JPH02139478A - Cellulosic textile product and production thereof - Google Patents

Abstract

PURPOSE:To obtain a textile product having durable hempen hand and heat insulating properties by distributing ceramic particles on the surface of a cellulosic textile product dyed in the form of a skein or product and covering the surface with a reactive type resin bondable to cellulose. CONSTITUTION:Ceramic particles (preferred example; Al2O3 or ZrO2 having high far infrared ray emitting effects), preferably an ion-modified ceramic particle-containing liquid is preferably fed to the surface of a textile product (e.g., cotton or knit or woven fabric) dyed in the form of a hank (or product) and the surface is simultaneously covered with a reactive type resin capable of covalent bonding to cellulose (or thereafter), preferably low-formalin type glyoxal resin, predried and heat-treated to provide a cellulosic textile product capable of keeping both hempen cool feeling excellent in resistance to washing and heat insulating properties for a long period.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is directed to dyed products or product dyed products made of cellulose fibers such as cotton or regenerated fibers that have a linen-like texture or, in addition, heat retention properties. The present invention relates to a cellulose-based fiber product to which the present invention has been applied, and a method for manufacturing the same.

[Prior art] In order to give fabrics made of synthetic fibers, cellulose fibers such as cotton and recycled fibers a linen-like dry and cool feel, suspensions and sols containing ceramic particles such as silica particles are used. A solution is applied together with various resins and catalysts such as urethane-based, silicone-based, urea-formalin-based, glyoxal-based, acrylic-based, epoxy-based, acetal, etc., and after dehydration and drying, crosslinking is formed by the action of the catalyst and high heat (so-called curing). It has been put into practical use to confine ceramic particles in the formed resin film.

[Problem that the invention seeks to solve]

Processing to give such a dry and cool feeling,
It is being considered to apply it not at the fabric stage, but at the skein-dyed stage or product-dyed stage. However, even if the above-mentioned treatments are applied to skein-dyed products, due to their bulkiness and amorphous shape, a large amount of moisture moves during drying, resulting in the resin flowing and creating unevenness in the resin film. . Therefore, a difference in texture occurs in the resulting product, which is undesirable. In addition, in the case of dyed products, there is no curing process other than embroidery, button attachment, etc. after drying and setting with steam, so even if ceramic particles and resin are applied, the ceramic particles The adhesion is insufficient and there is no washing durability.

In addition, it is expected that if far-infrared emitting ceramic particles, rather than just ceramic particles, are fixed to skein-dyed or product-dyed products, it will become a clothing material with high heat retention effect, but for the same reason as above. , it has not yet been put into practical use.

The present invention was developed in view of the above circumstances, and provides skein-dyed products and product-dyed products made of cellulose fibers that have been treated with ceramics to have excellent washing durability, giving them unprecedented dryness and heat retention properties. The purpose is to provide the manufacturing method.

[Means for solving problems]

In order to achieve the above object, the present invention covers the fiber surface of a cellulose-based textile product dyed with skein dyed or product dyed with ceramic particles distributed thereon, and the surface of the fiber is coated with a reactive resin capable of covalently bonding with cellulose. The first aspect is a process of treating the fiber surface of a cellulose-based textile product that has been skein-dyed or product-dyed with a liquid containing ceramic particles, and the above-mentioned treatment at the same time as or after the treatment with the liquid containing ceramic particles. A method for producing a cellulose-based fiber product, comprising a step of treating the cellulose-based fiber product with a resin liquid of a reactive resin capable of covalently bonding with cellulose, and a step of dehydrating and pre-drying the treated product, followed by curing. This is the second gist.

[Effect]

In other words, the present inventors have conducted research from various directions on methods for applying durable ceramic treatment to cellulose fiber products that are skein-dyed or product-dyed products. By supplying ceramic particles and dispersing them on the fiber surface, and then coating the top with a reactive resin that can covalently bond with cellulose, the ceramic particles will be uniform and strong with cellulose fibers. The inventors have discovered that because they are trapped in a resin film that adheres to the resin, it is possible to obtain assembled products and dyed products that have excellent washing resistance and a uniform texture, and have thus arrived at the present invention. Furthermore, it has been found that among ceramic particles, when ceramic particles with a particularly high far-infrared radiation effect are used, skein-dyed products and product-dyed products with excellent heat retention can be obtained, and their uses will be expanded.

Next, the present invention will be explained in detail.

