KR100466878B1 - Method of producing Cellulose conjugate fabrics having a different dyeing property - Google Patents

Abstract

According to the present invention, the cellulose acetate fabric is partially coated on both sides with an alkali-resistant coating resin and then saponified with alkali so that the portion protected by the coating resin remains as cellulose acetate fabric, and the remaining portion is converted into cellulose fabric and partially To a cellulose composite fabric having a dichroic dye,

When dyeing the dichroic cellulose composite fabric with a disperse dye, while having excellent physical properties such as hygroscopicity, drape, soft touch, it is possible to produce a cellulose / cellulose acetate composite fabric that can give a desired pattern.

Description

{Method of producing Cellulose conjugate fabrics having a different dyeing property}

The present invention relates to a method for producing a dichroic cellulose composite fabric, wherein the cellulose acetate fabric is partially coated with both alkali-resistant coating resins, and then protected by the resin for coating by saponification with alkali. Silver cellulose acetate fabric remaining, the remaining portion is converted to cellulose fabric to produce a partially cellulose composite fabric,

It relates to the production of a cellulose / cellulose acetate composite fabric having a desired pattern by dyeing the prepared chlorinated cellulose composite fabric with a disperse dye, while having excellent hygroscopicity, drape, soft touch and the like inherent physical properties.

In the conventional method for producing cellulose fiber from cellulose acetate, the whole fiber participates in the saponification reaction and is converted into cellulose fiber by treating in liquid flow, and thus, production of cellulose / cellulose acetate composite fiber was not possible.

In addition, in the case of using a composite fiber of polyester fiber and cellulose acetate, the whole fiber participates in the reaction at the same time, so that part of the pattern is made by printing. In case of dyeing by printing, heterogeneous materials with different dyeability are printed with the same dye, resulting in poor physical properties such as color fastness.

The present inventors have attempted to solve the above problems by applying the conventional coating technology used to impart the functionality of clothing fibers, such as water repellency, heat retention, to the celluloseation of cellulose acetate fibers. That is, if the cellulose acetate fiber is coated with a desired pattern with an alkali-resistant coating resin and then subjected to saponification reaction with alkali, the portion treated by the coating resin remains as cellulose acetate fiber, which can be dyed with a disperse dye or the like. The remaining part is celluloseized and has the same dyeability as rayon, so that it can be dyed by reactivity, direct dyes, etc., thereby obtaining a dichroic cellulose composite fiber, thereby completing the present invention.

Therefore, the present invention has excellent hygroscopicity, drape and soft touch of cellulose acetate and cellulose fabric by partially treating the cellulose acetate fabric with alkali-resistant coating resin and then saponifying with alkali without the problems of the prior art as described above. In the meantime, it is an object to provide a method for producing a cellulose fabric having a partially dyeing property.

According to the present invention to achieve the above object, by partially coating both sides of the cellulose acetate fabric with an alkali-resistant coating resin and saponifying with alkali, the portion protected by the coating resin remains as a cellulose acetate fabric, and the remaining portion It provides a method for producing a dibasic cellulose composite fabric, characterized in that it comprises a step of converting to a cellulose fabric,

The dibasic cellulose composite fabric and 0.5% owf of disperse dye with a bath ratio of 1:15, when the dyeing for 30 minutes at a temperature of 100 ℃ phosphate dye, characterized in that Provided is a method for producing a cellulose composite fabric.

[Equation 1]

7.04≤K / S (C) -K / S (N) ≤9.2

K / S (C): K / S value of the coated cellulose fiber

K / S (N): K / S value of uncoated cellulose fiber

Hereinafter, the present invention will be described in more detail.

As a raw material of the present invention, it is preferable to use a fabric containing cellulose diacetate having a degree of substitution of 2.0 to 2.75. In the present invention, the fabric includes a knitted fabric.

The present invention provides a solution of cellulose acetate by partially treating both sides of a portion to give a desired pattern to a fabric containing cellulose diacetate with an alkali-resistant coating resin and partially saponifying the fabric treated with the coating resin with alkali. And partially converting the fabric into a cellulose fabric.

As said alkali-resistant coating resin, a polyurethane resin, an acrylic ester resin, a polyamide resin, a polyolefin resin, a silicone resin, etc. are preferable, and are not specifically limited.

