JPH093786A - Dyeing of fabric consisting of cellulose-based fiber - Google Patents

Abstract

PURPOSE: To obtain a pattern having light and shade difference by impregnating a cellulose-based fiber fabric with a UV ray-polymerizable compound, partly irradiating UV rays and then dyeing in a bath. CONSTITUTION: This dyeing of cellulose-based fiber fabric is to immerse a cotton textile in 50-100g/l aqueous solution of a quaternary ammonium salt such as quaternary compound of dimethylaminoethyl methacrylate expressed by formula I or quaternary salt of potassium acrylate-3-sulfopropyl ester, etc., expressed by formula II and/or a UV ray-polymerizable compound having sulfonic groups, impregnate the cotton textile with 10-100wt.%, preferably 30-60wt.% of this aqueous solution, dry the textile, place a pattern material such as a paper board having a predetermined hole on the textile, irradiate UV rays of <=250nm wave length to polymerize the compound and fix the compound in the irradiated area, wash the textile with hot water to remove unreacted materials, dye the textile in a bath and obtain the textile having the pattern with light and shade difference between the nonirradiated and irradiated parts in the textile.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for dyeing a cloth made of cellulosic fibers, and more particularly to a method for forming a pattern pattern having different shades during dyeing.

[0002]

2. Description of the Related Art Various contrivances have been made in dyeing in order to enhance fashionability, and print printing is generally used as a method for drawing patterns and patterns. However, in the case of the same color shade pattern, it is extremely complicated to perform the print printing, and a simpler method is required.

Recently, the worn-out feeling and the retro feeling have come to meet the sensational needs of consumers, and the dyed fabric is further partially decolorized with a chemical agent, and stone-washed or sand-washed. A method of forming a shade pattern by partially decolorizing by a so-called physical stimulus has come to be adopted.

However, with such a conventional method, it is extremely difficult to form a shade pattern with an intended design at an intended position, and the only complicated printing method is the only method that can achieve this purpose. It was

[0005]

As described above, according to the prior art, it has been impossible to efficiently obtain a dyed product having the same color and a dark and light pattern that meets the sensational needs of consumers.

In view of the above circumstances, the present invention provides a method capable of efficiently dyeing a cloth made of cellulose fibers according to a desired design by a designer or the like with a shade pattern. It is intended to be provided.

[0007]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to achieve the above object. As a result, a cloth made of cellulose fibers is coated with a specific compound and partially exposed to ultraviolet rays. Upon irradiation, the compound adheres to the fiber only in this irradiated part, and then, when it is dyed, a difference in dyeability (dye dyeing ratio) occurs between the irradiated part and the non-irradiated part, resulting in a pattern with different shades. They have found that they can be formed and have completed the present invention.

That is, according to the present invention, an ultraviolet polymerizable compound containing a quaternary ammonium salt group and / or a sulfonic acid group is partially fixed to a cloth made of cellulose fiber by irradiation with ultraviolet rays, A method for dyeing a fabric made of cellulose fibers, which is characterized in that a modification treatment is applied so that the dyeing property differs between an ultraviolet-irradiated part and a non-irradiated part, and a pattern pattern with a different shade is formed by the subsequent dip dyeing. It is related to.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The fabric of the present invention is obtained by spinning or blending various cellulosic fibers such as natural cellulosic fibers and artificial cellulosic fibers (regenerated cellulosic fibers, semi-synthetic fibers). Textiles, knits, non-woven fabrics and the like, which have been spun and woven, are all used.

In the present invention, an ultraviolet-ray-polymerizable compound containing a quaternary ammonium salt group and / or a sulfonic acid group is first partially fixed to the above-mentioned cloth by irradiation of ultraviolet rays, and then irradiated with ultraviolet rays. A modification treatment is performed so that the dyeability differs between the unirradiated part and the unirradiated part. Although various methods of this modification treatment are possible, the most general method is to apply the above-mentioned UV-polymerizable compound to the entire surface of the above-mentioned cloth by means such as a dipping method and then to partially expose the applied surface to UV rays. It is a method of irradiation.

