JP2852495B2 - Morphologically stable processing of cellulosic fabrics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cellulosic woven fabric having an epoxy compound of a cellulosic fabric, which has a practically useful tearing strength, and has an excellent texture and a wash and wear property (hereinafter referred to as "W & W property"). It relates to the processing method.

[0002]

2. Description of the Related Art Conventionally, cellulosic fiber materials have been widely used as clothing materials because they exhibit better hygroscopicity and texture than synthetic fiber materials. However, the woven fabric of the cellulosic fiber material has advantages such as good texture and excellent hygroscopicity as compared with the woven fabric of the synthetic fiber material, but tends to wrinkle, shrinks when washed, and repeats washing. There are also many drawbacks such as the fibers becoming harder gradually, and many processing methods have been proposed since long ago.

For example, Japanese Patent Publication No. 49-18517 discloses a processing method in which formaldehyde vapor is used as a cross-linking agent, water and sulfur dioxide gas are used in combination as a catalyst, and sulfuric acid generated is used to promote the reaction at a high temperature. ing. However, this method has a drawback that the tear strength of the cellulosic fiber woven fabric is extremely reduced due to the effect of sulfuric acid generated and the crosslinking and immobilization of the cellulosic molecules by formaldehyde. The fact is that a decrease in strength is suppressed by mixing or knitting the fibers. Furthermore, “Processing Technology” magazine (Vol. 29, No. 6, 1994, published by Textile Co., Ltd.)
p. No. 389-395), a soft texture is first given to the cellulose fibers by mercurizing using liquid ammonia to uniformly swell the cross-section of the cellulose fibers so as to have a substantially circular cross-section and narrow the average fibril interval. Then, a method of applying a formaldehyde resin and removing ammonia is outlined.
However, since these are all processing methods using a formaldehyde gas or a low formaldehyde resin, formaldehyde remains on the fabric after processing, and there is a problem in terms of clothing hygiene and safety.

[0004] On the other hand, non-formaldehyde processing of cellulose fibers is described in the Journal of the Society of Textile Science, Vol.
11, 1969, P502-513, Vol. 26, N
o. 7, 1970, pp. 124-137), and also published in "Dyeing Industry" (Vol. 24, No. 2, 1976, p.
83, Vol. 24, no. 3,1976, P142-
147), studies using vinylsulfone-based derivatives have been reported respectively. However, a processing method for a cellulose-based fabric having both tear strength and high morphological stability that can withstand practical use has not yet been established. It is a fact.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to cellulose which has high W & W properties and tear strength, which are indicators of form stability, does not use formaldehyde, does not cause toxicity to the human body, and has excellent safety. The present invention provides a method for stably processing a woven fabric.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention relates to a method of preparing a cellulose-based fabric by using a nonionic silicone-based softening agent or a nonionic silicone-based softening agent with a nonionic urethane resin and / or a nonionic urethane prepolymer. A novel form-stable processing method for cellulosic fabrics, characterized by treating the modified cellulose with a mixed dispersion of ethylene glycol diglycidyl ether or diethylene glycol diglycidyl ether in the same bath.

The cellulosic fabric of the present invention refers to a fabric woven from cellulosic fibers obtained by singly or blending cellulosic fibers such as cotton, rayon and polynosic. However, it can also be applied to fabrics such as knits.

In the present invention, a nonionic silicone softening oil and ethylene glycol diglycidyl ether or diethylene glycol diglycidyl ether are added to a conventional mercerized or bleached cellulose-based fabric in order to prevent a decrease in tear strength. Or a non-ionic silicone softening oil, a non-ionic urethane resin and / or a modified non-ionic urethane prepolymer, and ethylene glycol diglycidyl ether or diethylene glycol diglycidyl ether. The same bath treatment is performed using the mixed dispersion solution. Since the mixed dispersion solution forms or fixes these films by heat treatment simultaneously with the crosslinking reaction on the fiber surface, the present invention has an effect of preventing a decrease in tear strength due to crosslinking. Further, the nonionic silicone-based softening oil agent, nonionic urethane-based resin and modified nonionic urethane prepolymer can be used as a fluorinated fluoropolymer used as a crosslinking catalyst with ethylene glycol diglycidyl ether or diethylene glycol diglycidyl ether. It is preferable to form an ion complex with a metal salt and to significantly lose water insolubility or dispersibility and not precipitate. Therefore, it is essential to use a nonionic one having no anionic or cationic dissociating group. It is. That is, the nonionic silicone softening agent used in the present invention includes methylhydrogenpolysiloxane, α,
ω-dihydroxymethylpolysiloxane, dimethylpolysiloxane, etc., and the nonionic urethane resin may be any nonionic resin obtained by polymerizing a urethane prepolymer with a chain extender. The modified nonionic urethane prepolymer is preferably a urethane prepolymer obtained by modifying the isocyanate groups at both ends of the urethane prepolymer with a phenol group or a ketone group. Although the same effect can be obtained by using a polyethylene emulsion, water repellency is so strong that a water spot is generated after finishing, which is not preferable.

