JPH09268482A - Ink jet dyeing and ink jet dyed material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a dyed material whose pattern is clear and sharp, having good fastness by subjecting a polyamide fiber structure to ink jet printing by ink using reaction dye having a monohalogenated triazine group as a coloring component. SOLUTION: Yellow-based, red-based, purple-based, blue-based or black-based reaction dye having at least one monohalogenated triazine group as a coloring component is compounded with a water-soluble organic solvent such as ethylene glycol in an amount of 3-60% based on total weight of ink, a buffer solution such as a mixture of acetic acid with sodium acetate and/or an acid generator such as ammonium sulfate to produce ink of yellow, blue, red, black, etc. A woven or knitted fabric or a nonwoven fabric comprising nylon 6, nylon 66 or a copolymer polyamide fiber consisting essentially of nylon 6 or nylon 66 is subjected to pretreatment with a non-reactive type water-soluble polymer such as a modified carboxymethylcellulose and subjected to ink jet dyeing by using the ink.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a sportswear such as ski wear and swimwear which, when dyeing a polyamide fiber structure by an ink jet method, can provide a dyed product with clear and sharp color expression and high quality and high fastness. The present invention relates to an inkjet dyeing method and an inkjet dyed product that are preferably used for dyeing.

[0002]

2. Description of the Related Art At present, the mainstream of printing is screen printing and roller printing. However, these methods are not suitable for high-mix low-volume production. Therefore, a printing method using a plateless ink jet has been proposed as an alternative method.

In ink jet dyeing inks,
Since nozzle clogging prevention and ejection stability are required, it is necessary for the dye used to simultaneously satisfy high solubility, high purity, long-term storage stability and the like.

On the other hand, in dyeing polyamide fibers such as nylon, which is represented by sportswear such as ski wear and swimwear, and particularly printing, it is required that the color is clear and that the fastness of the dyed product is good. To be done. Particularly in swimwear, chlorine resistance and high wet fastness are important characteristics.

Acid dyes are generally used as dyes used for dyeing polyamide fibers. It has been proposed to use a specific acid dye in JP-A-6-57650 and the like for inkjet use. However, a dye having a high solubility which is easily converted into an inkjet ink has a drawback that the wet fastness is generally insufficient. Have. Further, since commercially available dyes contain impurities such as water-soluble salts, purification is required to prepare a stable ink, which is economically problematic. Therefore, in the field where a high wet fastness is required such as a bathing suit, it is the present situation that none of the acid dyes usually used satisfy both the ink stability and the fastness.

[0006]

DISCLOSURE OF THE INVENTION As described above, the object of the present invention is to obtain various properties such as solubility and stability required as an ink for ink jet dyeing of a synthetic polyamide fiber structure and sharpness required as a dyed product. , Handle sharpness,
It is to solve the problem of simultaneously satisfying various characteristics such as color density and color fastness.

[0007]

The ink jet dyeing method of the present invention has the following constitution in order to solve the above problems.

That is, in inkjet dyeing a polyamide fiber structure, a reactive dye having at least one monohalogenated triazine group is used as a coloring component, and as a pretreatment, a water-soluble polymer which is non-reactive with the reactive dye is used. Is applied to a polyamide fiber structure.

The ink-jet dyed product of the present invention is
In order to solve the above-mentioned subject, it has the following composition.

That is, in inkjet dyeing a polyamide fiber structure, a reactive dye having at least one monohalogenated triazine group is used as a coloring component, and as a pretreatment, a water-soluble polymer which is non-reactive with the reactive dye is used. Is applied to a polyamide fiber structure, which is an inkjet dyed product dyed by an inkjet dyeing method.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The synthetic polyamide in the present invention means a polyamide comprising nylon 6, nylon 66 and a copolymer mainly composed of these. The fiber structure in the present invention refers to a woven fabric, a knitted fabric, a non-woven fabric, an artificial leather, or the like. Also, other natural fibers other than synthetic polyamide,
It may contain synthetic fibers and the like.

The reactive dye used in the present invention has at least one monohalogenated triazine group as a coloring component.