The UV-polymerizable compound used herein is a carbon-containing UV-polymerizable polymer containing a quaternary ammonium salt group and / or a sulfonic acid group as an ionic group.
Those having a carbon unsaturated double bond, for example, a methacrylic acid ester derivative or amide derivative having a quaternary ammonium salt group, a (meth) acrylic acid ester derivative having a sulfonate group, a quaternary ammonium salt group and a sulfonate group. There are methacrylic acid ester derivatives and amide derivatives having a.

As the methacrylic acid ester derivative or amide derivative having a quaternary ammonium salt group, dimethylaminoethyl methacrylate represented by the following formula (1) is used.
Quaternized product [trade name "QD manufactured by Nitto Kagaku Kogyo Co., Ltd.
M "], and methacrylamidopropyltrimethylammonium chloride represented by the following formula (2) [trade name" MAPTAC "manufactured by Nitto Chemical Industry Co., Ltd.] and the like.

As the (meth) acrylic acid ester derivative having a sulfonic acid group, an acrylic acid-3-sulfopropyl ester potassium salt represented by the following formula (3) [a product manufactured by Rasshihi (Nagase & Co., Ltd.)] First name "SP
A "], methacrylic acid-3- represented by the following formula (4)
Examples include sulfopropyl ester potassium salt [trade name "SPM" manufactured by Raschitsu (Nagase Sangyo Co., Ltd.)]. _{CH 2 = CH-COO-CH} 2 CH 2 CH 2 -SO 3 K ... (3)

The methacrylic acid ester derivative or amide derivative having a quaternary ammonium salt group and a sulfonic acid group is N- (3-sulfopropyl) -N-methacryloxyethyl-N represented by the following formula (5). , N-dimethylammonium betaine [trade name "SPE" manufactured by Raschitsu Corp. (Nagase & Co., Ltd.)], N- (3-sulfopropyl) -N-methacrylamidopropyl-N represented by the following formula (6): , N-dimethylammonium betaine [trade name "SPP" manufactured by Raschhi (Nagase & Co., Ltd.)]
And the like.

Such an ultraviolet-polymerizable compound is usually dissolved in water at a concentration of 50 to 100 g / liter to form an aqueous solution, and the cloth is dipped in the aqueous solution to 10 to 100% by weight of the aqueous solution with respect to the cloth. , Preferably 30-60
Apply at a weight percentage and then dry. Here, if the coating amount is too small, the effect of modifying the dyeability is low, and if it is too large, the texture of the fabric deteriorates, which is not preferable.

After coating in this way, the coating surface is partially irradiated with ultraviolet rays. For partial irradiation, it is preferable to use a blocker having a function of blocking ultraviolet rays. For example, paper, fiber cloth, plastic, (synthetic) leather, metal, and other materials that have the function of blocking UV rays, engraved according to the desired design, tangible objects such as leaves and shells A method of using as a shield, arranging this on a cloth, and irradiating ultraviolet rays from above is preferably adopted.

For the irradiation of ultraviolet rays, a low pressure mercury lamp may be used to irradiate the light emitted from the mercury lamp for several seconds to several tens of minutes, preferably for 30 seconds to 1 minute. The light emitted from a low-pressure mercury lamp generally has an energy of light having a wavelength shorter than 253.7 nm accounting for 85% or more of the total irradiation energy, that is, a light containing ultraviolet rays having a short wavelength of about 250 nm or less in high density. Is preferred.

When irradiated in this manner, the above-mentioned UV-polymerizable compound applied to the cloth is mixed with the cellulose constituting the cloth.
The radicals generated from the s-fibers are used as the base points for polymerization, and they are firmly and chemically fixed to the fiber cloth. On the other hand, the UV-polymerizable compound in the non-irradiated part does not cause fixation due to such polymerization, and spontaneously separates when immersed in a dyeing solution in a later step, but avoids adverse effects on the dyeing solution. Prior to dyeing, it is desirable to wash it with hot water or the like and remove it positively.

