JP2863893B2 - 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, cellulosic fiber material fabrics have advantages such as good texture and excellent moisture absorption as compared to synthetic fiber material fabrics, but they tend to wrinkle, shrink when washed, and even wash. There are many drawbacks, such as the fibers gradually becoming harder when repeated, 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 crosslinking agent, moisture and sulfur dioxide gas are used in combination as a catalyst, and sulfuric acid generated is used to carry out 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. Thereafter, a method of applying a low 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), a study using an epoxy compound was also conducted by Dyeing Industry (Vol. 24, N.
o. 2, 1976, P76-83, Vol. 24, N
o. 3,19769P142 to 147) each report a study using a vinyl sulfone derivative.
In fact, a method for processing cellulosic fabrics having both tear strength and high morphological stability that can withstand practical use has not yet been established.

[0005]

DISCLOSURE OF THE INVENTION The present invention has high W & W properties, which are indicators of form stability, and a tear strength (650 g or more: weft) that can withstand practical use and does not use formaldehyde. An object of the present invention is to provide a morphologically stable processing method for a cellulosic woven fabric which is excellent in safety without any problem.

[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 provides a cellulosic fabric with an epoxy compound of ethylene glycol diglycidyl ether and 4 to 22 oxyethylene chains.

Embedded image A novel form stable processing method for a cellulosic fabric characterized by treating with a mixed solution of an epoxy compound with at least one kind of polyethylene glycol diglycidyl ether represented by the following formula:

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, in order to obtain desired W & W property and tear strength, epoxy resin of ethylene glycol diglycidyl ether as an epoxy compound and polyethylene glycol diglycidyl ether having a long oxyethylene chain length is used as a cross-linking agent for a cellulosic fabric. A mixed solution of the compounds is used to crosslink the cellulose molecules. That is, the desired W &
Ethylene glycol diglycidyl ether is used to obtain W property, and polyethylene glycol diglycidyl ether having a long chain length of 4 to 22 oxyethylene chains is used to secure desired tear strength and to improve texture. Use By controlling the use ratio in a certain range, not only the desired W & W property and tear strength but also a unique texture can be provided.

The present inventors have conducted intensive studies from this viewpoint, and as a result, determined that the amount of each epoxy compound used per liter is the epoxy equivalent (hereinafter referred to as wpe).
(To be referred to as an epoxy ratio hereinafter) is 2.0 to 2.0.
2.5 (g / l) / w. p. e. And the epoxy ratio of ethylene glycol diglycidyl ether is 4% of the total epoxy ratio of the epoxy compound used.
When it is in the range of 5 to 60%, it has been found that not only a desired W & W property and a tear strength (weft: 650 g or more) that endure practical use can be obtained, but also a unique texture can be obtained. The epoxy compound as a cross-linking agent is suitable in terms of high safety and a well-balanced anti-wrinkling property and anti-shrink property in both wet and dry by usual impregnation, drying and curing. The length of the oxyethylene chain of polyethylene glycol diglycidyl ether is 4 oxyethylene chains.
It can be appropriately selected from the epoxy compounds in the range of 22 to 22 according to the desired wrinkle resistance, shrink resistance and texture. In addition, the concentration of these treatment liquids can be appropriately set within a range of 45 to 60% of the total epoxy ratio of the epoxy compound used, and a plurality of polyethylene glycol diglycidyl ethers having different chain lengths can be prepared according to a desired texture. Thus, it is possible to select within this concentration range and arbitrarily combine them. However, a combination of ethylene glycol diglycidyl ether and tetraethylene glycol diglycidyl ether is preferable in order to obtain a W & W property of a 3.5-grade or higher no-iron level. Further, a silicone-based soft finishing oil may be used in combination.

