JPH0643669B2 - Method for printing cellulosic fibers - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for printing cellulosic fibers. More specifically, the present invention relates to a printing method that, when printing cellulosic fibers, drastically reduces exhaust and wastewater pollution and yet produces high-quality printed products.

BACKGROUND ART Generally, in the printing of cellulosic fibers, a so-called half-emulsion paste is used as the base paste for printing, which is obtained by mixing a water-swollen mixture of one or more of sodium alginate, carboxymethyl cellulose (CMC) and carboxymethyl starch (modified starch) with a so-called emulsion paste made by emulsifying kerosene, mineral oil such as mineral turpentine and water with a nonionic or anionic surfactant.
To 600 parts of water, add dye, 50-200 parts of urea, 20-30 parts of an alkali such as sodium carbonate or baking soda, a reduction inhibitor, and water. Reactive and direct dyes are generally used as dyes. The viscosity of this color paste is generally in the range of 2,000-50,000 cp, as measured at 12 rpm using a rotational viscometer manufactured by Tokyo Keiki Co., Ltd. Such color paste is printed on fabric by hand printing or using a roller printing machine, flat screen printing machine, rotary printing machine, etc., and then, with or without drying, is subjected to a dye fixing treatment such as dry heat treatment or steaming to remove unfixed dyes and
The starch and other unwanted substances adhering to the fabric are removed in the washing (soaping) process, and then finishing processes such as drying and texture adjustment are carried out.

The reasons for using mineral turpene emulsion in the base glue include improving the screen transmittance of the color glue during printing by changing the fluidity from near-Newtonian when sodium alginate is used alone to closer to plastic flow, improving dye color development, improving color clarity, and improving the ease of removal of glue during soaping by suppressing the reaction between the glue and dye when using reactive dyes (this has a significant impact on the texture and various fastnesses of the finished product).

However, in the above-mentioned method using a mineral oil emulsion such as mineral turpentine, the mineral oil used in the emulsion has a strong odor and is flammable, which causes problems in terms of safety and hygiene during work. In addition, there are problems such as air pollution due to exhaust gases during the drying stage after printing, contamination of wastewater with the mineral oil when cleaning screens and tools or from residual color paste, and the inflow of odors into houses around the factory, especially from heated wastewater.
Environmental pollution, such as river pollution, has become a social problem.

The present inventors have conducted extensive research to solve the problems caused by the mineral oil emulsions used by printing factories, and have completed an emulsion paste for printing polyester fibers in Japanese Patent Publication No. 58-7757. However, when the method of the above patent is used for printing cellulosic fibers, which use the largest amount of mineral oil emulsion, although it solves the pollution problem, there are problems with print quality such as color development, and it cannot be applied as is. This is thought to be due to the fact that the properties of the fibers are very different, with polyester fibers being hydrophobic and cellulosic fibers being hydrophilic.

Disclosure of the Invention The present inventors have made extensive research to overcome the problems associated with printing on cellulosic fibers, and have completed the present invention. The present invention provides a method for printing on cellulosic fibers that has better color development and color retention than when using half-emulsion pastes made from mineral oils such as mineral turpentine.
The object of the present invention is to provide printed textiles having sharpness and desizing properties, and to solve the problems of hygienic safety during work and pollution caused by exhaust and wastewater.

According to the present invention, there is provided a method for printing cellulosic fiber materials with reactive or substantive dyes, which method comprises printing the fiber material with a printing paste containing an emulsion prepared by emulsifying a mixture of a hydrophobic substance which is liquid at room temperature and represented by the following general formula I and a hydrophobic substance which is solid at room temperature and represented by the following general formula II in a mixing ratio by weight of 5:95 to 95:5 with an emulsifier and water, and then drying or fixing the resultant mixture with or without drying:

In the above formula, _R1 and _R2 each independently represent a hydrogen atom or an acyl group from a saturated or unsaturated monoaliphatic carboxylic acid having 2 to 22 carbon atoms, and _R3 and _R4 each independently represent
Each independently represents a methyl group, an ethyl group, or a phenyl group, and l and m are 0 or a positive integer, and l+
m is an integer of 1 to 300. However, when _R1 and _R2 are both hydrogen atoms, l+m is an integer of 6 to 300.

A(OR ₅ ) _n II In the above formula, A represents a residue of a tri- to hexahydric alcohol, R ₅ represents an acyl group from a saturated or unsaturated fatty acid having 12 to 22 carbon atoms, and n is an integer of 1 to 3.

