JPH03875A - Softening treating of cellulosic fiber cloth - Google Patents

Abstract

PURPOSE:To impart good soft feeling having excellent washing durability to a cellulosic fiber cloth by impregnating a treating liquid containing a specific epoxy-modified organopolysiloxane and a metal salt acidic catalyst into the cloth and heat-treating the cloth. CONSTITUTION:The objective treated cloth can be produced by (1) applying a treating liquid containing (A) an epoxy-modified organopolysiloxane of formula I (R1 is univalent hydrocarbon group; R2 is univalent hydrocarbon group or OH: A is bivalent organic group; X is group of formula II or formula III: m is 5-400; n is 2-200: m+n is 10-400) (preferably a compound containing >=2 epoxy groups in one molecule) and (B) an acidic catalyst consisting of a metal salt (preferably zinc borofluoride, etc.) to a cellulosic fiber cloth, (2) preliminarily drying the cloth at 80-100 deg.C and (3) heating at 120-180 deg.C for 0.5-5min in dry state.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel processing method for imparting a very soft texture with excellent washing durability to a cellulose fiber fabric.

(Conventional technology) Conventionally, it has been used as a softener for cellulose fiber fabrics.

Generally, surfactant-based water-soluble oils or oils 2
Emulsifying and dispersing agents of water-insoluble oils such as waxes, fatty acid derivatives, higher alcohols, and silicone oils are often used. However, all of these softeners have the disadvantage that they have poor washing durability, and the softener falls off from the fibers after one to three washings, resulting in loss of flexibility.

Durable softeners include dihydroxydimethylpolysiloxane, which has hydroxyl groups introduced at both ends of dimethylpolysiloxane, methylhydrodiene polysiloxane, which has active hydrogen groups directly introduced into silicon, or epoxy-modified polysiloxane, which has epoxy groups introduced. together with
A method of reacting the hydroxyl groups of dihydroxymethylpolysiloxane with active hydrogen or epoxy groups by heat treatment on the fibers to form a network polymer silicone elastomer on the fibers, or amino-modified polysiloxanes in which amino groups are introduced into polysiloxanes. A method is known in which a film is formed by a curing reaction by heat treatment on a fiber by using a combination of a polysiloxane and an epoxy-modified polysiloxane into which an epoxy group has been introduced (Japanese Patent Publication No. 48-17514). However, with these methods, a highly elastic silicone film is formed on the fibers, so while the surface of the fibers has the smooth touch characteristic of silicone, the fabric as a whole does not have rebound elasticity. 1. This is different from the softening that is the objective of the present invention.

In addition, many of the silicone films formed by these methods have excellent film strength and water resistance, but when processed into fibers, the bond between the silicone film and the fibers is weak, so the silicone film is easily washed away by washing. The film peels off, and the durability of the texture is not necessarily sufficient, and the surface texture becomes rough and hard after about 100 washes.

On the other hand, octadecylethylene urea-based softeners have been known for a long time as fabric softeners that are said to react with the hydroxyl groups of cellulose. The softening effect is only about 5 times, and the softening effect tends to be lower than that of silicone softeners.

(Problems to be Solved by the Invention) The present invention was made in view of the above-mentioned current situation, and an object of the present invention is to impart a soft texture with extremely excellent washing durability to a cellulose fiber fabric. It is something.

(Means for Solving the Problems) In order to achieve the objects of the present invention, the present invention has the following configuration.

That is, in the present invention, the general formula [wherein R1 is a monovalent hydrocarbon group I] and R2 is a monovalent in the present invention, the general formula m+n is an integer of 10 to 400 as a processing agent. Abstract: A method for softening a cellulose fiber fabric, which is characterized by impregnating the cellulose fiber fabric with a treatment solution containing an epoxy-modified organopolysiloxane represented by the following and a metal salt acidic catalyst, followed by drying and heat treatment. That is.

The present invention will be explained in detail below.

What is the cellulose fiber fabric applied to the present invention?

It refers to woven and knitted fabrics made of fibers such as cotton, linen, rayon, and acetate, and also includes woven and knitted fabrics in the form of blends, twists, and weaves of these fibers and synthetic fibers or protein fibers such as wool and silk. shall be provided.