In addition, the saponification process in the present invention is a part of the cellulose diacetate fabric is partially coated treatment using an alkali-resistant coating resin at a temperature of 70 ^° C ~ 130 ^° C in an aqueous alkali solution of 32 to 40 wt% compared to the cellulose diacetate fabric, It is a process of saponifying the acetyl group of the uncoated cellulose diacetate with a hydroxyl group by processing once for 1 to 120 minutes. As described above, the aqueous alkali solution is 32 to 40wt% of cellulose diacetate fabric, if the weight loss is less than 32wt%, it is not suitable for rayon because the weight loss rate is not more than 34%. Because it can occur.

In addition, the saponification process of the present invention may be repeatedly treated twice for 1 to 120 minutes at a temperature of 70 ^° C ~ 130 ^° C with an aqueous alkali solution of 20 to 40 wt% compared to the cellulose diacetate fabric, the aqueous alkali solution The 20 to 40 wt% is due to the same reasons as in the one-time treatment, that is, the incompatibility as rayon when less than 20 wt% and the injuries of the fabric when it exceeds 40 wt%.

Alkaline treatment of cellulose diacetate as described above results in the saponification of converting the acetyl group to the hydroxy group, and crystallization occurs by rearranging and folding of the molecular chains of the diacetate which existed in an amorphous state. In general, the cellulose fibers of natural form have a crystal structure of cellulose I, and the regenerated cellulose fibers have a structure of cellulose II, whereas the cellulose fibers prepared by saponification of cellulose diacetate have a crystal structure of cellulose II and IV mixed. Crystallinity degree (specific gravity method) 14 ~ 34%, birefringence 0.012 ~ 0.024.

The properties of rayon prepared by the above method showed specific gravity 1.48-1.51 gm / cm ³ , tensile strength 1.2 ~ 2.5gf / de, elongation 20 ~ 50%, and standard moisture content 12-16%. .

In addition, examples of the alkali compound used for saponification of cellulose acetate in the present invention include alkali metal hydroxides such as sodium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, alkali metal carbonates such as sodium carbonate and the like. These alkali compounds may be used alone or in combination with a reaction rate modifier. Phosphorium-based saponification agents and quaternary ammonium saponification rate regulators are well known as reaction rate regulators. Commercially available examples of reaction rate regulators include phosphonium-based neorate NCB (NEORATE NCB); Quaternary ammonium KF NEORATE NA-40 (KF NEORATE NA-40: Korea Precision Products), DWK-1125 (DYK-1125: One-sided, Japan), Casein PES, Ka And serine PEL, casein PEF (Sungjin Chemical, Japan), and SNOGEN PDS (Daeyoung Chemical, Korea).

As described above, in the present invention, the cellulose acetate fabric is partially coated on both sides with an alkali-resistant coating resin and then saponified with alkali so that the portion protected by the coating resin remains as cellulose acetate fabric, and the remaining portion is converted into cellulose fabric. By doing so, it is possible to manufacture a dibasic cellulose composite fabric.

Therefore, the chlorinated cellulose composite fabric prepared as described above can be dyed by reactive or direct dyes like the cellulose fabric, and is protected by an alkali-resistant coating resin to prevent celluloseation. The non-acetate portion can be dyed with various disperse dyes.

In the present invention, the dibasic cellulose composite fabric and the disperse dye of 0.5% owf in a 1:15 bath ratio, dyeing for 30 minutes at a temperature of 100 ℃ not only have a desired pattern, but also cellulose and cellulose acetate It is possible to provide a cellulose / cellulose acetate composite fabric capable of exhibiting excellent physical properties such as hygroscopicity, drape, soft touch, and the like. The disperse dye in the present invention is not particularly limited.

In addition, the present invention is characterized by satisfying the following equation 1 when the dyeability evaluation as described above,

[Equation 1]

7.04≤K / S (C) -K / S (N) ≤9.2

K / S (C): K / S value of coated cellulose fabric

K / S (N): K / S value of uncoated cellulose fabric

The difference between the dyeing degree K / S value of the cellulose fabric coated with alkali-resistant coating resin and the dyeing degree K / S value of the cellulose acetate fabric not coated with alkali-resistant coating resin is 7.04 or more, 9.2 or less It means that it should be preferable, if less than 7.04 because the saponification of the coating site occurs a lot or the saponification of the uncoated site is insufficient because it is not suitable as rayon.