Reactive dyes having no monohalogenated triazine group have a problem that they are inferior in dyeing characteristics, ejection stability from nozzles and long-term storage stability, which are characteristic of inkjet dyeing.

That is, when the ink for ink-jet dyeing used in the present invention is in the neutral to acidic region, the reactive dye containing at least one monohalogenated triazine group has a basic structure similar to that of the polyamide fiber structure. It has good ink properties and good fastness of dyed products, as compared with the acidic dyes having the above and other reactive dyes having a reactive group. There is a reactive dye having a dichlorotriazine group as an analogue of a reactive dye having a monohalogenated triazine group, but when the ink is made to have an acidic to neutral region, it is dyed by hydrolysis due to its high reactivity. It is not suitable as an ink for inkjet dyeing, because the degree of deterioration in adhesion is large and color blurring of the dyed product occurs. Further, vinyl sulfone type dyes, which are often used for cotton, are inferior to the dyes used in the present invention in terms of hydrolysis stability and fastness of the dyed product. In particular, when used for a continuous type inkjet dyeing machine in which ink is circulated and reused, decomposition of dye and deterioration of dyeing property are remarkable. The reactive dye used in the present invention has at least one monohalogenated triazine group.
When an acidic dye having a similar structure having no reactive group is used in the present invention, the wet fastness tends to be inferior to that of the reactive dye used in the present invention.

Although the reason for this is not clear, in the reactive dye used in the present invention, there is a possibility that the monohalogenated triazine group, which is a reactive group, is covalently bonded to the amino group or amide group of the polyamide fiber and the affinity with the polyamide. It is possible to improve the sex.

When other reactive groups are used in combination as a polyfunctional type, they have less influence on ink characteristics and dyeing characteristics than reactive dyes containing only those reactive groups.
It is also possible to use polyfunctional reactive dyes containing one or more monohalogenated triazine groups.

As the reactive dye used in the present invention, for example,
C. I. Reactive Yellow-2, 3, 1
8, 81, 84, 85, 95, 102, 105, 13
5, 136, 137, 138, 143, 145, 15
1, 161, 167, 168, 175, C.I. I. Rea
ctive Red-3, 3: 1, 13, 24, 29,
31, 33, 43, 45, 55, 58, 120, 14
1, 183, 184, 193, 194, 195, 20
4, 217, 218, 220, 222, 223, 22
6, 228, 230, 235, C.I. I. Reactive
e Violet-1, 2, 38, C.I. I. React
ive Blue-2, 5, 13, 14, 15, 18,
25, 38, 39, 41, 49, 52, 71, 72, 1
12, 131, 160, 162, 171, 171: 1,
176, 182, 184, 190, 191, 192, 1
94, 198, 204, 211, 212, 214, 22
1, 222, 230, 231, 235, 236, 24
3, C.I. I. Reactive Black-1, 8,
13, 39, etc. can be used.

However, the present invention is not limited to these, and is not particularly limited as long as the dye structure contains at least one monohalogenated triazine group. The halogen of the group is also not particularly limited, but chlorine or fluorine is preferable.

Particularly preferred dyes for nylon 6 or nylon 66 include C.I. I. R
active Yellow-2, 85, 95, C.I.
I. Reactive Red-3: 1, 24, 33,
218, 226, 228, 235, C.I. I. React
iv Violet-1, 2, C.I. I. Reacti
ve Blue-5, 13, 15, 49, 72, 17
6, 198, C.I. I. Reactive Black-
A dye group consisting of 1, 8, 39 can be used.

These dyes are available as powders or liquid products, but liquid products have less impurities, and in many cases, there is an advantage that commercial products can be used without particular purification. Further, these dyes can be used not only individually, but also as a mixture of a plurality of dyes and toning.

For fluorescent colors and some vivid colors that cannot be produced by reactive dyes, it is possible to use them in combination with acid dyes.

The ink used in the ink jet dyeing method of the present invention contains a reactive dye containing at least one monohalogenated triazine group as an essential component, but the other components are not particularly limited and are suitable for the ink jet system. Various ink designs can be used. An ink in which a dye is dissolved in a water-based medium is a preferred example.