Due to such a modification treatment, in the portion irradiated with ultraviolet rays, the ultraviolet polymerizable compound fixed to the cloth contains a quaternary ammonium salt group or a sulfonic acid group. Therefore, it is used again depending on the kind of the ionic group. Depending on the type of dye,
Dyeing property (dyeing property) increases or, conversely, decreases. For example, in the case of containing a quaternary ammonium base, the dyeability is increased by using an acid dye and the dyeability is decreased by using a basic dye. Further, in the case of containing a sulfonic acid group, the dyeability is increased by using a basic dye or the like, and the dyeability is decreased by using an acid dye or a direct dye. on the other hand,
Since the non-irradiated part has almost no such ionic group, it exhibits normal dyeability, and eventually, the dyeability differs between the ultraviolet-irradiated part and the non-irradiated part.

Such an effect is obtained only when the light emitted from the low-pressure mercury lamp, that is, the ultraviolet rays having a short wavelength of about 250 nm or less is irradiated at a high density, and the high-pressure mercury arc lamp and the carbon arc lamp are used. If other light sources such as a black light, a xenon arc light, and an incandescent light bulb are used, the above-mentioned effects can hardly be obtained.

After the above-mentioned modification treatment, ordinary dip dyeing is carried out, and when dyed, the UV-irradiated portion is dyed in a darker or lighter color than the non-irradiated portion, and it follows the shape of an engraved or tangible object. The pattern has the same shade as the ivy design, and a new sensitized dyeing product can be obtained. For dip dyeing, a conventionally known method can be applied as it is, and the post-treatment after dyeing is not different from the conventional method. As the dye, a direct dye, a sulfur dye, a naphthol dye, a reactive dye, a vat dye, a fluorescent dye, an acidic dye, a basic dye and the like can be widely used.

[0022]

Industrial Applicability As described above, according to the dyeing method of the present invention, it is possible to design the pattern dyeing of the cloth made of the cellulose fiber with the difference in the shade between the UV-irradiated part and the non-irradiated part. Can be done as efficiently as possible. In particular, in the present invention, the density difference can be arbitrarily adjusted by controlling the coating amount of the UV-polymerizable compound, the irradiation time of the UV light, etc., so that the pattern can be made to stand out like a print or a slight difference in density can be obtained. It is also possible to make a tone-like tone with, and it is also possible to form a pattern with a blurred outline by installing the light shield away from the fabric.
An industrially highly valuable dyeing method can be provided.

[0023]

EXAMPLES Next, the present invention will be described more specifically by way of examples.

Example 1 A plain woven fabric made of cotton was used as a fabric, which was scoured by a conventional method and dissolved in water at a concentration of 60 g / liter to give an ultraviolet polymerizable compound represented by the above formula (1) [Nitto Kagaku Kogyo]. After dipping in an aqueous solution of trade name "QDM" manufactured by Co., Ltd. for 10 minutes, it was squeezed with a mangle to a pick-up amount of 80% by weight and dried at room temperature.

On this cloth, a ball paper with a thickness of 1 mm, in which many circles are cut out, is placed, and from the distance of 5 cm above the ball paper,
Low-pressure mercury lamp [trade name "UVB manufactured by Sen Special Light Source Co., Ltd.
-40 ", power 40 W, main wavelength 184.5 nm, 25
(3.7 nm) for 30 seconds.
After this irradiation, the unreacted UV polymerizable compound (QDM) was washed and removed by treating with hot water.

Then, a reactive dye (Procion Re
d MX-5B), with a dyeing concentration of 5% by weight to fiber,
After dyeing for 1 hour at a bath ratio of 1:50 and a temperature of 30 ° C., a fixing treatment was performed with 20 g / liter soda ash.
Then, the product was washed by boiling with Marcel soap and then dried to obtain a dyed cloth. In this dyed cloth, the part of the hollowed out circle, that is, the part irradiated with ultraviolet rays was dyed in a remarkably dark color, and a beautiful polka dot pattern was obtained.