The concentration of the treatment liquid of the nonionic silicone softening finishing oil to the cellulosic fabric is preferably 1 to 5% by weight in consideration of the feeling and the water absorption. or,
When a mixture of a nonionic silicone-based softening oil and a modified nonionic urethane resin and / or nonionic urethane prepolymer is used, the treatment concentration range is such that the feeling is not impaired and the tear strength is high. The total value of the concentrations is preferably in the range of 1 to 5% by weight in consideration of preventing the reduction.

As the crosslinking agent, ethylene glycol diglycidyl ether or diethylene glycol diglycidyl ether is highly safe and can obtain well-balanced wrinkle resistance and shrink resistance in both wet and dry conditions by ordinary impregnation, drying and heat treatment. It is preferred in that respect. The concentration of the processing solution can be appropriately set according to the desired wrinkle resistance and shrink resistance, and is usually 100 to 250 g.
/ L can be used, but in order to obtain a so-called no-iron level W & W property of 3.3 class or higher, 1
It is preferable to use in the range of 50 to 250 g / l. On the other hand, the washing resistance of the processed product is better when the treatment concentration of the cross-linking agent is higher, but the tear strength (weft) is 750 g, which retains the texture peculiar to the material used for the fabric and is practically usable. In order to maintain the above, the treatment concentration of the crosslinking agent should be 1
It is preferable to use in the range of 50 to 200 g / l.

As a catalyst for crosslinking the epoxy compound, an acid or an alkali can be used. Generally, an acid catalyst, for example, a strongly acidic metal salt such as zinc borofluoride or magnesium borofluoride is used.

[0012] The processing of the cellulosic fabric is carried out by a nonionic silicone softening agent or a nonionic silicone softening agent and a nonionic urethane resin and / or a nonionic urethane prepolymer. The woven fabric is immersed and impregnated in a mixed dispersion solution obtained by mixing and adding ethylene glycol diglycidyl ether or diethylene glycol diglycidyl ether to the denatured product, and the squeezing ratio is 80 with a roller.
%, And after drying at 80 to 120 ° C, 150 to 17
Heat treatment may be performed at 0 ° C. The heat treatment time is not particularly limited as long as the crosslinking reaction proceeds sufficiently, and can be appropriately set according to the basis weight of the cellulosic fabric.

Next, finishing processes such as washing with water and drying after the soaping process and finishing oil treatment are not particularly limited, and may be performed by a generally used method. In addition, a fluorescent whitening agent can be used to further increase the whiteness of the fabric. In this case, the fluorescent whitening agent is used in the same bath as the finishing oil according to the desired whiteness in the same manner as in a normal finishing process. What is necessary is just to add an appropriate amount of agent and to process. In the method of the present invention, since it is treated with a non-formaldehyde-based agent, there is no problem in hygiene, and it has tear strength that can withstand practical use that could not be achieved conventionally, and also has balanced wrinkle resistance and shrink resistance in both wet and dry. And a cellulose-based fabric having excellent W & W properties while retaining the moisture absorption and texture of the cellulose-based fiber.

[0014]

The present invention will be described below in detail with reference to examples, but the present invention is not limited to the scope of the examples.
The W & W properties, tear strength, water absorption, hand and whiteness were tested by the following methods.