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

However, in the case of processing of the pre-dyed product, it is preferable to use a 0.5 to 2.0% by weight aqueous solution of caustic soda as the alkali catalyst. The cross-linking treatment is performed by dipping and impregnating the cellulosic fabric after mercerization into the cross-linking treatment aqueous solution, squeezing with a roller at 80%, drying at 80 to 120 ° C., and curing at 100 to 130 ° C. or dry heat treatment at 100 ° C. Any of the wet heat treatment for stamming may be performed. 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 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. The method of the present invention, that is, by crosslinking the cellulose-based fabric with a mixed solution of an epoxy compound ethylene glycol diglycidyl ether and an oxyethylene chain having 4 to 22 polyethylene glycol diglycidyl ethers,
It has a tear strength that can withstand practical use that could not be achieved conventionally, and has well-balanced wrinkle resistance and shrink resistance in both dry and wet, and because it does not perform resin treatment as a pretreatment, it has cellulosic fiber A cellulosic woven fabric having excellent W & W properties while retaining moisture absorption and texture can be obtained.

[0013]

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.
In addition, W & W properties, tear strength, water absorption, texture, whiteness and color fastness 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 ~
Good for 4 people; Good for 2 or less; △ Bad for all; × 5) Color fastness Friction (dry, wet) JIS-L0849 Lightfastness JIS-L0842 20-hour exposure Sweat (acid, alkali) JIS-0848A method Washing JIS-L0844

(Example 1) Mercerized width 50
cm, cotton fabric of 10 m length (basis weight: 120 g / m ² , 8
No. 0 twin yarn, weft density 133 × 73 / in. 5) were prepared.

As a catalyst, an aqueous solution containing 4% by weight of zinc borofluoride, ethylene glycol diglycidyl ether (crosslinking agent 1) as trade name Denacol EX-810 (epoxy equivalent: 112, manufactured by Nagase Kasei Kogyo Co., Ltd.) and polyethylene Glycol diglycidyl ether (crosslinking agent 2)
Trade name Denacol EX821 (epoxy equivalent: 1
95, n: about 4, manufactured by Nagase Kasei Kogyo Co., Ltd.) (100.8 g / l, 214.5 g / l), (13
4.4 g / l, 156 g / l), (134.4 g / l,
253.6 g / l), (145.6 g / l, 234 g / l
l), (168 g / l, 195 g / l) were dissolved, and the epoxy ratio of each epoxy compound was (1) 0.9 + 1.1.
= 2.0 (g / l) / w. p. e. (2) 1.2 + 0.
8 = 2.0 (g / l) / w. p. e. (3) 1.2+
1.3 = 2.5 (g / l) / w. p. e. (4) 1.3
+ 1.2 = 2.5 (g / l) / w. p. e. (5) 1.
5 + 1.0 = 2.5 (g / l) / w. p. e. Thus, 50 liters of each of the five levels of the crosslinking treatment liquid were prepared.

Each of the above-mentioned 10 m-length cotton fabrics is immersed in the cross-linking treatment liquid one by one to impregnate each of the cross-linking treatment liquids. Curing was performed at 115 ° C. for 2 minutes in a baking machine to perform a crosslinking treatment.

Next, 1 g / l of Adecanol TS-403A (trade name, manufactured by Asahi Denka Kogyo KK) as a soaping agent.
Five cotton fabrics cross-linked with an aqueous solution are soaped, washed with water, and dried. Illuminal B is a fluorescent whitening agent.
An aqueous solution containing 0.3 wt.
Samples 1 to 5 were obtained by adding and mixing 5% by weight (active ingredient: 25%, meanwhile, manufactured by YAS & CO., LTD.) And finishing with a pad dryer. W & W of these samples
Table 1 shows the results of examining the properties, tear strength, water absorbency, hand and whiteness.

[0019]

[Table 1]

As apparent from Table 1, the total epoxy ratio of the epoxy compound is 2.0 to 2.5 (g / l) / w.
p. e. And the epoxy ratio of ethylene glycol diglycidyl ether is in the range of 45 to 45 of the total epoxy ratio.
Cotton fabric adjusted to a concentration range of 60% and cross-linked is
The W properties, tear strength, water absorption, texture and whiteness were all good.

(Comparative Example 1) The same 50% wide, 10m long cotton fabric (basis weight: 120 g / m ² , No. 80 double yarn, 133 weft density ×
73 / in. 6) were prepared.

