JP2001172868A - Deodorant cellulose fiber structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both a cellulose-based fiber structure and fiber product exhibiting deodorizing effect on basic low-molecular weight compounds such as ammonia, amine compounds, etc., and lower fatty acids such as acetic acid, isovaleric acid, etc., without impairing feeling of fabric such as woven fabric, knit fabric, nonwoven fabric, etc. SOLUTION: This deodorant cellulose-based fiber structure is characterized in that the fiber structure contains a cellulase fiber subjected to graft polymerization with 2-30 wt.% of a hydrophilic vinyl-based monomer and exhibits deodorizing effect simultaneously on both substances of offensive smell of basic low- molecular weight compounds such as ammonia and amine compounds and lower fatty acids.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fibrous structure made of cellulose fibers having excellent deodorizing properties for use in dress shirts, blouses, sports shirts, underwear, bedding, work clothes, uniforms, curtains, socks, gloves and the like. And textile products.

[0002]

2. Description of the Related Art Various attempts have been made to impart deodorant properties to cellulose fibers. For example, a method of fixing porous ceramic fine particles inside the fiber with a silane coupling agent (Japanese Patent Application Laid-Open No. 6-116862), a method of fixing a metal phthalocyanine compound (Japanese Patent Application Laid-Open Nos. 6953, JP-A-7-331596), sulfuric acid
Method for providing iron and L-ascorbic acid (Japanese Patent Laid-Open No. 61-2961)
Japanese Patent Application Publication No. Sho 63-222978), a method of providing an extract from a natural Camellia plant (Japanese Patent Publication No. 61-22978), and a method of metal-complexing carboxylated cellulose with copper or zinc (Japanese Patent Application Laid-Open No. 63-2).
No. 7090), a method in which a polyaldehyde vinyl carboxylate polymer is used in combination with a cellulose-reactive resin (JP-A-54-13109).
No. 9), a method of providing a low polymer of an alkyl methacrylate (JP-A-63-28871) and the like have been proposed.

[0003] However, water-insoluble compounds such as porous ceramic fine particles and metal phthalocyanine are fixed to cellulose fibers with a binder resin. In addition, ascorbic acid and extracts from natural plants have drawbacks such as deterioration due to heat treatment during processing and have no washing durability. On the other hand, the method of complexing carboxylated cellulose with a metal such as copper or zinc has washing durability, but has a drawback in that the fabric texture is hardened by carboxylation.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a cellulose fiber structure, which does not impair the texture of fabrics such as woven fabrics, knitted fabrics and non-woven fabrics, and is not affected by a binder and has a basic property such as ammonia and amine compounds. An object of the present invention is to provide a fiber structure and a fiber product characterized by exhibiting a deodorizing effect on low molecular weight substances and lower fatty acids such as acetic acid and isovaleric acid.

[0005]

In order to achieve this object, the fiber structure of the present invention has the following constitution. That is, 1. It is composed of cellulose fibers grafted with 2 to 30% by weight of a hydrophilic vinyl-based monomer, and exhibits a deodorizing effect on both odorants of basic low molecular weight compounds such as ammonia and amine compounds and lower fatty acids at the same time. Deodorant cellulose fiber structure. Further, 2. The hydrophilic vinyl monomer is a carboxylic acid vinyl compound, the absorbance ratio of 1711cm ^-1 and 1558cm ^-1 in the infrared spectrum is
2. The deodorant cellulose fiber structure according to the above 1, which contains 5 to 60% by weight of a graft-polymerized cellulose fiber between 100 and 80/0 and 20. Also, 3. 2. The deodorant cellulose fiber structure according to 1 above, which has a deodorant function for a basic low molecular compound, a lower fatty acid and nonenal, in which a metal compound having a photocatalytic function is added to the fiber structure.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

[0007] The cellulose fiber in the present invention is a fiber having a cellulose skeleton such as cotton, hemp and rayon.

[0008] The fiber structure and the fiber product in the present invention are made of woven fabric, knitted fabric, non-woven fabric, etc., made of cotton (cotton) mainly composed of cellulose fiber. In the process, fibers other than cellulose fiber are mixed. Is also good. As fibers other than cellulose fibers to be mixed, polyester fibers, polyamide fibers, nylon fibers, synthetic fibers such as acrylic fibers,
Examples include, but are not limited to, recycled or semi-synthetic fibers such as rayon fiber and triacetate fiber, and natural fibers such as silk and wool.