BEST MODE FOR CARRYING OUT THE INVENTION To explain the present invention in more detail, the emulsion used in the method of the present invention is effective when a hydrophobic substance of general formula I that is liquid at room temperature and a hydrophobic substance of general formula II that is solid at room temperature are mixed and emulsified and used as a base paste in a color paste.

Emulsifying either one of the compounds of general formula I and II does not produce any effect. The reason for this is thought to be as follows: In other words, when a color paste using only a sizing agent such as sodium alginate in the base paste is printed and dried, the sizing agent is thought to form a continuous solid film-like coating on the fiber, and therefore, in order for the dye to adhere to the fiber, it must pass through this dry coating and reach the fiber surface during the fixing process. This is particularly problematic in the dry heat fixing method, and in practice, although a large amount of an auxiliary agent with high dye dissolving power and hygroscopicity such as urea is used in combination, only insufficient dyeing is achieved. In the steaming fixing method,
It is easy to think that steam will cause the adhesive film to swell, but in reality, the steaming time is only about 7 to 8 minutes, which is too short for the adhesive film to swell and the dye to adhere. When using a half-emulsion base adhesive made from a mineral oil emulsion such as mineral turpentine,
The mineral oil evaporates during drying, leaving behind pores (microvoid structure) in the adhesive coating, which are said to promote the movement of dyes and the swelling of the adhesive during fixation.

As mentioned above, when only one of the general formula I or general formula II of the present invention is emulsified, the coloring property is hardly improved compared to the case of the base paste containing sodium alginate alone.
The reason why color development can be significantly improved only by mixing and emulsifying the compound of general formula II with the compound of general formula II is thought to be that the solid hydrophobic substance plays a role in inhibiting the continuous coating formation of the paste, while the liquid hydrophobic substance contributes to increasing the swelling speed of the paste and the migration speed of the dye during fixing processes such as steaming. In other words, mixing and emulsifying both solid and liquid substances leads to the formation of a discontinuous coating consisting of a different paste/liquid substance/solid substance, instead of the microvoid structure formed in the dried coating when using mineral turpene emulsion, and is thought to make dye fixation easier.

The compounds represented by general formula I, which are the first component of the sizing agent used in the present invention, include, for example, polyoxypropylene glycol, polyoxybutylene glycol, polyoxystyrene glycol, propylene oxide/butylene oxide copolymer, propylene oxide/styrene oxide copolymer, and mono- or diesters of these saturated or unsaturated aliphatic carboxylic acids having 2 to 22 carbon atoms, and these compounds can be used alone or in combination of two or more.

In the compound of general formula II, which is the second component of the sizing agent used in the present invention, the tri- to hexahydric alcohol which is the component constituting A includes glycerin, trimethylolpropane, trioxyisobutane, 1,2,3-pentatriol,
Examples of suitable alcohols include trihydric alcohols such as 2,3,4-pentatriol and trihydroxyethyl isocyanurate, tetrahydric alcohols such as diglycerin and pentaerythritol, pentahydric alcohols such as adonite, D-arabitol and xylide, and hexahydric alcohols such as D-sorbitol, D-mannitol and dipentaerythritol. Among these, glycerin, diglycerin, pentaerythritol, D-sorbitol and dipentaerythritol are particularly preferred. Examples of _R5 containing an acyl group from a saturated or unsaturated fatty acid having 12 to 22 carbon atoms include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and linolenic acid. One or more of these are used as the second component. The total content of the first and second components in the emulsion is 10 to 70% by weight, preferably 20 to 40% by weight.
It may be present in an amount of

The emulsifier may be a general surfactant that is usually used when emulsifying hydrophobic substances, for example, anionic surfactants such as sulfate esters of higher alcohols, sulfate esters of ethylene oxide adducts of higher alcohols, highly sulfated oils, ethylene oxide adducts or ethylene oxide/propylene oxide adducts of higher alcohols, ethylene oxide adducts or ethylene oxide/propylene oxide adducts of alkylphenols,
The surfactant can be appropriately selected from nonionic surfactants such as propylene oxide adducts, fatty acid esters or diisocyanate reactants thereof, and fatty acid esters of polyethylene glycol.

When using the above emulsion, it is convenient to mix it in advance with a water-swellable paste such as sodium alginate, CMC, or modified starch, and use this as the base paste for color paste.
It may be added directly when preparing the color paste. These emulsions are preferably used in the range of 10 to 50% by weight in the color paste.

The dyes used are reactive and direct dyes commonly used in printing cellulosic fibers. When the emulsion is used to print blended textiles, disperse dyes, cationic dyes, acid dyes, etc. may be used in combination. The color paste may also contain other commonly used agents such as moisture absorbents, dye solubilizers, pH adjusters, antifoaming agents, and reduction inhibitors.