As a catalyst, an aqueous solution containing 4% by weight of zinc borofluoride, ethylene glycol diglycidyl ether (crosslinking agent 1) as trade name Denacol EX-810 (epoxy equivalent: 112, manufactured by Nagase Kasei Kogyo KK) and polyethylene Glycol diglycidyl ether (crosslinking agent 2)
Trade name Denacol EX821 (epoxy equivalent: 1
95, n: about 4, manufactured by Nagase Kasei Kogyo Co., Ltd., respectively (100.8 g / l, 117 g / l), (89.6 g
/ L, 239 g / l), (156.8 g / l, 117 g)
/ L), (112 g / l, 292.5 g / l), (19
6g / l, 146.25g / l), (151.2g /
1, 321.75 g / l), and the epoxy ratio of each epoxy compound was (6) 0.9 + 0.6 = 1.5 (g).
/ L) / w. p. e. (7) 0.8 + 1.2 = 2.0
(G / l) / w. p. e. (8) 1.4 + 0.6 = 2.
0 (g / l) / w. p. e. (9) 1.0 + 1.5 =
2.5 (g / l) / w. p. e. (10) 1.75+
0.75 = 2.5 (g / l) / w. p. e. (11)
1.35 + 1.65 = 3.0 (g / l) / w. p. e.
Thus, 50 liters of each of the 6 levels of the crosslinking treatment liquid were prepared.

Each of the above-mentioned 10 m-length cotton fabrics is immersed in the cross-linking solution one by one to impregnate each of the cross-linking solutions, and then squeezed with a roller to a squeezing ratio of 80%, and then dried at 120 ° C. for 30 seconds. Curing was performed at 115 ° C. for 2 minutes in a baking machine to perform a crosslinking treatment.

Next, 1 g / l of Adecanol TS-403A (trade name, manufactured by Asahi Denka Kogyo KK) as a soaping agent.
Six cotton fabrics crosslinked with an aqueous solution are soaped, washed with water and dried, and used as a fluorescent whitening agent, Illuminas B
An aqueous solution containing 0.3 wt.
Samples 6 to 11 were obtained by adding and mixing 5% by weight (active ingredient: 25%, on the other hand, manufactured by Yushi Yushi Kogyo KK) and finishing with a pad drier. W & W of these samples
Table 2 shows the results of examining the properties, tear strength, water absorbency, hand and whiteness.

[0025]

[Table 2]

As is apparent from Table 2, the total epoxy ratio of the epoxy compound is 2.0 (g / l) / w. p. e.
If it is less than 5, even if the epoxy ratio of ethylene glycol diglycidyl ether is in the concentration range of 45 to 60% of the total epoxy ratio, the W & W property is poor, and the total epoxy ratio of the epoxy compound is 2.0 to 2.5. (G / l) / w. p.
e. The epoxy ratio of ethylene glycol diglycidyl ether is 45 to 6 of the total epoxy ratio.
If it is not within the range of 0%, the crosslinked cotton fabric has W & W properties,
Good tear strength cannot be obtained. Furthermore, the total epoxy ratio is 2.5 (g / l) / w. p. e. If the ratio exceeds 45%, even if the epoxy ratio of ethylene glycol diglycidyl ether is 45% of the total, a tear strength that can withstand practical use cannot be obtained.

(Example 2) (1) A 50 cm × 10 m (cotton / polynosic) blended yarn woven fabric (basis weight: 105 g / m ² , blending ratio: cotton) scoured and bleached by a conventional method and then subjected to a mercerizing treatment 45% /
Polynosic 55%, No. 50 single yarn, weft density: 114 × 80 / in. ) Was prepared.

The (cotton / polynosic) mixed-spun fabric was used for the cross-linking treatment liquid used in Sample 3 of Example 1, and the finishing oil was changed to Sofmin SN-12 (trade name: active ingredient: 20%,
Sample 12 was obtained in the same manner as in Example 1, except that the aqueous solution was changed to a 5% by weight aqueous solution of Miyoshi Oil & Fat Co., Ltd.).