The present invention is directed to thread-like cellulose fibers dyed with skein or product-shaped products dyed. The above-mentioned "cellulose fiber" refers to fibers mainly composed of cellulose, such as regenerated cellulose fibers such as cotton, viscose rayon, and copper ammonia rayon. Although one purpose of the present invention is to impart a dry feel and a cool feeling similar to linen, it is also possible to impart a more durable dry feel or cool feel to linen, or to increase heat retention. The present invention may also be applied to. Therefore, in the present invention, cellulose fibers include hemp. Note that the above-mentioned skein-dyed products and product-dyed products also include unfinished products obtained by performing scouring treatment or the like without using dyes.

The cellulose-based fiber product of the present invention is obtained by subjecting the fiber surface of the above-mentioned collected product or product-dyed product to ceramic treatment, for example, as follows.

(1) Bonding of ceramic particles to the surface of cellulose fibers Ion-modified ceramic particles are supplied to the surface of cellulose fibers of skein-dyed products or product-dyed products. The surface of cellulose fibers is not particularly ionized, and there seems to be no need to ionize the ceramic particles, but it is preferable to ionize the fibers in relation to the resin that will be applied to the fiber surface in the next step. It is. As for the supply method, the solution containing ion-modified ceramic particles may be supplied in the same manner as the dye solution is supplied in dyeing. The above-mentioned ion-modified ceramic particle-containing liquid is a dispersion liquid in which ceramic particles are dispersed in a dispersion medium such as water in a suspended state or a sol state;
Alternatively, it is an aqueous solution such as a colloidal solution. The ceramic particles are TiO□.

S to,,ZrO,,ZnO,AP! ,,O,,Sn
O
or ZrO□, etc. are used. Examples of the liquid containing ion-modified ceramic particles include commercially available cation-modified colloidal silica (CLA-530, manufactured by Kyoei Yuushi Kagaku Kogyo Co., Ltd.) and cation-modified titanium oxide solution (PCY).
, manufactured by Nikko Chemical Laboratory), cation-modified aluminum oxide solution (PCY-2, manufactured by Nikko Chemical Laboratory), and the like. Note that two or more types of ceramic particles may be supplied to the fiber surface by mixing different types of ceramic particles into the ion-modified ceramic particle-containing liquid. Further, different types of ion-modified ceramic particle-containing liquids may be mixed and used.

The particle diameter of the ceramic particles used is 5 to 50 mμ.
It is preferable to set it to about (millimicrons). In other words, if the particle size is smaller than 5 mμ, the modification effect of the obtained product is not sufficient, whereas if the particle size is larger than 50 mμ, coarse stiffness becomes strong and there is a tendency for the ceramic particles to easily separate from the fiber surface. It is from. In addition, the blending amount of ceramic particles is 0.02 to 4.0
%ohf (pure weight relative to fiber weight, the same applies hereinafter), particularly preferably set to 0.2 to 3.0% ohf.

Within this range, the modification effect is particularly high.

(2) Fixation of ceramic particles with resin A reactive resin capable of covalently bonding with cellulose and a catalyst suitable for crosslinking the resin are supplied to the textile article to which ceramic particles have been supplied as described above.

Then, by proceeding with the crosslinking reaction three-dimensionally in the curing process, which will be described later, the ceramic particles are filled into the amorphous region of the fiber, and a resin film is formed to cover the fiber surface, so that the ceramic particles are firmly attached to the fiber. Fix it. In order to form the above-mentioned resin film, the blending amount of the resin used is 0.7 to 10.0% owf, particularly 2.0 to 7.0% owf.
It is preferable to set it to about 0% owf (all calculated in terms of pure content).

Examples of the resin include cationic polyamide epichlorohydrin resins, polyurethane resins, glyoxal resins, and glyoxal resins are particularly preferred. However, ordinary glyoxal-based resins produce formalin when reacting with cellulose, which is unfavorable in terms of formalin regulations for clothing. Therefore, in the present invention, low formalin type glyoxal resins are particularly suitable. Incidentally, the glyoxal resin has the following structural formula, and forms a coexisting bond with recellulose through the following reaction. This reaction formula is shown below.

Structure of normal glyoxal resin> Structure of low formalin type glyoxal resin Reaction of glyoxal resin and cellulose> Normal type In this way, when the above resin is supplied to the surface of cellulose fiber, Forms strong covalent bonds with the surface of cellulose fibers to form a highly durable resin film. Therefore, since the ceramic particles are wrapped in this resin film, they do not easily fall off from the fiber surface, and their characteristics do not change even after repeated washing.