As a typical component of the ink, it is preferable to contain a water-soluble organic solvent in addition to the dye and water as the main medium. For example, ketones or keto alcohols such as acetone and diacetone alcohol; ethers such as dioxane;
Oxyethylene or oxypropylene addition polymers such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol; ethylene glycol, propylene glycol, trimethylene glycol, butylene glycol, hexylene glycol 2-6 alkylene groups such as
Alkylene glycols containing 1 carbon atom;
Triols such as 6-hexanetriol; thiodiglycol; glycerin; lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether Lower dialkyl ethers of polyhydric alcohols such as triethylene glycol dimethyl (or ethyl) ether and tetraethylene glycol dimethyl (or ethyl) ether; sulfolane, N-methyl-2-pyrrolidone, 1,3-dimethyl-2- Imidazolidinone or the like can be used. Ethylene dilicol, 1,3-propanediol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol and sulfolane can be preferably used. These water-soluble organic solvents have little effect on the sticking rate of the reactive dye having a monohalogenated triazine group to the fiber, and are highly effective in preventing nozzle clogging.

The content of these water-soluble organic solvents is preferably 3 to 60% by weight, more preferably 5 to 50%, and further preferably 10 to 10% by weight based on the total weight of the ink.
It is in the range of 40%.

If necessary, various surfactants, p
An H regulator, a preservative and the like can be added to the ink.
Further, when the dye is made into an ink, treatments such as purification and filtration can be performed as necessary.

The pH of the ink is not particularly limited, but from the viewpoint of preventing the hydrolysis of the reactive dye and improving the storage stability and color developability of the ink, the pH of the ink for ink jet dyeing is preferably 1 to 8, and more preferably. Is 3 to 7. Moreover, it is preferable to use at least one of a buffer solution and an acid generator for pH adjustment. The acid generator refers to a compound whose pH value is reduced by heating, and for example, ammonium sulfate, ammonium tartrate, ammonium carbonate, ammonium acetate and the like can be used. As the buffer solution, one composed of a mixture of acetic acid, a weak acid such as sodium acetate, and a salt thereof can be used.

The ink jet method used in the present invention is not particularly limited, and various methods can be used. Typical methods include an on-demand method and a continuous method. As the on-demand system, a piezo type and a thermal type such as a bubble jet can be used. As the continuous system, a charge amount deflection type, a Hertz system or the like can be used.

Next, in the present invention, prior to ink jet dyeing, in order to prevent bleeding, improve surface color density, and improve quality, the fiber structure is pretreated with the reactive dye and a non-reactive water-soluble polymer. It is to be given.

The non-reactive water-soluble polymer used in the present invention is an anionic or nonionic compound, which is a water-soluble polymer having no hydroxyl group, has a small number of hydroxyl groups in the total molecular weight, or has a hydroxyl group. However, it means a water-soluble polymer having a small hydroxyl group reaction activity. For example, as those having no hydroxyl group, alginates, polyacrylates, etc., those having few hydroxyl groups or having low reactivity of hydroxyl groups include highly etherified carboxymethyl cellulose type, highly alkylated methyl cellulose, and modified gum type sizing agent. Can be used.

In the present invention, when a reactive water-soluble polymer having a high hydroxyl group reaction activity is used, the monohalogenated triazine group in the reactive dye reacts with the hydroxyl group, and the adhesion of the reactive dye to the fiber is lowered. There's a problem.

Further, in the present invention, an anionic dye having a sulfonic acid group is preferably used as the reactive dye. When a cationic water-soluble polymer is used, an ionic interaction with the reactive dye may occur, which may reduce the fixing property of the dye to the fiber.

Further, in the present invention, the pretreatment liquid containing the reactive dye and the non-reactive water-soluble polymer used in the pretreatment is weakly acidic or neutral from the viewpoint of improving the dyeability to the fiber. Is preferred.