In the case of blended spinning, twisted twisting, mixed weaving, etc., it is desirable that at least 20% or more of cellulose fibers be contained.

[In the formula, Rt is a monovalent hydrocarbon group + R2 is monovalent m+
n is an integer from 10 to 400. ] An epoxy-modified organopolysiloxane is used. The organopolysiloxane used here needs to contain at least two epoxy groups in one molecule in order to react effectively with cellulose. For each siloxane unit in the general formula, 1 m is 5 to 300. n is 4 to 50
, and m+n is preferably in the range of 10 to 300.

Many of these epoxy-modified polysiloxanes are commercially available, and are commercially available in emulsified or dispersed form for fiber processing applications. .

For example, boron MF-118, MF-18 (Shin-Etsu Chemical ■ product), Nikka silicone EP-1010゜EPC-
812 (Nicca Chemical ■ product), High Softer -350 (
There are many products such as Meisei Kagaku ■ products), and these are generally used for the purpose of temporary soft texture processing.

The amount of epoxy-modified polysiloxane used in the method of the present invention can range from 0.1 to 20% by weight based on the weight of 1 m fiber as a solid content.

Usually, it is suitable to use it in a range of about 1 to 5% by weight.

As the metal salt-based acidic catalyst used in combination with the above-mentioned treatment agent in the present invention, salts such as chlorides of zinc, magnesium, aluminum, etc., nitrates, borofluorides, etc. can be used.

Preferred are zinc chloride, magnesium chloride, aluminum chloride, and zinc nitrate. These include zinc borofluoride and 1:1 magnesium fluoride. Among these, zinc borofluoride is particularly preferably used. The appropriate amount of the metal salt-based acidic catalyst is 3 to 40% by weight based on the epoxy-modified polysiloxane, but the amount used varies slightly depending on the activity of the catalyst used.

In the method of the present invention, a treatment liquid consisting of an emulsion or dispersion of the epoxy-modified polysiloxane and a metal salt-based acidic catalyst is applied to a cellulose-based fiber fabric.

As for the application method, an impregnated padding method, a kiss roll method, a spray method, etc. may be employed as appropriate depending on the situation.

After applying the treatment liquid, preliminary drying is performed at 80 to 100 t, followed by dry heat treatment at 120 to 180 t' for about 3Q seconds to 5 minutes. Perform soaping treatment as necessary.

The present invention has two or more configurations.

(Function) In textile processing applications, epoxy-modified polysiloxane is used as a softener in finishing processing, either alone or in combination with other softeners, in addition to being used as a crosslinking agent or curing agent for dihydroxydimethylpolysiloxane or amino-modified polysiloxane. Generally, they are used in combination, and in this case, they have little washing durability. However, like the method of the present invention.

By adding appropriate metal salt acidic catalysts.

The fact that the washing durability is dramatically improved is thought to be due to the metal salt-based acidic catalyst exerting some kind of significant effect on the epoxy-modified polysiloxane and cellulose fiber.

Regarding this effect, the inventors of the present invention speculate as follows. That is, the metal salt acidic catalyst used in the method of the present invention is considered to play a role in promoting the reaction between the epoxy groups of the organopolysiloxane and the hydroxyl groups of cellulose.

It is understood that the organopolysiloxane is covalently bonded to the cellulose molecules via epoxy groups, increasing its washing resistance.

It is known that epoxy groups react with hydroxyl groups of cellulose under metal salt-based acidic catalysts1, for example, BBN.
BRITO et al. (Text, Res, J,, 31,
757 (1961)) conducted research on various epoxy resins using zinc borofluoride as a catalyst. but,
All of these are mainly intended to impart anti-wrinkle or anti-shrink effects through crosslinking with cellulose.

Moreover, the main skeleton of these epoxidized components is composed of an organic compound. In the present invention, the main skeleton is an inorganic siloxane, and an epoxy group is introduced as a reactive group into a polysiloxane with excellent flexibility and smoothness. Cellulose is This is an attempt to make the material softer, smoother and more durable by reacting with hydroxyl groups. In view of the durability improvement effect achieved by the method of the present invention, it is assumed that even in the cough organopolysiloxane whose main skeleton is inorganic, the hydroxyl groups and epoxy groups of cellulose react with the epoxy compound of the organic substance skeleton mentioned above. . Also 4
When polyester fibers are treated in the method of the invention. Since the durability against washing is relatively low, it is assumed that the reaction in the two-strand processing method is mainly a reaction with the hydroxyl group of the cellulose fiber, and there are not so many monopolymerization reactions.