The color paste containing the emulsion useful in the present invention is printed onto a woven or knitted fabric of cellulosic fibers by hand printing or using a roller printing machine, rotary printing machine, flat screen printing machine or the like, and then the resulting fabric is subjected to a fixing treatment such as a steaming method, a dry heat fixing method or an alkali shock method either as is or after drying. Thereafter, unfixed dye, sizing agent and other impurities adhering to the fabric are removed in a washing (sobbing) step, and the resulting fabric is then subjected to finishing treatments such as drying and texture adjustment.

In the method for printing cellulosic fibers of the present invention, dye color development, sharpness of pattern edges, and removability can be obtained that are equal to or better than those obtained when a color paste containing an emulsion of 30-70% by weight of mineral oil such as mineral turpentine, 70-30% by weight of water, and 1-5% by weight of an emulsifier is used. Moreover, since the method does not contain mineral oil, problems of hygiene and safety in the workplace and exhaust and wastewater pollution are completely eliminated.

The present invention will be further explained below with reference to examples, in which "%" and "parts" represent % by weight and parts by weight, respectively.

Examples 1 to 17 Compounds of general formula I shown in Table 1, compounds of general formula II shown in Table 2
The compound and emulsifier are weighed and placed in a stainless steel container, heated to 70-80°C and melted, and then boiling water is gradually added to the mixture while stirring with a homomixer.
The temperature is lowered to °C to complete the preparation of the emulsion.

Volatility was evaluated by weighing 10 g of the compound into a petri dish, treating it in a dryer (Perfect Oven manufactured by Tabai) at 170° C. for 1 minute, and measuring the residual rate.

The emulsion composition is shown in Table 3.

The emulsions with the compositions in Table 3 all had a viscosity of 2000 to 40,000 cp.
The resulting mixture was in the form of a white paste having a viscosity of 1000 kJ/s (measured at 12 rpm using a BM type viscometer manufactured by Tokyo Keiki).

Separately, for comparison, a mineral turpene emulsion having the following composition was prepared using a homomixer.

A polka dot pattern was printed on a scoured and bleached cotton broadcloth using a color paste containing the emulsion shown in Table 3 prepared above, using a test automatic screen printing machine (manufactured by Tsujii Senki Kogyo Co., Ltd.), and after drying at 100°C for 2 minutes, it was fixed in a high temperature (HT) steamer (manufactured by Tsujii Senki Kogyo Co., Ltd.) at 103°C for 7 minutes. The color paste composition is as follows:

After fixing, the printed item is washed with water and soaped with Lipotol.
The fabric was soaped with 2 g of RK-5 (manufactured by Nicca Chemical Co., Ltd.) in a bath ratio of 1:30 at 90°C for 10 minutes, then washed with water and dried.

Furthermore, for comparison, a color paste was prepared using the mineral turpene emulsion described above as the emulsion in the above composition, and another color paste was prepared using the above composition but without using any emulsion, but with the sodium alginate base paste increased to 400 parts, and these were treated in the same way to obtain printed products.

Table 4 shows the dyeing density of the printed part of each printed fabric, when the surface optical density of the printed item obtained using color paste without mineral turpene emulsion is set to 100.
The sharpness of the pattern edge as judged visually and the softness (feel) of the printed area as judged by the feel were also recorded.

The color paste using the emulsion of the present invention has less odor than the color paste using the turpene emulsion of Example 16 (Comparative Example), and has the same or better color development (dyeing concentration) as Examples 14, 15, 16 and 17, and also has good sharpness and feel. Overall, the textile printed by the method of the present invention is extremely excellent and has no defects compared to conventional methods.

Examples 18 to 20: A floral pattern was printed on a scoured polynosic rayon fabric using a color paste containing emulsion No. 9 shown in Table 3, using a Tsujii automatic screen printing machine. The print was dried at 100°C for 2 minutes and then fixed in an HT steamer at 103°C for 7 minutes. After fixing, the print was washed with water and washed with soaping agent Lipotol RK-5 (2 g/ml) in a bath ratio of 1:30.
The fabric was soaped at 90°C for 10 minutes, then washed with water and dried.

The color paste composition is as follows:

Furthermore, for comparison, color pastes were prepared in which the emulsion of the present invention was replaced with a turpentine emulsion, and color pastes in which the amount of sodium alginate base paste was increased to 400 parts without adding any emulsion, and these were treated in the same manner.

The results are shown in Table 5.