Further, as described in Japanese Patent Laid-Open No. 60-99081, it has been proposed to perform a water repellent pretreatment as an ink jet pretreatment, but according to the study by the present inventors, this is done. In the pretreatment, the dye ink tends to be attached to the surface of the fiber, and especially for elastic knit fabrics with elastic yarns used for swimwear etc., the inside is not dyed when the fabric is pulled It was found to be prone and unfavorable.

As the pretreatment agent, in addition to the water-soluble polymer, other agents such as a pH adjusting agent such as ammonium sulfate, a surfactant, a leveling agent and the like can be added as required.
The treatment liquid may be an aqueous treatment liquid, an emulsion treatment liquid, or a solvent treatment liquid, and the treatment method is not particularly limited, and it can be applied by a pad method, a coating method, a spray method, an inkjet method or the like. After application, the ink is usually dried and then subjected to inkjet dyeing. However, a water-adjusted cloth may be used for controlling bleeding and controlling the swelling of the cloth when the ink is applied.

The amount of the water-soluble polymer added as a pretreatment agent is preferably 0.1 to 20%, more preferably 0.5 to 10%, based on the weight of the cloth.

Furthermore, it is also possible to use porous fine particles together as a pretreatment agent. As an example of porous fine particles, silica, alumina, alundum, porous ceramics, zeolite, magnesia, carbon, pearlite,
Shirasu or the like can be used, but is not limited thereto.

It is preferable that the cloth provided with the ink by the ink jet method according to the present invention is subsequently subjected to the steps of fixing the dye to the fiber and removing the dye. As a fixing method, that is, a coloring method, a conventional method may be used, and for example, a steaming method, an HT steaming method or the like is adopted. Steaming with saturated steam is preferably used as a coloring condition for the synthetic polyamide.

After color development, it is preferable to perform soaping to remove the pretreatment agent and the unfixed dye, but it is necessary to optimize the cleaning agent and the cleaning conditions in order to prevent white spot contamination. If necessary, as a post-treatment, in order to further improve wet fastness, chlorine fastness, light fastness, etc., polyamine-based, polycation-based fixative, tannin or synthetic tannin-based fixative, ultraviolet absorber, antioxidant , A light stabilizer and the like can be used.

The fabric dyed according to the present invention exhibits excellent dyeing properties, color vividness, pattern sharpness and dyeing fastness, and therefore can be preferably used not only for general clothing but also for sports such as skis and swimwear.

[0041]

The present invention will be described in more detail with reference to the following examples. All "%" in the text are% by weight.

[Example 1 and Comparative Example 1] (1) Inkjet device An inkjet printer having the following specifications by a piezo type on-demand system was used.

Number of colors: 4 colors Color Nozzle diameter: 50 microns Resolution: 8.0 dots / mm Printing method: Nozzle moving method (2) Ink preparation Ink A (monochlorotriazine type ... Inventive) Reactive dye (CI Reactive Blue) 2): 10% ethylene glycol: 20% buffer solution: 50% water: 20% The above components were mixed and stirred to obtain an ink (A) as an example. As the buffer solution, 0.1 at pH 5.5
N acetic acid / sodium acetate was used. As comparative examples, the following inks (B) to (D) containing the same dye base were obtained with the same formulation.

Ink B (dichlorotriazine type ... Comparative example) Reactive dye (CI Reactive Blue 1): 10% Ethylene glycol: 20% Buffer solution: 50% Water: 20% Ink C (vinyl sulfone type ... Comparative example) Reaction Dye (CI Reactive Blue 19): 10% Ethylene glycol: 20% Buffer solution: 50% Water: 20% Ink D (acid dye ... Comparative example) Acid dye (CI Acid Blue 25): 10% Ethylene glycol: 20% Buffer Solution: 50% Water: 20% C.I. I. Reactive Blue2, C.I.
I. ReactiveBlue1, C.I. I. React
ive Blue 19, and C.I. I. AcidBlue
The 25 chemical formulas are shown in formulas (I) to (IV), respectively.

[0045]

Embedded image

Embedded image

Embedded image

Embedded image (3) Fabric pre-treatment Nylon 6, 100% woven fabric, sodium alginate 1.0
% Aqueous solution was pretreated by the pad-dry method (adhesion amount: 0.6%).