(2) A cross-woven fabric having a width of 50 cm and a length of 10 m, which has been subjected to scouring, bleaching and mercerizing using a cotton thread as a warp and a polynosic thread as a weft (basis weight: 1).
08 g / m ² , No. 50 single yarn, weft density: 114 yarns x 80
Book / in. ) Was prepared.

Separately, a 2.0% by weight aqueous sodium hydroxide solution was used as a catalyst, and ethylene glycol diglycidyl ether (crosslinking agent 1) was trade name Denacol EX.
-810 (epoxy equivalent: 112, manufactured by Nagase Kasei Kogyo Co., Ltd.) and polyethylene glycol diglycidyl ether (crosslinking agent 3) as trade name Denacol EX832
(Epoxy equivalent: 280, n: about 9, manufactured by Nagase Kasei Kogyo Co., Ltd.).
4 g / l, 280 g / l) and the epoxy ratio was 1.2 + 1.0 = 2.2 (g / l) / w. p. e. After being dissolved and impregnated with a crosslinking treatment liquid, the mixture was squeezed with a roller to a squeezing ratio of 80%, steamed at 100 ° C. for 3 minutes to perform a crosslinking reaction, and then washed with water to remove unreacted materials. Dry at 140 ° C. for 30 seconds. Finishing process is
Sample 13 was obtained in the same manner as in Example 1.

(3) 50 cm width bleached by a conventional method
× Polynosic fabric of 10 m length (basis weight: 110 g / m
² , 50th single yarn, weft density: 130 x 82 / i
n. 3) were prepared.

As a catalyst, an aqueous solution containing 4% by weight of zinc borofluoride, ethylene glycol diglycidyl ether (crosslinking agent 1) as trade name Denacol EX-810 (epoxy equivalent: 112, manufactured by Nagase Kasei Kogyo KK) and polyethylene Glycol diglycidyl ether (crosslinking agent 2)
Trade name Denacol EX821 (epoxy equivalent: 1
95, n: about 4, manufactured by Nagase Kasei Kogyo Co., Ltd.) and as polyethylene glycol diglycidyl ether (crosslinking agent 4), trade name Denacol EX861 (epoxy equivalent: 5)
87, n: about 22, manufactured by Nagase Kasei Kogyo Co., Ltd.)
Each epoxy compound (112 g / l, 140 g /
1, 293.5 g / l), (134.4 g / l, 168
g / l, 293.5 g / l), (156.8 g / l, 2
24 g / l, 176.1 g / l), and the epoxy ratio was respectively (14) 1.0 + 0.5 + 0.5 = 2.0 (g /
l) / w. p. e. (15) 1.2 + 0.6 + 0.5 =
2.3 (g / l) / w. p. e. (16) 1.4 + 0.
8 + 0.3 = 2.5 (g / l) / w. p. e. And the mixture of three kinds of crosslinking agents was adjusted to 50 liters each. Each of the above-mentioned polynosic fabrics was added to the mixed solution for 1 part.
After being immersed one by one and impregnated with the crosslinking treatment liquid, the mixture was squeezed with a roller to a squeezing ratio of 80%, dried at 130 ° C. for 30 seconds, and then cured at 100 ° C. for 3 minutes to perform a crosslinking treatment. Then, two sheets of polynosic fabric cross-linked with 1 g / l aqueous solution of ADEKANOL TS-403A (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.) as a soaping agent are each soaped, washed with water, and dried, and a finishing oil agent, Fine Soft, a trade name SE-4G (Daiichi Kogyo Seiyaku Co., Ltd., active ingredient 15)
%) With a 70 g / l aqueous solution using a pad dryer to obtain Samples 14, 15, and 16.

Table 3 shows the results of examining the W & W properties, tear strength, water absorption, hand and whiteness of the samples 12 to 16 obtained as described above.

[0034]

[Table 3]

As apparent from Table 3, the total epoxy ratio of the epoxy compound is 2.0 to 2.5 (g / l) / w.
p. e. And the epoxy ratio of ethylene glycol diglycidyl ether is 45% of the total epoxy ratio.
The cellulosic woven fabric adjusted to a concentration range of 架橋 60% and cross-linked was excellent in W & W properties, tear strength, water absorption, hand and whiteness.