According to the method of the present invention, printed products excellent in dyeing strength, sharpness and feel were obtained.

Examples 21 to 23 A floral pattern was printed on a scoured and bleached cotton broadcloth fabric using a color paste containing emulsion No. 9 shown in Table 3 on a Tsujii automatic screen printing machine, and after drying for 2 minutes at 100°C, the prints were fixed for 60 minutes at 103°C in an HT steamer. After fixing, the prints were washed with water and soaped for 10 minutes using Sunmol 120 (a soaping agent manufactured by Nicca Chemical Co., Ltd.) in a bath ratio of 1:30 at 60°C, then washed with water and dried.

The color paste composition is as follows:

Furthermore, for comparison, color paste was prepared by replacing the above emulsion with mineral turpene emulsion, and color paste was prepared by increasing the amount of sodium alginate base paste to 400 parts without adding emulsion, and the same treatment was carried out.

The results are shown in Table 6.

According to the method of the present invention, printed products excellent in dyeing depth, sharpness and feel were obtained.

INDUSTRIAL APPLICABILITY The present invention can be used to produce high-quality cellulosic fiber prints, and can significantly reduce environmental pollution.

Claims (11)

[Claims] 1. The method of claim 1, wherein a cellulosic fiber material is printed with a reactive dye or a direct dye by mixing the fiber material with a compound of the following general formula I in a weight ratio of 5:95 to 95:5:
A method for printing a cellulosic fiber material, comprising printing with a printing paste containing an emulsion prepared by emulsifying a mixture of a hydrophobic substance which is liquid at room temperature and a hydrophobic substance which is solid at room temperature and is represented by the following general formula II with an emulsifier and water, and then drying or fixing the printed material with or without drying. In the above formula, _R1 and _R2 each independently represent a hydrogen atom or an acyl group from a saturated or unsaturated monoaliphatic carboxylic acid having 2 to 22 carbon atoms, and _R3 and _R4 each independently represent
Each independently represents a methyl group, an ethyl group, or a phenyl group, and l and m are 0 or a positive integer, and l+
and m is an integer of 1 to 300. However, when _R1 and _R2 are both hydrogen atoms, l+m is an integer of 6 to 300. A( _OR5 ) _nII In the above formula, A represents a residue of a tri- to hexahydric alcohol, _R5 represents an acyl group derived from a saturated or unsaturated fatty acid having 12 to 22 carbon atoms, and n is an integer of 1 to 3. 2. The method according to claim 1, wherein the substance of general formula I is selected from polyoxypropylene glycol, polyoxybutylene glycol, polyoxystyrene glycol, propylene oxide/butylene oxide copolymers, propylene oxide/styrene oxide copolymers, and mono- or diesters of these saturated or unsaturated aliphatic carboxylic acids having 2 to 22 carbon atoms. 3. In the general formula II, A is glycerin, trimethylolpropane, trioxyisobutane, 1,2,3
-pentatriol, 2,3,4-pentatriol,
2. The method of claim 1, wherein the hydroxyl group is selected from the group consisting of residues of trihydroxyethyl isocyanurate, diglycerin, pentaerythritol, adonite, D-arabitol, xylide, D-sorbitol, D-mannite, and dipentaerythritol. 4. The method of claim 1, wherein in general formula II, _R5 is an acyl group from lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and linolenic acid. 5. The method according to claim 1, wherein the component represented by general formula I and the component represented by general formula II are present in the emulsion in an amount of 10 to 70% by weight in total. 6. The method of claim 5, wherein said amount is 20 to 40% by weight. 7. The method according to claim 1, wherein the emulsifier is selected from anionic surfactants such as sulfate esters of higher alcohols, sulfate esters of ethylene oxide adducts of higher alcohols, highly sulfated oils, ethylene oxide adducts or ethylene oxide/propylene oxide adducts of higher alcohols, ethylene oxide adducts or ethylene oxide/propylene oxide adducts of aluminylphenols, and nonionic surfactants such as fatty acid esters or diisocyanate reactants thereof, and fatty acid esters of polyethylene glycol. 8. The method according to claim 1, wherein the emulsion is used in combination with sodium alginate, carboxymethyl cellulose or a water-swellable product of modified starch in a printing paste. 9. The method according to claim 1, wherein the emulsion is present in the printing paste in an amount of 10 to 50% by weight. 10. The method of claim 1, wherein the printing paste is printed onto the textile material by hand printing or by using a roller printing machine, a roller printing machine or a flat screen printing machine.
The method described in section. 11. The method according to claim 1, wherein the fixing treatment is carried out by steaming, dry heat fixing or alkaline shock.