1) W & W property JIS L1096-19
79 6.23 Method A Tumble dry 2) Tear strength JIS L1096-1979
15.5 Method D 3) Water Absorption Test A sample was cut into a width of 3 cm and a length of 15 cm, and the tip was immersed vertically in a 200 ml beaker containing 100 ml of ion-exchanged water for 1 minute for 1 minute, and then taken out. After standing for 1 minute to allow enough water to be sucked up, the height of this sucked up was measured. 4) Texture and whiteness Five persons inspected by sensory test and judged according to the following criteria. All 5 are good; ◎ 3 ~
4 good; ○ 2 good or less; △ Bad for all; ×

(Example 1) Mercerized cotton fabric 50 cm wide and 2 m long (basis weight: 120 g / m 2, # 80 double yarn, weft density 133
Book x 73 / in. 5) were prepared. An aqueous solution containing 14% by weight of a nonionic silicon-based softening oil TX5-15P (active ingredient: 34%, manufactured by Kyoeisha Chemical Co., Ltd.) was prepared, and the aqueous solution was divided into five containers, each of which was used as a catalyst. Zinc oxide was added to contain 4% by weight, and then, as a crosslinking agent, ethylene glycol diglycidyl ether (trade name: Denacol EX-810 (epoxy equivalent: 1)
12, manufactured by Nagase Kasei Kogyo Co., Ltd.)
150g / l, 175g / l, 200g / l, 250g
/ L to prepare a mixed dispersion of five levels containing 4.76% by weight of a nonionic silicone softening agent.

The above-mentioned cotton fabric is added to the mixed dispersion solution for 1
The sheets were immersed one by one, squeezed with a roller to a squeezing ratio of 80%, dried at 120 ° C. for 1 minute, and baked in a baking machine, and cured at 165 ° C. for 2 minutes to perform a crosslinking treatment.

Next, trade name Adecanol TS-403
A (Asahi Denka Kogyo Co., Ltd.) 1 g / l aqueous solution, each of the five cross-linked cotton fabrics was soaped, washed with water and dried. Illuminal BSN (trade name, manufactured by Showa Kako Co., Ltd.) was used as a fluorescent whitening agent. In an aqueous solution containing 0.3% by weight, a finishing oil agent (trade name: Silicoran AN-980S (active ingredient: 25)
%, On the other hand, 5% by weight of Sharp Oil & Fats Industry Co., Ltd.), finish processing with a pad drier, and prepare samples I-1, II-1, III-1, IV-1, and V-. 1 was obtained. Table 1 shows the results of examining the W & W properties, tear strength, water absorbency, hand and whiteness of these samples.

[0019]

[Table 1]

As is clear from Table 1, 4.76% by weight of a nonionic silicone softening oil was added, the concentration of the crosslinking agent was adjusted to a concentration range of 150 g / l to 200 g / l, and the mixture was processed in the same bath. The cotton fabric had good W & W properties, tear strength, water absorption, hand and whiteness.

Example 2 Mercerized 50 cm × 2 m cotton / polynosic blended spun yarn fabric (blend rate: 45% cotton / 55% polynosic, No. 60 single yarn, weft density: 90 × 88 / I
n. 5) were prepared.

As a crosslinking agent, ethylene glycol diglycidyl ether (trade name: Denacol EX-810 (epoxy equivalent: 112, manufactured by Nagase Kasei Kogyo Co., Ltd.)) was used.
An aqueous solution containing 5 g / l was prepared, and the aqueous solution was divided into five containers, each of which was added as a catalyst so as to contain 4% by weight of zinc borofluoride, and then a nonionic silicone softening finish TX5-15P (active ingredient) : 34%, manufactured by Kyoeisha Chemical Co., Ltd.) at 20 g / l, 30 g / l, and 100 g / l, respectively.
1,147 g / l, 180 g / l, and 0.68% by weight of a nonionic silicone softening oil,
Five levels of mixed dispersions containing 1.02%, 3.4%, 5%, and 6.12% by weight were prepared.

Each of the above-described woven fabrics is immersed in the mixed dispersion solution one by one, and squeezed with a roller so as to have a squeezing ratio of 80%.
After drying and heat treatment at 120 ° C. for 1 minute, the mixture was cured in a baking machine at 165 ° C. for 2 minutes to carry out a crosslinking treatment.

Then, trade name Adecanol TS-403
A (Asahi Denka Kogyo KK) 1 g / l aqueous solution, each of the five crosslinked fabrics was soaped, rinsed and dried, and used as a fluorescent whitening agent Illuminal BSN (Showa Kako Co., Ltd.)
And an aqueous solution containing 0.3% by weight of a finishing oil agent (silicalan AN-980S (active ingredient: 25%, manufactured by Sharp Yushi Kogyo Co., Ltd.)). Finishing with sample I-
5, II-2, III-2, IV-2 and V-2 were obtained.
Table 2 shows the results of examining the W & W properties, tear strength, water absorbency, hand and whiteness of these samples.