It should be noted that there is no problem in supplying the resin and the supply of the ceramic particles in a separate step or at the same time.

(3) Dehydration and pre-drying After the textiles supplied with the above resin are subjected to centrifugal dehydration,
Pre-drying is carried out using hot air drying, such as hanging, net conveyor, tunnel drying, or high frequency drying.

(4) Curing After the above pre-drying, curing is performed by continuing drying under certain conditions. The above drying is carried out by hot air drying at a temperature of about 90 to 130"C. Through this drying, a crosslinking reaction proceeds three-dimensionally within the resin supplied to the surface of the cellulose fibers, and the encapsulated ceramic particles are The tree Bl in the confined state becomes missing.

By fixing the ceramic particles, the cellulose-based fiber products obtained in this way have a dry, cool feel similar to linen, even if they are cotton or recycled fibers. This texture remains intact even after repeated washing. Furthermore, when a linen product is subjected to the above-described treatment, it has the advantage that the texture of the linen product itself is further strengthened and its washing resistance is improved.

Furthermore, since these fiber products are made of cellulose fibers, they also have excellent water absorbency. Therefore, the cellulose-based fiber product of the present invention can be used as a material for summer clothing, sports clothing, underwear, etc., and has an unprecedented feel and function. Furthermore, if ceramic particles with a high far-infrared radiation effect are used, not only will the above-mentioned texture be added, but the heat retention will also be enhanced. Therefore, it is a particularly excellent material for underwear and the like.

Next, examples will be described together with comparative examples.

[Examples 1 to 7, Comparative Examples 1 to 12] First, a cotton yarn (30/1) was prepared as a test yarn. Then, total dyeing was carried out using the following chemicals and following the usual procedure.

medicine Scouring - 35% hydrogen peroxide 5 cc/l.

Bleaching - Caustic soda 2 g/1 Polyoxyethylene allyl phenyl ether type activator 1 g/2 Dyeing - Cibacron Yellow F-3R0,
14%owfScarlet P-3G O, 07%
owf81ue F-R0,05%owf (all manufactured by Ciba Geigy) Crystal Glauber's Salt 60g/f! Sequestering agent: 2 g/2 Soda ash: 10 g/f Washing - Polyoxyethylene allyl phenyl ether type activator: 0.5 g/42 In other words, using the above chemicals, scouring and bleaching are performed at 100°C for 30 minutes, followed by dyeing. The temperature was started at 30°C, raised to 60"C in 30 minutes, and held for 10 minutes.

Then, soda ash was gradually added and held for 30 minutes after the entire amount was added. Thereafter, washing was performed at 90°C for 10 minutes, followed by washing with hot water and water to complete the treatment.

Then, using the thread dyeing machine used for dyeing, ceramic particles were supplied onto the fiber surface of the thread, and at the same time, a resin liquid was supplied. Feeding was carried out for 40'C x 10 minutes.

The following ceramic particles and resin liquid were prepared. After the name of a substance, the ionic properties of that substance are indicated by A (anion).

They were distinguished by the symbols C (cation) and N (nonion).

<Ceramic particles> ■ Colloidal silica: CLA-530 (manufactured by Kyoei Yuushi Kagaku Kogyo Co., Ltd.) (C) 5% o
wf ■Anion-modified colloidal silica: 5yntharesin K-45 (manufactured by Bayer) (
A) 5% owf <Resin liquid> ■Polyamide epichlorohydrin resin: Boramin 12
0X (manufactured by Toho Chemical Co., Ltd.) (C) 5% oivf ■Polyurethane resin: M4041 (C) 5% owf Elastron Catalys 1-64 0.25% owf Cateogen ES-L O, 5% ohf Unigard M-130, 25% owf (manufactured by Dai-ichi Kogyo Co., Ltd.) ■Polyurethane resin: Elastron H38 (A) 5% owf Elastron Caclyst 640.25% ouf (manufactured by Dai-ichi Kogyo Co., Ltd.) ■Vinyl acetate copolymer resin: Marbosol E100 (manufactured by Matsumoto Yushi Co., Ltd.) (N) 5%o
wf ■Vinyl acetate copolymer resin: Vinyl)) Is (manufactured by Kyoei Yushi Kagaku Kogyo Co., Ltd.) 5% oiy
f ■Polyacrylate resin: Marbosolt 1 (manufactured by Matsumoto Yushi Co., Ltd.) (A) (N) 5% 0 revision ■Polyacrylate resin: Meikaset HA-1 (manufactured by Kaisei Chemical Co., Ltd.) (N) 5%ow
f ■Modified polyvinyl alcohol resin: KYN-187 (manufactured by Ippo Ltd.) (N) 5% owf ■Water glass: Sodium silicate No. 3 (manufactured by Keihin Kasei Co., Ltd.) (A) 10% oi+f [Phase] Glyoxal resin: Sumitetsu Thresin N5-19 (C) 10% Sumitex Accelerator Resin: Riken Resin MS-71 (C) 10% 03% owf 10% owf Riken Fixer MX-23% owf ■Glyoxal resin: Riken Resin MS-26 (C) 10% 0 3% owf Riken Fixer LTC-282% owf (manufactured by Miki Riken Co., Ltd.) [Phase] Glyoxal resin: Fixapret COC10%owfConden
sol FB 2% owf (manufactured by BASF) The certified yarn supplied with the ceramic particles and resin was taken out from the dyeing machine and dehydrated and dried under the following conditions to obtain the intended dyed product.

