type cationic dye having the same raw material but not forming a complex salt was used as the dye, and its concentration was adjusted based on the absorbance so as to be the same as in Example 1. From the results in Table 1, it can be seen that the cationic dye of the present invention that forms a water-soluble or water-dispersible complex salt (dispersed cationic dye) exhibits an agglomerating effect on textiles pretreated with a metal salt, and has a small dot diameter. Bleeding is prevented. On the other hand, regular type cationic dyes have approximately the same dot diameter as the blank (untreated) on fabrics pretreated with metal salts, and have no bleeding prevention effect. Further, the coloring property is inversely proportional to the dot diameter, and the smaller the dot diameter, the better the coloring property. Therefore, the method of the present invention not only prevents bleeding but also significantly improves color development.

[Table] Example 2 A knitted fabric made of short acrylic fibers (structure: Motsuku Milano) was pretreated with the chemicals shown below (1). (1) Pretreatment agent a: Calcium chloride (CaCl ₂ 2H ₂ O) 50
g/l b: Barium chloride (BaCl ₂ 2H ₂ O) 50g/
l c: Polyamine type (Sun Fixtures 414C:
Sanyo Chemical Co., Ltd.) 50g/l Padded (squeezing rate 60%) - Drying (100℃ x 10 minutes)
A pretreated cloth was obtained. Next, a dispersed cationic dye was prepared using the method described below. First, 20 parts of C, I Basic Violet 27 dyestuff, polyoxyethylene aralkyl phenyl ether sulfate, and polyoxyethylene aralkyl phenyl ether were mixed in a 1:1 ratio.
60 parts and 120 parts of water were added to obtain a liquid dye. Using this dye, the following three types of ink compositions were prepared. (2) Ink composition

【table】

[Table] The viscosity of INK A, B, and C was measured using an E-type viscometer (100 rpm). 2.3cp, 2.6cp, respectively
It was 8.9cp. Pass → Deaeration → Inkjet → Fixation (100℃×
30 minutes) was treated in the same manner as in Example 1,
The dot diameters are shown in Table 2. Comparative Example 2 As a comparative example, a knitted fabric without pretreatment was prepared in Example 2.
The results are shown in Table 2. Table 2 and the results show that the dots using the pretreatment and ink of the present invention have significantly smaller dot diameters and are more effective in preventing bleeding than the untreated dots. Therefore, a sharp and clear pattern was obtained.

[Table] Example 3, Comparative Examples 3 to 4 The same dyeing treatment as in Example 1 was carried out using barium chloride as a pretreatment agent, except that the following fabric was used as the fabric. However, the color development conditions were those normally used for each fiber material. Example 3: Acrylonitrile fiber Comparative example 3: Polyethylene terephthalate fiber As Comparative example 4, an acrylonitrile fiber fabric was dyed using CI Disperse Blue 329 under normal conditions. Table 3 shows the L value before and after dyeing and the dot diameter for evaluating the bleeding prevention effect.

[Table] As is clear from Table 3, the ink of Example 1 showed a good effect on fabrics made of any fiber material in terms of the bleeding prevention effect. However, the ink of Example 1 composed of a dispersed cationic dye dyed the acrylonitrile fiber fabric of Example 3, but hardly dyed the polyethylene terephthalate fiber fabric of Comparative Example 3. Further, as in Comparative Example 4, the acrylonitrile fiber fabric was not dyed with the disperse dye. Example 4 20 parts of CIBasic BIue 75 was dissolved in 300 parts of water. When 40 parts of sodium ligninsulfonate is added to this solution, the complex salt is precipitated and dispersed. This was further finely dispersed using a ball mill to obtain a dye liquid. 25 parts of this dye solution, 25 parts of ethylene glycol, and 50 parts of ion-exchanged water were mixed, passed through a 5μ cut filter, and then degassed under vacuum (30 mmHg) to obtain an inkjet ink. Using this ink, an inkjet print sample was prepared using the same inkjet conditions and pretreated cloth as in the example. The dot diameter was 630μ for Blang, 250μ for the fabric pretreated with calcium chloride, 230μ for the fabric pretreated with barium chloride, and 270μ for the fabric pretreated with potassium chloride. That is, a good bleed prevention effect was obtained in combination with the pretreatment of the present invention. (Effects of the Invention) The present invention can form clear patterns on various knitted fabrics from thin to thick fabrics without substantially reducing the ejection performance of the inkjet during inkjet or spray dyeing. In addition, it not only has an effect of preventing bleeding, but also significantly improves color development, which is of great practical value.

Claims (1)

[Claims] 1. When performing inkjet or spray dyeing using a cationic dye, at least one anionic substance selected from the following A, B, and C that can form a complex salt with the cationic dye is added as an ink component. An inkjet or spray dyeing method characterized in that the fibrous structure is previously provided with a water-soluble metal salt or a cationic substance that coagulates the anionic substance. A Condensate of naphthalene sulfonic acid and formalin B Sulfonated products of lignin and lignin derivatives C Polyoxyethylene aralkylphenyl ether sulfates