JPH04370270A - Natural cellulose fiber holding inorganic metallic compound and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title fiber having excellent washing resistance, maintaining deodorizing and antimicrobial effects for a long period of time by holding a water-insoluble inorganic metallic compound in the interior of cellulosic, fiber. CONSTITUTION:Cellulosic fiber is impregnated with an aqueous solution of metallic salt such as copper, silver, zinc, titanium or zirconium, for example, by immersion method (or vat method), the metallic salt is permeated into the yarn, treated with an aqueous solution of an acidic or alkali metallic salt and the water-soluble metallic salt is converted into the water-insoluble salt to give cellulosic yarn maintaining deodorizing and antimicrobial effects for a long period of time and having excellent washing resistance.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to natural cellulose fibers containing inorganic metal compounds and a method for producing the same.

0002

[Prior art and its problems] A method of deodorizing by reacting malodorous components such as ammonia, hydrogen sulfide, mercaptan, and trimethylamine with metal compounds such as zinc, aluminum, and copper and converting them into other substances has been known for a long time. .

On the other hand, copper compounds are known to have antibacterial and antifungal effects, oxides such as zirconium and cerium have ultraviolet absorbing ability, and zirconium oxides and carbides absorb light. It is known that these metal compounds have the property of dissipating heat, and various methods have been devised to utilize the properties of these metal compounds to impart various functionalities to fibers.

For example, attempts have been made to knead the above metal compounds into synthetic fibers such as nylon and polyester to impart functionality to the fibers. According to this method, the above-mentioned metal compound is blended when manufacturing synthetic fibers, so the desired performance is imparted to the synthetic fibers to a satisfactory extent, but it is not possible to impart the desired performance to natural fibers such as natural cellulose fibers. This kneading method cannot be applied to such cases.

Therefore, for natural cellulose fibers, a method is proposed in which a metal compound is coated on the surface of the cellulose fibers with a resin such as polyurethane (Japanese Patent Publication No. 2-102).
74, etc.), a method of supporting a reaction product of a transition metal and tannic acid on cellulose fibers (Japanese Unexamined Patent Publication No. 1-292)
No. 169, Japanese Unexamined Patent Publication No. 1-266275, etc.) have been proposed. However, none of these methods can produce natural cellulose fibers that can maintain the provided functionality over a long period of time. That is, when the former method is carried out using, for example, a zinc compound as the metal compound, the resulting deodorizing fiber has a hard finish and poor texture, and also has poor washing fastness, making it difficult to repeat this process. If you wash your clothes with a dry cloth, the deodorizing properties will drop by more than half after about 10 washes. In the latter method, tannic acid is used to bridge the cellulose fibers and transition metals, but repeated washing prevents the transition metals from gradually desorbing from the cellulose fibers due to hydrolysis, etc. Moreover, the functional fibers obtained by this method also have poor washing fastness. Therefore, as above,
When the latter method was carried out using a zinc compound as the metal compound, the resulting deodorizing fibers were repeatedly washed, resulting in 10
The deodorizing performance decreases by more than half after just a few washes.

Furthermore, JP-A-55-137210 discloses a method in which copper ions are bonded to ion exchange groups present in the surface layer of fibers having ion exchange ability, and a water-insoluble compound is further generated from the copper ions. , a sterilizing fiber containing this in the surface layer of the fiber is disclosed. however,
The hydroxyl groups of natural cellulose fibers have no ion exchange ability at all, and it is impossible to apply the invention of the above-mentioned publication to natural cellulose fibers as is. The present inventor applied the invention of the above-mentioned publication to natural cellulose fibers as is, impregnated the cellulose fibers with water-soluble metal salts, dried them, and washed them with water. As a result, most of the metal ions were washed away. It turned out that this technology could not fundamentally solve the shortcomings.

[0007]

[Means for Solving the Problems] An object of the present invention is to provide natural cellulose fibers that can maintain the various functions imparted by various metal compounds over a long period of time, and a method for producing the same.

That is, the present invention provides a natural cellulose fiber in which a water-insoluble inorganic metal compound is held inside the cellulose fiber, and a form of the water-insoluble inorganic metal compound after metal ions are introduced into the inside of the cellulose fiber. The present invention relates to a method for producing natural cellulose fibers containing a water-insoluble inorganic metal compound.