Features and other advantages of the present invention as described above will become more apparent from the following examples. However, the present invention is not limited to the following examples.

In the following Examples, physical properties such as a loss ratio of cellulose acetate are measured by the following method.

* Reduction rate: The weight change of the sample before and after alkali treatment was measured and obtained by the following equation. % Reduction = (weight before treatment-weight after treatment) / (weight before treatment) X 100

Deacetylation: Deacetylation was confirmed by infrared spectroscopy using an infrared spectrometer (MAGNA 750, Nicolet, USA). At this time, deacetylation was confirmed by the presence or absence of the carbonyl band of the acetyl group which appears at 1760 cm ^-1 .

* Dyeing (Severity, K / S): Disperse dyes CI Disperse Blue 56 (CI Disperse Blue 56, Reform Blue FBL, Japan Chemicals, Japan) 0.5% owf concentration at 100 ^o C for 30 minutes after dyeing Soaping and rinsing were performed at 70 ^° C. to complete dyeing. The staining degree indicating how deeply colored the color is evaluated using K / S. This value is determined from the K / S equation by measuring the spectral reflectance (R) of the sample after staining. The larger this value, the greater the deep color effect, which indicates that the color is well developed.

Therefore, the dyeing obtained in the present invention was measured using a spectrophotometer (Color-Eye 7000A, Machbeth, USA) to measure the reflectance (R) and then substituted it into the equation K / S = (1-R) ² / 2R. K / S value was obtained and the dyeability was evaluated using this value.

Example 1

Plain fabric consisting of cellulose diacetate fibers with an acetyl substitution degree of 2.55 (56.9% superoxide) (slope 75d / 20f, weft 120d / 33f, stomach density 75 / inch, SKYRON, SK Chemicals, Korea) After scouring and drying, 140 parts of acrylic coating resin BONCOAT AC-503 (VONCOAT AC-503, manufactured by Nippon Ink Chemical Co., Ltd., Japan), 3 parts of VONCOAT V and 3.5 parts of 25% aqueous ammonia solution are added. Viscosity 3,000 cps coating solution was prepared and then coated on the desired portion using a floating knife coater (Mathis, Switzerland), then turned over, and the same portion was once again partially coated. Partially-coated fabric was added to the liquid dyeing machine, and water was added to the liquid dyeing machine. Then, 40 wt% of caustic soda, distillate, quaternary ammonium salt, and phosphonium salt (1 g / L) were added at 30 ^o C. After heating to 2 ^o C / min up to 100 ^o C in 30 minutes and then cooled to 2 ^o C / min up to 30 ^o C, drained, washed with water.

In addition, in order to determine the reduction rate of the coated part and the untreated part, the coated sample and the untreated sample were taken out together, put together in a reducer solution bath (Bath), and treated in the same manner as above to remove the coating resin, and then measured the respective reduction rate.

As a result of the reduction rate measurement, the cellulose acetate fibers coated with the acrylic coating resin had a weight loss of 5.4%, and the untreated portion had a weight loss rate of 40.2%.

In the case of the carbonyl band, while the raw parts is larger appears in the acetyl group from the result of each analysis, infrared spectroscopic spectrum of the coated fiber portion and an untreated portion diacetate fibers of the coated portion of the acetyl group at 1760cm ^-1 1760cm ^-1 The carbonyl band disappeared completely, indicating that all acetyl groups were substituted with hydroxy groups.

Also dispersing the saponified fabric in the above embodiment the dye siahyi discharge pulse Blue 56 (CI Disperse Blue 56, Reform Blue FBL, Japan Chemical) 0.5% owf concentration to 100 ^o C in one after the conventional method dyed for 30 minutes at 70 ^o Soaping and rinsing were performed in C to complete dyeing.

To find out how deep it was dyed, measure the reflectance (R: Reflectance) using a spectrophotometer (Color-Eye 7000A, Machbeth, USA) of the dyeing product after dyeing, and then use the equation K / S = (1-R ) ² / 2R was substituted to obtain the K / S value is shown in Table 1.

As a result of the above dyeing, the coated part was dyed by the disperse dye, and the untreated part was celluloseated, so that the dye was not dyed at all by the disperse dye.