The graft-polymerized cellulose fiber in the present invention is a cellulose fiber having a graft ratio of 2 to 30% by weight and a hydrophilic vinyl-based monomer graft-polymerized in a cotton state. It can simultaneously deodorize both basic low molecular weight compounds and lower fatty acid odorous substances. If the graft ratio of the cellulose fibers is less than 2% by weight, the effect is not sufficient. On the other hand, if it exceeds 30% by weight, the hardening of the cotton and the decrease in the elongation occur, and the subsequent spinning process is difficult to pass.

In the present invention, the hydrophilic vinyl monomer has a polymerizable vinyl group in its molecular structure and has an acidic group such as carboxylic acid and sulfonic acid and / or a salt thereof, a hydroxyl group, an amide group and the like. It is a monomer having a hydrophilic group.

Among these, preferred are carboxylic acid vinyl compounds, specifically, carboxylic acid vinyl compounds, such as acrylic acid, methacrylic acid, maleic acid, and the like.
Examples thereof include crotonic acid and butenetricarboxylic acid, and metal salts thereof. These may be used alone or in combination. Of these, methacrylic acid and acrylic acid are preferred from the viewpoint of graft polymerizability.

When these monomers are graft-polymerized to a cotton fiber, these monomers are used together with these monomers as a polymerization initiator such as a redox system such as hydrogen peroxide and a ferrous iron salt, a peroxide such as potassium persulfate or ammonium,
Azo-based polymerization initiators such as 2,2-azobis hydrochloride and cerium salts such as diammonium cerium nitrate are used. As the polymerization initiator, a method of adding the polymerization initiator into a processing bath, a method of previously applying the polymerization initiator to fibers, and the like can be employed.

As a method for graft-polymerizing a hydrophilic vinyl monomer in the state of cotton, cellulose fibers are immersed in a processing bath such as an Overmeyer processing machine and heat-treated. The processing conditions are usually 50 ° C. or higher and 150 ° C. 180mi below 5min
n or less, preferably from 30 ° C. to 120 ° C. for 30 min to 120 min. The processing atmosphere is preferably a nitrogen gas atmosphere. Thereafter, a deactivation treatment and a washing treatment of the polymerization initiator, an oil agent application, and a drying treatment are performed as necessary.

As the graft polymerization method, radiation,
A method using an active energy ray such as an electron beam, an ultraviolet ray, and a microwave can also be adopted.

When the graft polymerization of a hydrophilic vinyl monomer is carried out in the state of a fabric such as a woven fabric, a knitted fabric, or a nonwoven fabric,
When dyeing using a reactive dye or a direct dye, etc., the texture becomes hard, the dye and the fiber are repelled by ions, the color becomes lighter, the light fastness is poor, and the color matching at the time of dyeing becomes difficult. Although there is a problem, if cotton mixed with a hydrophilic vinyl-based monomer in the state of cotton as in the present invention is mixed with other cotton by blending, blending, etc., less texture hardening, less tendency to lighten, and light resistance This has the effect of improving the robustness.

When the cotton grafted in the state of cotton in the present invention is mixed with ordinary raw cotton, it is important that the cotton obtained by graft polymerization of a carboxylic acid-based vinyl monomer has an infrared spectrum (hereinafter referred to as IR spectrum). ) absorbance ratio of 1711cm ^-1 and 1558cm ^-1 in is that is between 100 to 80/0 to 20. If the absorbance ratio between 1711 cm ^-1 and 1558 cm ^-1 is less than 80, the graft-polymerized cotton may be hardened and agglutinated, which may hinder the subsequent spinning process.

1711 cm ^-1 in the infrared spectrum (hereinafter referred to as IR spectrum) is the absorption derived from the carboxylic acid [--COOH].

1558 cm ⁻¹ in the infrared spectrum (hereinafter referred to as IR spectrum) is the absorption derived from the conversion of carboxylic acid [—COOH] to alkali metal salt [—COONa].

Next, the mixing ratio of cotton graft-polymerized with a carboxylic acid-based vinyl monomer will be described. As the mixing ratio increases, the amount of carboxylic acid [-COOH] increases,
The effect of the deodorant function is large for basic low molecular weight compounds such as ammonia and amine compounds and lower fatty acids such as acetic acid and isovaleric acid, but if the mixture ratio is too high, the texture becomes hard and the color tends to become pale. . In consideration of these, the mixing ratio of the graft-polymerized cotton is usually 5 to 60% by weight, and from the balance between cost and performance, it is preferably 10 to 5% by weight.
0% by weight.