Dehydration conditions> Dehydration was performed using a centrifugal dehydrator to bring the moisture content to 50%.

Drying Conditions> Hot air drying was performed at 110'C for 30 minutes to complete preliminary drying, and then curing was continued for an additional 30 minutes.

Then, each yarn was made into a knitted fabric with the same specifications using a dosing machine, and a practical washing test (JIS 021?, 103 method) was conducted to examine the texture after practical washing. The results are shown in the first section below.
Shown in the table.

(Hereinafter, blank spaces) From the above results, it can be seen that all the products using the cationic resin have a good texture. Among these, it can be seen that the products of Examples 3 to 7 using glyoxal resin are particularly excellent in yarn unwinding properties and are practical. On the other hand, it can be seen that all comparative products using anionic or nonionic resins had poor thread unwinding properties or poor texture after washing, and could not achieve the object of the present invention.

[Example 8] Cotton yarn (20/2) was circularly knitted into a knitted fabric, then cut into a predetermined shape according to a pattern and sewn to obtain a molded article in the shape of a women's sweater. Then, this molded product was dyed using a drum dyeing machine under the following conditions.

<Medicines> Scouring - Scouring agent 2 g/1 Caustic soda 2 g/! Bleach - 35% Hydrogen Peroxide 3 cc/e Stabilizer PDN 3g/l Dyeing - 3umif
ix 5upra Yellow 3RF 0.15
%Br111. Red 3BF 0.04%Blue
8RF 0.07% (manufactured by Sumitomo Chemical Co., Ltd.) Crystalline Glauber's Salt 50g/f Soda Ash 15 Gel Cleaning - Cleaning Agent
2g/2, that is, using the above agent, scouring at 95°C for 20 minutes, then bleaching at 95°C.
I went for X45 minutes.

After staining at 50°C for 60 minutes, washing was carried out at 90°C.
CX was carried out for 15 minutes to complete the treatment.

Then, using the drum dyeing machine used for dyeing, the following ceramic particles and resin liquid were successively supplied to the fiber surface of the molded article. Feeding was carried out for 10 minutes at 40°C.

Ceramic particles> CLA-5305%owf Resin liquid> Sumitex Resin N5-19 10%owf Sumitex Accelerator x-80wf wf ivf 3% Drying (1
00°CX 30 minutes) and curing (105”CX 3
0 minutes) to obtain the desired dyed product.

[Comparative Example 13] After supplying ceramic particles and resin liquid, drying was carried out at 100%
No curing was performed except for 30 minutes at °C (normal drying conditions). Other than that, the dyed product was obtained in the same manner as in Example 8 above.

A practical washing test (JIS 0217,103 method) was conducted on the 8 products of Examples and 13 products of Comparative Examples thus obtained to examine changes in texture and silicon content due to washing.

These results are shown in Table 2 below.

Note that the above silicon content was measured using a fluorescent X-ray analyzer (manufactured by Rigaku Denki Kogyo Co., Ltd.).

(Hereinafter, blank space) From the above results, it can be seen that the product of Example 8 has excellent washing resistance. On the other hand, since the product of Comparative Example 13 was not cured, the silica particles fell off immediately and the texture did not have wash resistance, making it impractical.

Regarding Example 3 and Example 8, formalin?
To determine whether the volume would be a problem, the amount of formalin eluted was measured according to the acetylacetone method. The results are shown in Table 3 below.