The natural cellulose fiber of the present invention is characterized in that an inorganic metal compound is held inside the cellulose fiber. Conventional techniques involve coating resin with a mixture of metal compound powder, interposing a third substance such as tannic acid that adsorbs or reacts with fibers, and forming complexes with the third substance and metal ions. method and required some kind of intervening substance. On the other hand, in the present invention, in order to change the metal ion into an insoluble metal compound and hold it inside the cellulose fiber,
No support media such as resins or other chemicals are required. The metal compound-holding cellulose fibers of the present invention do not easily lose the metal compounds even after repeated washing, and the metal compounds are not simply attached to the cellulose fibers, but are encapsulated in the amorphous structure of the fibers. It behaves as if it were.

[0010] In the present invention, natural cellulose fibers include cotton, hemp, etc., and may be a blend of these and synthetic fibers such as polyester. Further, the fiber form is not particularly limited, and includes all forms such as thread, woven fabric, knitted fabric, and nonwoven fabric.

[0011] The inorganic metal compound held inside the cellulose fibers is not particularly limited as long as it is water-insoluble, and examples include copper, silver, zinc, titanium, zirconium,
vanadium, molybdenum, tungsten, chromium, iron,
Hydroxides of transition metals such as cobalt, nickel, manganese, germanium, and cerium; hydroxides of amphoteric metals such as aluminum, silicon, tin, and antimony; hydroxides of magnesium, etc.; carbonates of metals other than alkali metals; Examples include phosphates, silicates, aluminates, and zirconates. One or more types of these metal compounds are held inside the cellulose fiber.

[0012] In the present invention, such a metal compound is contained in the cellulose fiber in an amount of 0.01 to 10% by weight, preferably 0.1% by weight.
It is preferable that the gripping amount is 5% by weight.

The natural cellulose fibers of the present invention are produced by introducing metal ions into the cellulose fibers and then converting them into the form of water-insoluble inorganic metal compounds. The details differ depending on the type of metal compound to be used, and are as described below.

A general method consists of a first bath treatment in which cellulose fibers are impregnated with water-soluble metal salts and a second bath treatment in which the water-soluble metal salts in the fibers are insolubilized.

In the first bath treatment, the fibers are treated with an aqueous solution of the metal salt in order to impregnate and adhere the water-soluble metal salt to the fibers. Methods for treating fibers with an aqueous metal salt solution include a dipping method, a pad method, a spray method, a coating method, etc., but the dipping method and the pad method are practically preferred.

In the case of the immersion method, specifically, the fibers are immersed in an aqueous metal salt solution containing 0.01 to 10% by weight of metal, and treated at room temperature to 100° C. for 3 seconds to 10 minutes. The treatment conditions at this time vary depending on the type of fiber, and the treatment may be performed under the optimum conditions for the target fiber. After the dipping treatment, the fibers are subjected to a second bath treatment, but prior to the second bath treatment, the fibers may be subjected to a water washing treatment and a drying treatment. In the present invention, since the metal salt is water-soluble, it is desirable to proceed to the second bath treatment after only the drying step.

The pad method is particularly suitable for woven and knitted fabrics. Specifically, when using the pad method, the metal is 0.
．． The fibers are immersed in a metal salt aqueous solution containing 01 to 10% by weight, treated at room temperature to 100°C for 3 seconds to 10 minutes, and then squeezed with a mangle or the like to achieve a predetermined uniform squeezing rate. The processing conditions at this time may be appropriately selected from the optimum conditions for the target fiber. After the pad treatment, the fibers are subjected to a second bath treatment, but prior to the second bath treatment, the fibers may be subjected to a water washing treatment and a drying treatment. In this method as well, as with the dipping method, it is desirable to proceed to the second bath treatment after only the drying step.

In the second bath treatment, the water-soluble metal salt is treated with any one of an alkali, an acid, and an aqueous solution of an alkali metal salt to convert the water-soluble metal salt impregnated into the fiber into a water-insoluble metal compound. Convert it to Although a dipping method, a pad method, a spray method, a coating method, etc. can be applied to this method, the dipping method and the pad method are practically preferred. The dipping method can be applied to all types of fibers, but the pad method is particularly suitable for woven and knitted fabrics.