The fabric made of the mixed yarn of the graft-polymerized cotton is subjected to a usual subbing and dyeing process. At this time, 1711 cm ^{-1 in} the IR spectrum of the fiber in the final product
The absorbance ratio at 1558 cm ^-1 is [-COOH / -COONa] = [70 to 20/3
0-80]. Outside this range, no deodorizing effect can be obtained for both odorants of basic low molecular weight compounds such as ammonia and amines and lower fatty acids such as acetic acid and isovaleric acid. Normal acids and alkalis are used for the adjustment.

Both the acid form and its metal salt form, such as the carboxylic acid [-COOH] and alkali metal salts of carboxylic acids such as [-COONa] and [-COOKa], are obtained by graft polymerization of a hydrophilic vinyl monomer. The presence of both cellulose fibers has a high deodorizing effect on both basic odor substances such as ammonia and amine compounds and lower fatty acids such as acetic acid and isovaleric acid. Can be obtained.

Furthermore, deodorizing effects can be obtained by applying a metal salt compound having a photocatalytic function to nonenal, which is one of the body odor substances.

By adding a metal compound having a photocatalytic function to a fibrous structure and a fiber product in which cellulose fibers in which a hydrophilic vinyl-based monomer is polymerized in the form of cotton are added, such as ammonia and amine compounds. It is possible to obtain a fiber structure and a fiber product having a deodorizing function even with respect to basic low molecular compounds, lower fatty acids such as acetic acid and isovaleric acid and aldehyde compounds such as nonenal, formaldehyde and acetaldehyde.

As the metal compound having a photocatalytic function,
Examples include, but are not limited to, acidic titanium oxide, titanium oxide photocatalyst, aluminum sulfate, and the like. If the amount of the metal compound applied is too large, the dehydration effect before the application can be satisfied with lower fatty acids such as acetic acid and isovaleric acid and basic low molecular weight compounds such as ammonia and amine compounds. The odor effect cannot be obtained. Further, when the amount of the metal compound having a photocatalytic function is too large, the hand becomes hard. With these things in mind,
Usually, a basic low-molecular compound, a lower fatty acid, nonenal, by giving a metal compound having a photocatalytic function to 0.1 to 3% by weight with respect to 100% by weight of a fiber structure and a fiber product in which a graft-polymerized cellulose fiber is mixed. A deodorizing effect can be obtained for all of the aldehyde compounds without being affected by decomposition of the binder. In addition, the nonenal deodorizing property of the metal compound having a photocatalytic function is remarkably effective in a fabric containing a hydrophilic vinyl-based monomer-grafted cotton.

As a method for applying a metal compound having a photocatalytic function to a cellulose fiber structure, spray treatment,
Any method such as padding, immersion, and impregnation may be used. The drying temperature is about 80 ° C or more and 200 ° C or less, 30 seconds or more and 60 minutes, preferably about 95 ° C or more and 120 ° C or less, 1 minute or more and 30 minutes or more.
It is desirable to carry out in min or less. After drying, curing may be optionally performed. The curing is preferably performed at about 130 ° C. or more and 180 or less and for 30 seconds or more and 10 minutes or less.

The adhesive used for fixing the metal compound having a photocatalytic function includes a polyurethane-based cross-linkable resin, an acrylic-based cross-linkable resin, a silicone-based cross-linkable resin, and the like.
Examples thereof include an epoxy-based cross-linkable resin, a polyamide-based cross-linkable resin, and a polyester-based cross-linkable resin, and may be used alone or in combination.

[0027]

The present invention will be specifically described below with reference to examples. The evaluation method of the fiber structure and the fiber product in Examples and Comparative Examples is as follows.

Measurement method of ammonia deodorization rate: 5 g of fiber is put in 3 L of Tedlar bag (made of vinylidene fluoride film) and sealed, and 2 L of nitrogen gas is further put. Next, enclose ammonia to a concentration of 100 ppm, 60 mi
After leaving for n, the ammonia concentration was measured using a gas detector tube. From the rate of decrease in the concentration, the deodorization rate of ammonia was calculated.