(Example) Next, the method of the present invention will be explained with reference to an example, but the present invention is not limited thereto.

Example 1 A boblin fabric made of 40-count cotton yarn in both warp and weft (warp density: 133 threads/inch 9, weft thread density: 72 threads/inch) was coated with normal wool,
Desizing, scouring, bleaching, mercerizing.

Prepare the dyed cloth as an untreated cloth, apply the resin liquid of the following formulation 1 with a mangle, and squeeze it (squeezing ratio 70).
%) L, after pre-drying for 2 minutes at 100°C, 16
Dry heat treatment was performed at 0° C. for 2 minutes to obtain 9 soft processed fabrics of the present invention.

[Formulation 1] [Formulation 3] The processed fabrics of the present invention and comparative fabrics thus obtained were washed (5 and 20 times according to the JIS L-0213,103 method), and the slit width was measured using a handle ometer. The total hand value was measured using 10 carp and 5 pieces, and the bending resistance was evaluated using the average value. The results are shown in Table 1.

Magnesium chloride 8 g/l (hexahydrate salt, first grade reagent) For comparison with the present invention, the following formulation 2. Comparative Example 1 was prepared in exactly the same manner as in Example 1 except that Formulation 3 was used. A processed fabric of Comparative Example 2 was obtained.

[Formulation 2] As is clear from Table 1, the fabric processed by the method of the present invention exhibits almost no change in stiffness even after washing, indicating that the fabric has a very durable soft texture.

Example 2 A knitted fabric with a jersey texture using a 40-count spun yarn made of 60% hemp (ramie) and 40% cotton was usually subjected to hair burning.

An untreated cloth that has been scoured, bleached, and dyed is prepared, and a resin solution of the following formulation 4 is applied with a mangle, squeezed (squeezing ratio 75%), and heated at 100°C for 2.5 minutes. After pre-drying, dry heat treatment was performed at 150℃ for 2 minutes.
A flexible processed fabric of the present invention was obtained.

[Formulation 4] Magnesium chloride 9g/l (hexahydrate, grade 1 reagent) The jersey knitted fabric processed in this way has very good flexibility, and the irritation that stings the skin, which is characteristic of Lamy, is Almost disappeared due to the added flexibility effect.

In addition, almost no change in this flexibility was observed even after repeated washing 20 times.

Example 3 Viera texture fabric using 50 count spun yarn consisting of 65% rayon and 35% polyester (warp density 1+r)
J 2/inch, weft density 98 threads/inch) is prepared as an untreated fabric after the usual burning, desizing, scouring, bleaching, and dyeing, and the resin liquid of the following formulation 5 is sprayed onto it. (Grant rate 50%).

After pre-drying at 80°C for 2 minutes, dry heat treatment at 140°C for 2 minutes and nonionic surfactant 1g/i! Soaping treatment was carried out at 60° C. for 10 minutes to obtain a soft processed fabric of the present invention.

[Formulation 5] Zinc borofluoride 6 g/1 (45% aqueous solution, grade 1 reagent) The softened fabric of the present invention thus obtained has durable flexibility with excellent drapability. was. The texture was similar to that of 100% rayon.

(Effects of the Invention) The present invention involves reacting an organopolysiloxane containing an epoxy group in one molecule structure with cellulose fiber using a metal salt acidic catalyst.

With this configuration, it is possible to impart to the cellulose fabric a very durable and good soft feel that cannot be obtained by ordinary softening treatment methods.

Claims (1)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 is a monovalent hydrocarbon group, R_2 is a monovalent hydrocarbon group or -OH group, A is a divalent organic group, is a ▲ mathematical formula, chemical formula, table, etc. ▼ group or ▲ a mathematical formula, chemical formula, table, etc. shall be. ] A method for softening a cellulose fiber fabric, which comprises impregnating the cellulose fiber fabric with a treatment solution containing an epoxy-modified organopolysiloxane represented by the formula and a metal salt acidic catalyst, followed by drying and heat treatment.