In the case of the pad method, specifically, the fibers after the first bath treatment are immersed in an aqueous solution containing 0.01 to 10% by weight of an alkali, acid, or alkali metal salt, and the fibers are heated at room temperature to 70% by weight.
After processing at ℃ for 3 seconds to 5 minutes, the mixture is squeezed using a mangle or the like to achieve a predetermined uniform squeezing rate. The processing conditions at this time may be appropriately selected from the optimum conditions for the target fiber.

After padding, soaping or washing with water is performed to completely remove alkali, acid, or alkali metal salt, and then drying is performed. In this way, the natural cellulose fiber of the present invention is produced which behaves as if the water-insoluble inorganic metal compound was encapsulated inside the amorphous region of the fiber.

The metal species of the metal compound to be held inside the fibers include transition metals such as copper, silver, iron, cobalt, nickel, manganese, zinc, titanium, zirconium, cerium, vanadium, molybdenum, germanium, and tungsten, and aluminum. , magnesium, the water-soluble metal salt in the first bath is a mineral acid salt such as chloride, oxychloride, sulfate, nitrate, or an organic acid salt such as acetate or formate of the metal. It has a good form, and an alkaline aqueous solution is used in the second bath. Examples of the alkali include alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide, and preferably sodium hydroxide.

The metal species of the metal compound to be held inside the fibers is zinc, titanium, zirconium, vanadium,
In the case of an amphoteric metal element such as molybdenum, tungsten, aluminum, silicon, tin, antimony, etc., an amphoteric element oxidation prepared by dissolving the amphoteric metal element or its salt with alkali hydroxide or ammonium hydroxide in the first bath It is preferable to use an aqueous solution containing the substance as an anion, and use an acid aqueous solution in the second bath. Examples of the acid include mineral acids such as hydrochloric acid and sulfuric acid, water-soluble organic acids such as formic acid and acetic acid, and preferably acetic acid.

[0023] Also, after the natural cellulose fibers are impregnated with a water-soluble metal salt in the first bath, they are passed through an aqueous solution of a different type of water-soluble metal salt in the second bath to form water-insoluble inorganic metal salts within the fibers. You can also do that. Here, the water-soluble metal salts in the first bath refer to all water-soluble metal salts except alkali metals, and the water-soluble metal salts in the second bath are those that react with the metal salts in the first bath to become water-insoluble. This refers to all inorganic metal salts such as carbonic acid, phosphoric acid, pyrophosphoric acid, metasilicic acid, silicic acid, zinc acid, aluminic acid, titanic acid, molybdic acid, vanadic acid, zirconic acid, etc., and sulfuric acid. Examples include alkalis and the like.

When the metal compound held inside the fiber is, for example, a zinc compound or a copper compound, the fiber has a deodorizing, antibacterial, and antifungal effect, and when the metal compound is an aluminum compound or a magnesium compound, the fiber has a deodorizing, antibacterial, and antifungal effect. A zirconium compound imparts a deodorizing effect, a zirconium compound imparts heat storage, ultraviolet protection, and far infrared radiation effects to the fiber, and an antimony compound imparts a flame retardant effect to the fiber. When the purpose of gripping the insoluble inorganic metal compound according to the present invention is deodorization, after insolubilizing the water-soluble metal compound impregnated into cellulose fibers, heat treatment is performed with an aqueous solution of polycarboxylic acid such as butanetetracarboxylic acid. The deodorizing effect is further enhanced.

[0025]

According to the present invention, natural cellulose fibers can be produced that can maintain the various functions imparted by various metal compounds over a long period of time. Since the insoluble inorganic metal compound is held in the natural cellulose fiber of the present invention, it has excellent washing fastness, and even after repeated washing, the metal compound is difficult to detach from the fiber, making it difficult to remove various metals. The various functions imparted by the compound can be maintained over a long period of time. Furthermore, the natural cellulose fiber of the present invention has a satisfactory texture.

[0026]

[Examples] The present invention will be further clarified by the following Examples and Comparative Examples.