Measurement method of trimethylamine deodorizing rate: 3 g of Tedlar bag (made of vinylidene fluoride film) and 5 g of fiber
And sealed, and then 2 L of nitrogen gas. next,
Trimethylamine was sealed to a concentration of 20 ppm, left for 60 minutes, and then the concentration of trimethylamine was measured using a gas detector tube. The deodorizing rate of trimethylamine was calculated from the decreasing rate of the concentration.

Measurement method of acetic acid deodorization rate: 5 g of fibers are sealed in 3 L of Tedlar bag (made of vinylidene fluoride film), and the mixture is further sealed with 2 L of nitrogen gas. Next, add 20 pp of acetic acid
m, and left for 60 minutes, and then the acetic acid concentration was measured using a gas detector tube. From the concentration decrease rate, the acetic acid deodorization rate was calculated.

Measuring method of deodorizing rate of isovaleric acid: 5 g of fiber is put in 3 L of Tedlar bag (made of vinylidene fluoride film), sealed, and 2 L of nitrogen gas is put. Next, isovaleric acid was sealed to a concentration of 20 ppm, left for 60 minutes, and then the isovaleric acid concentration was measured using a gas detector tube. The deodorizing rate of isovaleric acid was calculated from the concentration decreasing rate.

Evaluation method of nonenal deodorizing property: Deodorizing property was evaluated on a six-point scale by six subjects, and the average score was displayed. 1: Odorless. 2: I don't know what smell, but it's the strength to feel something slightly. 3: A weak smell that tells what the smell is. 4: The smell is clearly felt. 5: Strong smell. 6: Strong smell.

Dyeability: The dyeing density and uniformity were evaluated by a four-point evaluation method when a cotton fabric was dyed under the same conditions. A: Stained uniformly without changing dyeing concentration. ：: The dyeing density is slightly low, but the dyeing is moderately uniform. Δ: The dyeing density was low and the dyeing was not uniformly performed. ×: The staining concentration is significantly light. Lack of uniformity.

Texture: The texture as to whether the texture is hard was determined by a three-point evaluation method by eight experts and displayed as the average score. A: Not hard. ○: Normal. X: Hard.

Measurement of IR spectrum: IR microscopy (BIO-RAD)
FTS-40: Japan Bio-Rad Laboratories) was used to determine the absorbance ratio between 1711 cm ⁻¹ and 1558 cm ⁻¹ .

Measurement of graft ratio (GT%): From the absolute dry weight (W0) before the reaction, the absolute dry weight (W1) after graft polymerization and washing.
Calculated from the rate of weight increase. Graft rate (GT%) = (W1-W0) x 100 / W0

Method for producing fibers grafted with hydrophilic vinyl monomer: scoured cotton is converted to methacrylic acid.
20.0 g / l, ferrous ammonium sulfate 0.6 g / l, hydrogen peroxide 0.
Graft polymerization treatment was carried out using a 3 g / l aqueous solution at a bath ratio of 1:40 and 80 ° C. × 60 min using an Overmeyer processing machine. After this,
Water washing and hot water washing were repeated. The graft ratio at this time is about 10.1
5%. The treated cotton is hereinafter referred to as “GTI cotton”.

"GTI cotton" was immersed in an aqueous solution of sodium hydroxide 0.1 g / l at a bath ratio of 1:40, 90 ° C. × 10 min, using an Overmeyer machine. Thereafter, washing with water and washing with hot water were repeated. The treated cotton is hereinafter referred to as “GTII cotton”.

The scoured cotton was treated with 35.0 g of methacrylic acid /
l, an aqueous solution containing 1.5 g / l of ferrous ammonium sulfate and 0.8 g / l of hydrogen peroxide was immersed in a bath ratio of 1:40 at 80 ° C. for 60 minutes using an Overmeyer processing machine. Thereafter, washing with water and washing with hot water were repeated. The graft ratio at this time was about 35.01%.
The treated cotton is hereinafter referred to as “GTIII cotton”.

The absorbance ratio [-COOH / -COONa] of the IR spectrum of the above-mentioned GTI to III cotton was measured. Table 1 shows the results of the spinnability in the spinning process.

[0041]

[Table 1]

Example 1 50% by weight of "GTI cotton" and 50% by weight of raw cotton
From 40th spun yarn is made from broad woven fabric (warp 40th cotton yarn × weft 40th cotton yarn / warp density 130 yarns / 2.54cm ×
Weft density: 70 yarns / 2.54 cm).