Comparative Example 1 As a fabric, a plain fabric made of scoured cotton which was not coated with a UV-polymerizable compound (QDM) was placed on a vowel similar to that of Example 1.
Ru paper was placed, ultraviolet rays were irradiated using a low-pressure mercury lamp, and the same dyeing as in Example 1 was performed. As a result, the color density was extremely low as a whole, and only a polka dot pattern with a very slight contrast was obtained. This polka dot pattern had an insufficient contrast, and contrary to Example 1, the ultraviolet irradiation part was dyed in a lighter color.

Example 2 Under the same conditions as in Example 1, the UV polymerizable compound (QD
M) and ultraviolet irradiation treatment (a plain woven fabric made of scoured cotton) is treated with an acid dye (Orange).
II), dyeing density 5% by weight to fiber, bath ratio 1: 5
After dyeing for 1 hour under the conditions of 0 and temperature of 30 ° C., it was washed with water and dried to obtain a dyed cloth. In the same manner as in Example 1, this dyed cloth was dyed in a marked dark color in the hollowed-out circle portion, that is, in the portion irradiated with ultraviolet rays, and a beautiful polka dot pattern with high contrast was obtained.

Example 3 A plain weave fabric made of cotton was used as a fabric, which was scoured by a conventional method and dissolved in water at a concentration of 20 g / liter to give an ultraviolet polymerizable compound represented by the above formula (4) [Nitto Kagaku Kogyo]. After soaking for 15 minutes in an aqueous solution of "SPM" manufactured by Co., Ltd., the amount of pick up is 80% by weight with a mangle.
It was squeezed and dried at room temperature.

On this cloth, a ball paper having a thickness of 1 mm in which a large number of circles are cut out is placed, and from the distance 5 cm above the ball paper,
Low-pressure mercury lamp (trade name "UVB manufactured by Sen Special Light Source Co., Ltd.
-40 ", power 40 W, main wavelength 184.5 nm, 25
(3.7 nm) and irradiated with ultraviolet rays for 1 minute. After this irradiation, the unreacted UV polymerizable compound (SPM) was washed and removed by treating with hot water.

Then, the basic dye (Methylen
Blue) was used for dyeing at a dyeing concentration of 5% by weight with respect to the fiber, a bath ratio of 1: 100, and a temperature of 30 ° C. for 1 hour. Then, it was washed with water for 30 minutes and dried to obtain a dyed cloth.
In this dyed cloth, the part of the hollowed out circle, that is, the part irradiated with ultraviolet rays was dyed in a remarkably dark color, and a beautiful polka dot pattern was obtained.

Example 4 In the same manner as in Example 1 except that the aqueous solution of the ultraviolet-polymerizable compound (QDM) was replaced with the aqueous solution of the ultraviolet-polymerizable compound (SPM) of Example 3, immersion treatment and exposure to ultraviolet light were carried out. After the irradiation treatment and the washing treatment with hot water, the same reactive dye as in Example 1 was used for dyeing. Contrary to Example 1, the obtained dyed cloth was dyed in a hollow circle portion, that is, a portion irradiated with ultraviolet light was light-colored and a non-irradiated portion was red and dark-colored. A beautiful polka dot pattern with a contrast of was obtained.

Claims (1)

[Claims] 1. A fabric made of cellulosic fibers, comprising a fourth
A UV-polymerizable compound containing a quaternary ammonium salt group and / or a sulfonic acid group is partially fixed by irradiation with UV rays, and modified so that the dyeability is different between the UV-irradiated part and the non-irradiated part, A method for dyeing a cloth made of cellulosic fibers, which comprises forming a pattern pattern having different shades by subsequent dyeing.