Example 1 A cotton fabric with a basis weight of 120 g/m2 was scoured, bleached, and mercerized, then dipped in an aqueous solution containing 1.16% zinc chloride, squeezed with a mangle, and dried at 100°C to obtain a zinc chloride-holding cotton fabric. I got it. The fabric was then soaked in sodium hydroxide 1.0
% for 3 seconds, squeezed with a mangle, immediately washed with water and dried to obtain a cotton fabric holding zinc hydroxide. The zinc hydroxide content of the fabric as determined by atomic absorption method is 4100 mg.
/kg.

Comparative Example 1 Using the same cotton fabric as in Example 1, the same treatment as in Example 1 was carried out except that zinc chloride was not added to the treatment solution, and a cotton fabric was obtained.

Example 2 A polyester/cotton blend fabric with a basis weight of 150 g/m2 was dyed after normal bleaching treatment, dipped in an aqueous solution containing 1.6% zinc chloride, squeezed with a mangle, and then soaked in water. After immersing in an aqueous solution containing 1.0% sodium oxide for 3 seconds, squeezing with a mangle, and further immersing in an aqueous solution containing 6.9% butanetetracarboxylic acid and 1.2% sodium carbonate,
Squeezed with mangle. Dry this at 120°C, then dry at 160°C.
After curing for 2 minutes, a zinc hydroxide-holding butanetetracarboxylic acid crosslinked fabric was obtained. The zinc hydroxide content of the fabric was determined by atomic absorption method to be 3100 mg/kg.

Comparative Example 2 Using the same fabric as in Example 2, the same treatment as in Example 2 was carried out except that zinc chloride and butanetetracarboxylic acid were not added to the treatment solution to obtain a fabric.

Example 3 A cotton fabric with a basis weight of 120 g/m2 was scoured, bleached, and mercerized, then immersed in an aqueous solution containing 10% aluminum chloride, squeezed with a mangle, and dried at 60°C to obtain an aluminum chloride grip fabric. Ta. Next, the fabric was immersed in an aqueous solution containing 1.0% sodium hydroxide for 3 seconds, squeezed with a mangle, immediately washed with water, and dried to obtain an aluminum hydroxide-held cotton fabric. The aluminum hydroxide content of the fabric was determined by weight measurement to be 18,500 mg/kg.

Comparative Example 3 Using the same cotton fabric as in Example 3, the same treatment as in Example 3 was carried out except that aluminum chloride was not added to the treatment solution, and a cotton fabric was obtained.

Example 4 A cotton fabric with a basis weight of 120 g/m2 was scoured, bleached, and mercerized, then immersed in an aqueous solution containing 20% zirconium oxychloride, squeezed with a mangle, and dried at 50°C to obtain a zirconium oxychloride gripping fabric. I got it. Next, the fabric was immersed in an aqueous solution containing 1.0% sodium hydroxide for 3 seconds, squeezed with a mangle, immediately washed with water, and dried to obtain a cotton fabric holding zirconium hydroxide. The zirconium hydroxide content of the fabric was determined by weight measurement to be 43000 mg/kg.

Comparative Example 4 Using the same cotton fabric as in Example 4, the same treatment as in Example 4 was carried out except that zirconium oxychloride was not added to the treatment solution, and a cotton fabric was obtained.

Example 5 After scouring, bleaching and mercerizing a cotton fabric with a basis weight of 120 g/m2, it was immersed in an aqueous solution containing 0.45% magnesium chloride hexahydrate, squeezed with a mangle, and then the fabric was soaked in sodium hydroxide. After being immersed in an aqueous solution containing 0.5% for 3 seconds, it was further immersed in an aqueous solution containing 2.5% butanetetracarboxylic acid and 0.45% sodium carbonate, and then squeezed with a mangle. This was dried at 120°C and cured for 2 minutes at 160°C to obtain a butanetetracarboxylic acid crosslinked fabric holding magnesium hydroxide. The magnesium hydroxide content of the fabric was determined by atomic absorption method to be 1200 mg/kg.

Comparative Example 5 Using the same cotton fabric as in Example 5, the same treatment as in Example 5 was carried out except that magnesium chloride and butanetetracarboxylic acid were not added to the treatment solution to obtain a cotton fabric.