Example 2 The blending ratio of “GTI cotton” was 25% by weight, and the blending ratio of raw cotton was 75% by weight.
From 40th spun yarn is made from broad woven fabric (warp 40th cotton yarn × weft 40th cotton yarn / warp density 130 yarns / 2.54cm ×
Weft density: 70 yarns / 2.54 cm).

Example 3 The mixing ratio of "GTI cotton" was 10% by weight, and the mixing ratio of raw cotton was 90% by weight.
From 40th spun yarn is made from broad woven fabric (warp 40th cotton yarn × weft 40th cotton yarn / warp density 130 yarns / 2.54cm ×
Weft density: 70 yarns / 2.54 cm).

Comparative Example 1 A spun yarn of 40th yarn was prepared from a blending ratio of "GTI cotton" of 70% by weight and a blending ratio of unprocessed cotton of 30% by weight, and a broad woven fabric (40th cotton yarn × weft 40th cotton yarn) was prepared. / Warp density 130 yarns / 2.54 cm × weft density 70 yarns / 2.54 cm).

Comparative Example 2 The mixing ratio of "GTI cotton" was 4% by weight, and the mixing ratio of raw cotton was 96% by weight.
From 40th spun yarn is made from broad woven fabric (warp 40th cotton yarn × weft 40th cotton yarn / warp density 130 yarns / 2.54cm ×
Weft density: 70 yarns / 2.54 cm).

The woven fabrics obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were refined, bleached with chlorite, and dyed with a reactive dye at pH 5. The fiber was treated with an aqueous solution of sodium hydroxide 0.1 g / l at a bath ratio of 1:40 and at room temperature for 10 minutes to obtain a fiber product.

Comparative Example 3 The woven fabric obtained in Example 3 was refined and then bleached with chlorite.
Stained at pH 5 with direct dye. A textile product was obtained.

With respect to the woven fabrics of Examples 1 to 3 and Comparative Examples 1 to 3, the dyeing results, hand, absorbance ratio, ammonia
Table showing deodorization rate results of trimethylamine, isovaleric acid, and acetic acid
See Figure 2.

[Table 2]

Titanium oxide (particle diameter: 10 nm, manufactured by Ishihara Sangyo Co., Ltd.) and a self-crosslinkable acrylate-based binder (Boncoat AB885, Dainippon Japan) were added to the fiber product obtained in Example 2 so as to give the amount shown in Table 3. (Manufactured by Ink Co., Ltd.), followed by drying at 100 ° C. for 2 minutes and curing at 145 ° C. for 3 minutes to obtain Examples 4 to 5 and Comparative Examples 4 to 5.

[0051]

[Table 3]

The deodorizing rates (%) of the fiber products obtained in Examples 4 to 5 and Comparative Examples 4 to 5 were measured, and the results are shown in Table 4.

[0053]

[Table 4]

[0054]

The fibrous structure of the present invention, in which cotton of the cellulosic fibers grafted with the hydrophilic vinyl monomer is mixed, has an excellent texture and deodorant properties, and is not affected by the decomposition of the binder. It is possible to provide a functional cellulosic fiber product.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kiyoshi Mori No. 50, Inukai, Daimon-cho, Imizu-gun, Toyama Prefecture Toyobo Co., Ltd. Shogawa Plant F-term (reference) 4L031 AA02 BA08 BA13 CA09 DA13 4L033 AA02 AB01 AB09 AC10 BA17 BA98 DA02 DA06 DA07

Claims (3)

[Claims] 1. The method according to claim 1, wherein the hydrophilic vinyl monomer is 2 to 30% by weight.
% Deodorant cellulose fiber structure containing graft-polymerized cellulose fibers and simultaneously exhibiting deodorizing effects on both odorants of basic low molecular weight compounds such as ammonia and amine compounds and lower fatty acids . Wherein said hydrophilic vinyl monomer is a carboxylic acid vinyl compound, the absorbance ratio of 1711cm ^-1 and 1558cm ^-1 in the infrared spectrum is graft-polymerized is between 100 to 80 / 0-20 The deodorant cellulose fiber structure according to claim 1, which contains 5 to 60% by weight of cellulose fibers. 3. The fibrous structure is provided with a metal compound having a photocatalytic function, and has a deodorizing function with respect to basic low molecular weight compounds, lower fatty acids and nonenal.
The deodorant cellulose fiber structure according to the above.