(Example 3) 50 m of the same cotton broad woven fabric as used in Example 1 was treated with a yellow dye (trade name: Unislon Y
(3GK, manufactured by Sumitomo Chemical Co., Ltd.) 7.4 g /
l, green dye (trade name: Unislon Olive7X,
2.9 g / l, red dye (trade name: Unislon Red 2BK, manufactured by Sumitomo Chemical Co., Ltd.) 1.4
g / l, anti-migration agent sodium alginate 2% solution 25 g / l, penetrant trade name Invazin PBN
(INVADINE PBN, Ciba-Geigy) 5g
After being immersed in an aqueous solution of / l, it was squeezed, dried at 120 ° C for 2 minutes, and cured at 220 ° C for 1 minute. Next, sodium sulfate 30 g / l, caustic soda (48%)
After reducing and squeezing with an aqueous solution containing 45 g / l and 30 g / l hydrosulfite, steaming was performed at 100 ° C. for 40 seconds and dried at 120 ° C. for 2 minutes to obtain a dyed cotton fabric. After the dyed cotton fabric is divided into 5 equal lengths of 10 m each,
Except that the catalyst of Example 1 was changed to a 1% aqueous solution of caustic soda, the same treatment as in Example 1 was performed until the finishing treatment with the same combination of crosslinking agents to obtain Samples 17 to 21. Table 4 shows the results of examining the W & W properties, tear strength, water absorbency, texture, and color fastness of these samples.

[0037]

[Table 4]

As is apparent from Table 4, even in the dyed cotton fabric, the catalyst was used as an aqueous caustic soda solution and the total epoxy ratio of the epoxy compound was 2.0 to 2.5 (g / l) / w. p.
e. And the epoxy ratio of ethylene glycol diglycidyl ether is 45-6 of the total epoxy ratio.
Cotton fabric adjusted to a concentration range of 0% and cross-linked is W & W
The properties, tear strength, water absorption, texture and color fastness were all good.

[0039]

The method for processing a cellulosic woven fabric according to the present invention employs the above-mentioned constitution. The cellulosic woven fabric is prepared by crosslinking a cellulosic fabric with an epoxy compound of ethylene glycol diglycidyl ether and a chain having 4 to 22 oxyethylene chains as a crosslinking agent. The cross-linking treatment is carried out using a mixed solution of polyethylene glycol diglycidyl ether, which is a long epoxy compound, with one or more epoxy compounds, so that the cellulosic fabric obtained by the conventional processing method can be stably processed. Compared to the product, it has high W & W properties, and at the same time has sufficient tear strength and excellent texture to withstand practical use. or,
Since the processing is performed with an epoxy compound that is a non-formaldehyde cross-linking agent, the safety is extremely high. Therefore, the cellulosic fabric processed by the processing method of the present invention is suitable as a material for sanitary materials such as uniforms such as shirts and uniforms, hospital bed sheets and white coats, bedding materials such as sheets and futon covers, and general clothing. Can be used for

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-50-40896 (JP, A) JP-A-59-94681 (JP, A) JP-B-41-12080 (JP, B1) (58) Field (Int.Cl. ⁶ , DB name) D06M 13/00-13/535

Claims (2)

(57) [Claims] 1. A cellulosic woven fabric is treated with an epoxy compound of ethylene glycol diglycidyl ether. A process for processing a cellulosic fabric, characterized by treating with a mixed aqueous solution of an epoxy compound with at least one kind of polyethylene glycol diglycidyl ether wherein n is an integer of 4 to 22. 2. The total epoxy ratio, expressed as a value obtained by dividing the amount of each epoxy compound used per liter of solution by the epoxy equivalent, is 2.0 to 2.5 (g / l) /
w. p. e. 2. The method according to claim 1, wherein the epoxy ratio of ethylene glycol diglycidyl ether is in the range of 45 to 60% of the total epoxy ratio of the epoxy compound used. .