On the other hand, the formalin regulation values based on the Ministry of Health and Welfare (No. 34) are as follows, and it can be seen that all of the specific products can be applied to various types of clothing except for infant clothing.

<Formalin regulation value> For infants...A-Ao≦0.05 Underwear: 75 PPM or less For middle table...300PPM or less For outer clothing: 500 PPM or less *Note that PPM=μg/g.

[Example 9] A molded article in the shape of a women's sweater was made using cotton yarn (20/2), and a dyed article was made in the same manner as in Example 8.

Then, using the drum dyeing machine used for dyeing, the following ceramic particles and resin liquid were subsequently supplied to the fiber surface of the molded product. Feeding was carried out for 10 minutes at 4°C.

<Ceramic particles> Cation-modified aluminum oxide solution (PCY-2, manufactured by Nikko Chemical Laboratories) Solid content equivalent: 2.0% owf <Resin liquid> Sumitex Resin N5-19 (manufactured by Sumitomo Chemical) 1
5% oivf Sumitex Accelerator X-80 (same as above) 5%ow
f After washing with hot water and water, centrifugal dehydration and tumble drying (1
00 x 30 minutes) and curing (105”c x t
o minutes) to obtain the desired dyed product.

[Example 10.11] Using the ceramic particles used in Example 9,
Other than that, a dyed product was obtained in the same manner as in Example 4 (
Example 10). Further, a skein-dyed product was obtained in the same manner as in Example 7 except that the same ceramic particles used in Example 9 were used (Example 11). Then, each of these is knitted (texture: jersey, weight: 210g
/Bo) did.

[Comparative Examples 14 and 15] Products were dyed in the same manner as in the first part of Example 9 to produce untreated dyed products (comparative example 14 products) that were not treated with ceramic particles or resin liquid. In addition, according to the usual method, untreated dyed products (comparative example 15 products) that were not treated with ceramic particles and resin liquid were made and knitted (texture: jersey, basis weight: 320 g/rrf).
did.

The following tests were conducted on these dyed products and certified knitted products.

<Heat retention evaluation test> The power consumption of the heater was measured using a Thermolab ■ model (manufactured by Kato Chick Co., Ltd.) while maintaining the plate temperature at 36.5'C. The environment was 20″C x 65% R1+ with no wind.

Therefore, the higher the heat retention effect, the smaller the value.

<Far-infrared radiation ability evaluation test> The far-infrared rays emitted from each dyed product and finished product were measured using a far-infrared power meter (manufactured by Optex). Measurements were performed when each product was heated to 28°C and 100°C.

<Washing resistance of imparted ceramic particles> Practical washing (J
The amount of aluminum before and after (IS 0217,103 method) was measured using a fluorescent X-ray analyzer (manufactured by Rigaku Denki Kogyo Co., Ltd.).

The results of these tests are shown in Table 4 below.

From the above results, it can be seen that the tested product has better heat retention than the comparative product, and moreover, the ceramic particles supplied to the fiber surface hardly fall off even after repeated washing.

[Effects of the Invention] As described above, in the cellulose-based fiber product of the present invention, the ceramic particles are coated and fixed with a special resin while being distributed on the fiber surface, so that they do not fall off when washed. Therefore, even after repeated washing, the linen-like dry feel and cool sensation derived from ceramic particles, as well as the heat retention provided by far-infrared radiation, are maintained for a long time, something that could not be achieved with conventional skein-dyed or product-dyed products. It achieves excellent effects.

Claims (4)

[Claims] (1) Cellulose, characterized in that ceramic particles are distributed on the fiber surface of a cellulose-based textile product dyed with skeins or product dyed, and the surface is coated with a reactive resin capable of covalently bonding with cellulose. Textile products. (2) The cellulose-based fiber product according to claim 1, wherein the ceramic particles are a far-infrared emitting substance. (3) The reactive resin capable of covalently bonding with the cellulose is
Claim (1) is a low formalin type glyoxal resin.
) or the cellulose-based fiber product described in (2). (4) A process of treating the fiber surface of the skein-dyed or product-dyed cellulose-based textile product with a solution containing ceramic particles, and simultaneously or after the treatment with the ceramic particle-containing solution, the cellulose-based textile product is shared with cellulose. a step of treating with a resin liquid of a reactive resin capable of binding;
A method for producing a cellulose-based fiber product, comprising the steps of dehydrating and pre-drying the treated product, followed by curing.