(4) Inkjet dyeing In the apparatus of (1) above, printing with inks (A) to (D) was performed on the pretreated fabric of (3) immediately after ink preparation and after leaving the ink for one month at room temperature. went. After applying the ink, color development processing was performed for 20 minutes with saturated steam at 102 ° C., and then soaping processing was performed.

The dyeing property was evaluated on the basis of the degree of coloring before and after soaping, in three grades of ◯ Δ ×.

The fastnesses of the dyeings obtained by the above (1) to (4) were compared. With respect to the change with time, the degree of coloring of the dyed product immediately after the ink preparation and the dyed product with the ink left at room temperature for 1 month was evaluated in three grades of ◯ Δx. Table 1 shows the results.

[0049]

[Table 1] * 1) According to JIS L 0842.

* 2) According to JIS L 0884 (effective chlorine concentration 20 ppm).

* 3) In accordance with JIS L 0844, the relative evaluation of the inks (A) to (D) was evaluated according to the three grades of ◯, Δ and × from discoloration and fading, contamination and discoloration.

As is clear from Table 1, the reactive dye having a monohalogenated triazine group has a high dyeing property and exhibits a good fastness as compared with the acid dye having a similar structure and other reactive dyes. . In addition, the changes over time also include inks B and C that use dichlorotriazine and vinyl sulfone type reactive dyes.
Was better than

[Example 2 and Comparative Example 2] As ink,
Four color inks were prepared using reactive dyes of the following composition. Yellow ink Reactive dye (CIReactive Yellow 2): 10% Ethylene glycol: 20% Buffer solution: 50% Water: 20% Blue ink Reactive dye (CIReactive Blue 49): 10% Ethylene glycol: 20% Buffer solution: 50% Water: 20% red ink reactive dye (CIReactive Red 45): 10% ethylene glycol: 20% buffer solution: 50% water: 20% black ink reactive dye (CIReactive Black 8): 10% ethylene glycol: 20% buffer solution: 50% Water: 20% A nylon 6 knit containing a polyurethane (registered trademark "Operon" manufactured by Toray DuPont Co., Ltd.) for wearing as a cloth was pretreated with the following formulation.

Pretreatment A (Example 3) Modified carboxymethylcellulose (“Sunrose MAC10SH” manufactured by Nippon Paper Industries Co., Ltd.): 1% Water: 99% Pretreatment B (Comparative Example: Cationic water-soluble polymer) Polyallylamine: 1% Water: 99% Pretreatment C (Comparative example: Water-soluble cationic polymer containing many hydroxyl groups) Polyvinyl alcohol: 1% Water: 99% Pretreatment D (Comparative example: Hydrophobic polymer) Fluorine-based water repellent Oil (Asahi Glass Co., Ltd. “Asahi Guard AG71
0 ″): 0.5% water: 99.5% Using the same color inkjet device as in Example 1, three print patterns were printed, and color development and soaping were performed.

Table 2 shows the quality of the obtained image.
The following shows the results evaluated in three grades.

[0056]

[Table 2] As shown in Table 2, the pretreatment A of the present invention had a high quality image. Pretreatments B and C did not provide sufficient color density, and pretreatment D treated with a water repellent resulted in a noticeable white eye direction between adjacent dots.

Example 3 Inks having the following two types of compositions were prepared.

Ink E (with acid generator) Reactive dye (CIReactive Yellow 2): 10% Ethylene glycol: 20% Ammonium sulfate: 1% Buffer solution: 50% Water: 19% Ink F (Alkaline ink) Reactive dye (CIReactive Yellow) 2): 10% Ethylene glycol: 20% Sodium carbonate: 1% Water: 69% The same sample and procedure as in Example 1 were used to print on a pretreated fabric using a color inkjet device, and then color development and soaping were performed. The stability of the ink was evaluated based on each ink immediately after the adjustment (within 1 hour) as a reference, and the color development of the dyed product by the ink and the dye fixation rate after standing at room temperature for 1 week were evaluated in three grades of ◯ Δ ×. Table 3 shows the results.

[0059]

[Table 3] As shown in Table 3, the acidic ink had more excellent ink stability.