[0025]

[Table 2]

As is apparent from Table 2, the woven fabric obtained by adding 1 to 5% by weight of a nonionic silicone softening oil and adjusting the concentration of the crosslinking agent to 175 g / l is W & W.
The properties, tear strength, water absorption, hand and whiteness were all good.

Example 3 A cross-woven fabric having a width of 50 cm and a length of 2 m obtained by mercerizing using a cotton yarn as a warp and a polynosic yarn as a weft (basis weight:
100g / m2, No. 50 single yarn, weft density: 133 x 7
3 / in. 5) were prepared.

Silicon Softener # 100 (trade name) which is a nonionic silicone softening agent (active ingredient: 25
%, Manufactured by Matsumoto Yushi Kogyo Co., Ltd.)
5% by weight of Elastron MF-25 (active ingredient: 25%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), which is a modified nonionic urethane prepolymer, and UPM-212HN, a nonionic urethane resin ( Active ingredient: 20%, on the other hand, 5% by weight of Yushi Kogyo Co., Ltd. dispersed in water, 1% by weight of a nonionic silicone softening finishing oil and a modified nonionic urethane prepolymer Was mixed with 1.25% by weight of a non-ionic urethane resin at a concentration of 1% by weight, and divided into five containers. 100 g / l, 150 g / l, 150 g / l of Denacol EX-850 (epoxy equivalent: 121, manufactured by Nagase Kasei Kogyo Co., Ltd.) which is a diethylene glycol diglycidyl ether of an epoxy compound as a cross-linking agent is used as a crosslinking agent.
75 g / l, 200 g / l, and 250 g / l were added to obtain a treatment solution. The above-mentioned woven fabric is immersed in the five treatment liquids, squeezed with a roller at a squeezing ratio of 80%, and squeezed at 100 ° C. for 5 minutes.
And dried at 165 ° C. for 2 minutes.

The treated mixed woven fabric was treated in the same manner as in the finishing treatment of Example 1 to obtain samples I-3, II-3, III-3, IV-
3, V-3 was obtained. Table 3 shows the results of examining the W & W properties, tear strength, water absorbency, hand and whiteness of these samples.

[0030]

[Table 3]

As is apparent from Table 3, 1% by weight of the nonionic silicone softening agent, a nonionic urethane resin and a modified nonionic urethane prepolymer were mixed and used at 2.25% by weight. Even if the crosslinker concentration is 150 ~
A cross-woven fabric crosslinked at a concentration range of 200 g / l has W
& W property, tear strength, water absorption, texture and whiteness were all good.

(Example 4) A bleached polynosic fabric having a width of 50 cm and a length of 2 m (basis weight: 120 g / m 2, No. 50 single yarn, weft density: 13)
0 × 82 / in. ) Was prepared.

Nonionic silicone soft finishing oil TX
5-15P (active ingredient: 34%, manufactured by Kyoeisha Chemical Co., Ltd.)
Is dissolved in an aqueous solution containing 8% by weight of UPM-212HN, a nonionic urethane resin (active ingredient: 20%, manufactured by Sharp Yushi Kogyo Co., Ltd.) so as to be 10% by weight. An aqueous dispersion solution containing 2.72% by weight of a softening finish oil and 2% by weight of a nonionic urethane resin was prepared.
Prepared in one container.

Example 1 was prepared by adding a mixed aqueous dispersion of the nonionic urethane resin and the nonionic silicone softening agent to the aqueous dispersion.
Denacol EX-810 (epoxy equivalent: 112, manufactured by Nagase Kasei Kogyo Co., Ltd.) which is a cross-linking agent of Denacol EX-850 (epoxy equivalent: 121, Nagase Kasei Kogyo Co., Ltd.), a diethylene glycol diglycidyl ether. The same procedures as in Example 1 were carried out, except that Samples I-4, II-4, III-4, IV-4, V-
4 was obtained. Table 4 shows the results of examining the W & W properties, tear strength, water absorbency, hand and whiteness of these samples.

[0035]

[Table 4]

As is clear from Table 4, 2.72% by weight
Containing a nonionic urethane-based resin and 2% by weight of a nonionic silicone-based softening oil and having a crosslinking agent concentration of 150 to 2
The polynosic fabric crosslinked in the range of 00 g / l is
The W & W properties, tear strength, water absorbency, texture and whiteness were all good.

(Example 5) A cross-woven fabric having a width of 50 cm and a length of 2 m, which was obtained by using a cotton yarn for a warp and a polynosic yarn for a weft (weight: 100 g / m 2, No. 50 single yarn, weft density: 133 × 73 / in.) Were prepared.