Example 2

Plain fabric consisting of cellulose diacetate fibers with an acetyl substitution degree of 2.55 (56.9% superoxide) (slope 75d / 20f, weft 120d / 33f, stomach density 75 / inch, SKYRON, SK Chemicals, Korea) After refining, 140 parts of polyurethane (PU) coated resin Hyrex R-SCC (Bokwang Chemical, Korea) and 2 parts of thickener Hyex VS are added. After the coating solution was prepared, the double-side coating treatment was performed in the same manner as in Example 1, and the alkali treatment was performed in the same manner as in Example 1.

As in the alkali treatment results above, the portion coated with polyurethane (PU) resin gained 10.2% reduction, and the untreated portion obtained 40% reduction.

In the same manner as in Example 1, dyeing was carried out using a disperse dye, and the K / S values are shown in Table 1. As in the result of Example 1, it was confirmed that the part coated with the PU resin was dyed with the disperse dye, and the untreated part was celluloseated and not dyed at all with the disperse dye.

Comparative Example 1

Plain fabric consisting of cellulose diacetate fibers with an acetyl substitution degree of 2.55 (56.9% superoxide) (slope 75d / 20f, weft 120d / 33f, stomach density 75 / inch, SKYRON, SK Chemicals, Korea) After scouring and drying, 15 times the amount of diacetate fiber was added to the liquid dyeing machine, and 40 wt% caustic soda was added to the diacetate fiber.

The prepared diacetate fiber scouring paper was added to a liquid dyeing machine, and then heated to 30 ^° C. at 2 ^° C / min, treated at 100 ^° C. for 30 minutes, and cooled to 2 ^° C / min up to 30 ^° C. and then drained. Water was added at room temperature and washed with water to remove residual alkali and dried the fibers. Through this saponification process, a fiber having a weight loss ratio of 40.2% relative to the initial diacetate fiber weight was obtained.

Infrared spectral analysis as in Example 1 confirmed that the acetyl group was completely substituted with a hydroxyl group.

In addition, it was stained using a disperse dye as in Example 1 and the results are shown in Table 1.

Table 1 shows the results of the loss ratio and dyeability of the fibers prepared by the examples and the comparative examples.

division Reduction rate (%) Dyeability (K / S) Double side coating Unprocessed part Double side coating Unprocessed part Example 1 5.4 40.2 9.44 0.24 Example 2 10.2 40.0 7.24 0.20 Comparative Example 1 - 40.2 - 0.22

As will be apparent from the above examples and comparative examples, the cellulose acetate / cellulose composite fabric prepared by the present invention has dye transferability, so that only a certain part can be dyed to have a desired pattern, and inherently cellulose acetate and cellulose It is possible to provide a product that exhibits excellent hygroscopicity, drape, and soft touch.

Claims (6)

And partially coating both sides of the cellulose acetate fabric with an alkali-resistant coating resin, and then saponifying with alkali so that the portion protected by the coating resin remains as the cellulose acetate fabric, and the remaining portion is converted into the cellulose fabric. A method for producing a dibasic cellulose composite fabric characterized by the above-mentioned. The dye-containing cellulose composite fabric according to claim 1, wherein the dye-containing cellulose composite fabric is dyed at a temperature of 100 ° C. for 30 minutes using a 0.5% owf dispersion dye at a temperature of 100 ° C. A method for producing a dibasic cellulose composite fabric, characterized by satisfying the formula (1). [Equation 1] 7.04≤K / S (C) -K / S (N) ≤9.2 K / S (C): K / S value of the coated cellulose fiber K / S (N): K / S value of uncoated cellulose fiber The method for producing a dibasic cellulose composite fabric according to claim 1, wherein a polyurethane resin, an acrylic ester resin, a polyamide resin, a polyolefin resin, or a silicone resin is used as the coating resin. . The method according to claim 1, wherein the alkali treatment temperature during alkali saponification is 70 to 130 ^° C., the alkali treatment time is 1 to 120 minutes, and the alkali concentration is 20 to 40 wt% based on the cellulose acetate fabric. A process for producing a dibasic cellulose composite fabric, characterized in that it is treated twice. The method for producing a dibasic cellulose composite fabric according to claim 1, which is prepared by copper bath and bathing treatment of strong alkali and weak alkali during saponification with alkali. The method for producing a dibasic cellulose composite fabric according to claim 1, wherein a reaction rate modifier such as quaternary ammonium salt or phosphonium salt is added during saponification with alkali.