[0060]

EFFECTS OF THE INVENTION According to the present invention, for a cloth mainly composed of a polyamide structure, a dyed product having a clear and sharp pattern, a sufficient color density, and good fastness Can be obtained. Further, the inkjet ink according to the present invention has excellent short-term or long-term stability, and does not affect the dyeing characteristics even when stored at room temperature. Furthermore, with the ink of the present invention, it is possible to perform inkjet dyeing with high reliability of ejection performance without causing clogging or the like in the head nozzle.

Claims (15)

[Claims] 1. An inkjet dyeing method for a polyamide fiber structure, wherein a reactive dye having at least one monohalogenated triazine group is used as a coloring component, and as a pretreatment, a water-soluble polymer not reactive with the reactive dye is used. Is applied to a polyamide fiber structure. 2. The reactive dye is C.I. I. Reactive Y
ellow-2, 3, 18, 81, 84, 85, 95,
102, 105, 135, 136, 137, 138, 1
43, 145, 151, 161, 167, 168, 17
5. The inkjet dyeing method according to claim 1, wherein the method is at least one selected from the group consisting of 5. 3. The reactive dye is C.I. I. Reactive R
ed-3, 3: 1, 13, 24, 29, 31, 33, 4
3, 45, 55, 58, 120, 141, 183, 18
4, 193, 194, 195, 204, 217, 21
8, 220, 222, 223, 226, 228, 23
At least 1 selected from the group consisting of 0 and 235
The inkjet dyeing method according to claim 1, wherein the number is at least one. 4. The reactive dye is C.I. I. Reactive V
It is at least 1 sort (s) or more selected from the group which consists of iolet-1,2,38, It is characterized by the above-mentioned.
The inkjet dyeing method described. 5. The reactive dye is C.I. I. Reactive B
lue-2, 5, 13, 14, 15, 18, 25, 3
8, 39, 41, 49, 52, 71, 72, 112, 1
31, 160, 162, 171, 171: 1, 176,
182, 184, 190, 191, 192, 194, 1
98, 204, 211, 212, 214, 221, 22
The inkjet dyeing method according to claim 1, wherein the method is at least one selected from the group consisting of 2,230,231,235,236,243. 6. The reactive dye is C.I. I. Reactive B
The inkjet dyeing method according to claim 1, wherein the ink is at least one selected from the group consisting of rack-1, 8, 13, and 39. 7. A reactive dye containing C.I. I.
One or more selected from the group consisting of Reactive Yellow-2, 85 and 95, C.I. as a magenta or red component. I. Reactive Red-3:
One or more selected from the group consisting of 1, 24, 33, 218, 226, 228 and 235, and C.I. I. Reactive Blue-5,
The inkjet dyeing method according to claim 1, wherein at least one selected from the group consisting of 13, 15, 49, 72, 176, and 198 is used in combination. 8. The pH of the ink containing the reactive dye is 3 to 7.
The inkjet dyeing method according to any one of claims 2 to 7, wherein: 9. The pH of the ink is adjusted by using a buffer solution and / or an acid generator.
The inkjet dyeing method according to any one of 1 to 8. 10. A polyamide fiber structure comprising a fiber structure provided with 0.1 to 20% of a water-soluble polymer which does not react with the reactive dye, and is used. The inkjet dyeing method described. 11. The treatment liquid used for pretreating the polyamide fiber structure has a pH of 3 to 7, and the treatment liquid does not contain an alkali or an alkali generator. The inkjet dyeing method according to any one of claims. 12. The polyamide is nylon 6 or nylon 6.
6. The inkjet dyeing method according to claim 1, wherein the inkjet dyeing method is 6 or a copolyamide mainly composed of these. 13. The fiber structure is a woven fabric, a knitted fabric or a non-woven fabric mainly containing polyamide.
1. The inkjet dyeing method according to any one of 1. 14. The inkjet dyeing method according to claim 1, wherein the fibrous structure is a polyamide knit fabric containing elastic yarn. 15. An inkjet dyed product dyed by the inkjet dyeing method according to any one of claims 1 to 14.