Silicon Softener # 100 (trade name) which is a nonionic silicone-based softening oil agent (active ingredient: 25
%, Manufactured by Matsumoto Yushi Kogyo Co., Ltd.) and Elastron MF-2 which is a modified nonionic urethane prepolymer.
5 (active ingredient: 25%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) at 2% by weight + 1% by weight = 3% by weight, 3% by weight + 1% by weight = 4% by weight, 10% by weight + 5% by weight = 15% by weight , 8% by weight +
12% by weight = 20% by weight, 10% by weight + 14% by weight = 2
4% by weight and dispersed in water to obtain 0.5 + 0.25 = 0.75% by weight of a modified nonionic silicone softening agent and a modified nonionic urethane prepolymer, respectively.
0.75 + 0.25 = 1.00% by weight, 2.5 + 1.2
5 = 3.75% by weight, 2 + 3 = 5% by weight, 2.5 + 3 =
Five kinds of aqueous dispersions containing 5.5% by weight were prepared.

Each of the aqueous dispersions was treated with zinc borofluoride 4
Wt%, trade name: Denacol EX850 (epoxy equivalent: 121, manufactured by Nagase Kasei Kogyo) as a crosslinking agent
5 g / l was added to prepare 5 kinds of mixed dispersion solutions.

Each of the above-mentioned mixed woven fabrics is immersed in the mixed dispersion solution one by one, and squeezed with a roller at a squeezing ratio of 80% to obtain 12
After drying at 0 ° C for 1 minute, it is baked in a baking machine 165
Curing was performed at 1.5 ° C. for 1.5 minutes to perform a crosslinking treatment.

Then, trade name Adecanol TS-403
A Five cloths cross-linked with a 1 g / l aqueous solution (manufactured by Asahi Denka Kogyo KK) were soaped, washed with water, and dried.
Then, the same finishing processing as in Example 1 was performed to perform sample I-5.
II-5, III-5, IV-5 and V-5 were obtained. Table 5 shows the results of examining the W & W properties, tear strength, water absorbency, hand and whiteness of these samples.

[0042]

[Table 5]

As is apparent from Table 5, the cross-woven fabric cross-linked at a total concentration of the nonionic silicone softening agent and the modified nonionic urethane prepolymer in the range of 1 to 5% by weight is W & W. Properties, tear strength, water absorption,
Both the texture and the whiteness were good. If the total concentration of the modified nonionic silicone softening agent and the modified nonionic urethane prepolymer is less than 1% by weight, the drop in tear strength cannot be prevented. become worse.

[0044]

According to the present invention, the method for stabilizing the form of a cellulosic woven fabric according to the present invention has the above-mentioned constitution. A nonionic silicone softening oil or a nonionic silicone softening oil is added to a cellulose woven fabric. Since a non-ionic urethane resin and / or a modified non-ionic urethane prepolymer is mixed and dispersed with ethylene glycol diglycidyl ether or diethylene glycol diglycidyl ether, a cross-linking treatment is performed. Compared to the cellulosic woven fabric obtained, it has a high W & W property and at the same time has sufficient tear strength to withstand practical use. Further, since the crosslinking treatment is performed with an epoxy compound which is a non-formaldehyde-based crosslinking agent, the safety is extremely high. Therefore, the cellulosic woven fabric processed by the form stability processing method of the present invention is suitable as a material for sanitary materials such as uniforms such as shirts and uniforms, bed sheets for hospitals, white coats and the like, and bedding materials such as sheets and futon covers. Can be used for

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-52-91993 (JP, A) JP-A-3-124882 (JP, A) JP-A 4-249151 (JP, A) 25795 (JP, B1) (58) Fields investigated (Int. Cl. ⁶ , DB name) D06M 13/00-13/535 D06M 15/00-15/715

Claims (2)

(57) [Claims] 1. A cellulosic fabric characterized by being impregnated with a mixed dispersion of a nonionic silicone softening oil and ethylene glycol diglycidyl ether or diethylene glycol diglycidyl ether, followed by heat treatment. Morphologically stable processing method. 2. A method for preparing a cellulosic fabric from a nonionic silicone softening oil, a nonionic urethane resin and / or a modified nonionic urethane prepolymer, and ethylene glycol diglycidyl ether or diethylene glycol diglycidyl ether. And a heat treatment.