Example 6 After scouring, bleaching, and mercerizing a cotton fabric with a basis weight of 120 g/m2, the fabric was added to an aqueous sodium zincate solution prepared by mixing and stirring 5% basic zinc carbonate and 30% sodium hydroxide. After soaking for 3 minutes, squeeze with a mangle, 1
After drying at 00°C, a sodium zincate-supported cotton fabric was obtained. Next, the fabric was immersed in a 0.4% acetic acid aqueous solution for 3 seconds, squeezed with a mangle, washed with water, and dried to obtain a cotton fabric holding zinc hydroxide. The zinc hydroxide content of the fabric was determined by atomic absorption method to be 25,700 mg/kg.

Comparative Example 6 Using the same cotton fabric as in Example 6, the same treatment as in Example 6 was carried out except that sodium zincate was not added to the treatment solution to obtain a cotton fabric.

Example 7 A cotton fabric with a basis weight of 120 g/m2 was scoured, bleached, and mercerized, then dipped in an aqueous solution containing 1% cupric chloride, squeezed with a mangle, dried at 80°C, and prepared with cupric chloride. A gripping fabric was obtained. Next, the fabric was immersed in an aqueous solution containing 1.0% sodium silicate for 3 seconds, squeezed with a mangle, immediately washed with water, and dried to obtain a cupric silicate-holding cotton fabric. The cupric silicate content of the fabric was determined by atomic absorption method to be 4800 mg/kg.

Comparative Example 7 Using the same cotton fabric as in Example 7, the same treatment as in Example 7 was carried out except that cupric chloride was not added to the treatment solution to obtain a cotton fabric.

Example 8 A cotton fabric with a basis weight of 120 g/m2 was scoured, bleached, and mercerized, then immersed in an aqueous solution containing 8% zinc chloride, squeezed with a mangle, and dried at 80°C to obtain a zinc chloride-holding fabric. Ta. Next, the fabric was immersed in an aqueous solution containing 1.0% sodium aluminate for 3 seconds, squeezed with a mangle, immediately washed with water, and dried to obtain a cotton fabric holding zinc aluminate (aluminum oxide zinc oxide hydrate). The zinc aluminate content of the fabric was determined by atomic absorption method to be 38,100 mg/kg.

Comparative Example 8 Using the same cotton fabric as in Example 8, the same treatment as in Example 8 was carried out except that zinc chloride and sodium aluminate were not added to the treatment solution to obtain a cotton fabric.

Comparative Example 9 The same cotton fabric as that used in Examples 1 and 3 to 8 was used.
The mercerized fabric was designated as untreated fabric 1. Further, an untreated fabric 2 was prepared by mercerizing the same fabric as the polyester/cotton blend fabric used in Example 2.

Comparative Example 10 Untreated fabric 1 was immersed in an aqueous solution containing 1.16% zinc chloride, squeezed with a mangle, and dried at 100°C to obtain a zinc chloride-holding cotton fabric. The zinc chloride content of the fabric was determined by atomic absorption method to be 5600 mg/kg.

[Washing Conditions] The fabrics obtained in Examples 1 to 8, the fabrics obtained in Comparative Examples 1 to 8, and untreated fabrics 1 to 2 were each washed in a domestic washing machine under the following conditions. That is, household detergent [New Beads, manufactured by Kao Corporation] 2g/
l.Using a simple method in which washing for 10 minutes with room temperature water is considered one wash, 10 washes are 100 minutes, 30 washes are 300 minutes, and 50 minutes.
Washed for 500 minutes, washed with water, dehydrated, dried, 10 times washed fabric (L-10), 30 times washed fabric (L-30), 50 times washed fabric (L-10), 30 times washed fabric (L-30),
A twice-washed fabric (L-50) was obtained. However, for the fabrics obtained in Example 4 and Comparative Example 4, a detergent to which no fluorescent agent was added [Monogen Uni, manufactured by P&G] was used, and the other conditions were the same.

[Deodorizing performance evaluation] Examples 1 to 3 and 5 to 8
Deodorization of the fabrics obtained in Comparative Examples 1 to 3, 5 to 8, and 10, untreated fabrics 1 to 2, and the respective 10-times washed fabrics, 30-times-washed fabrics, and 50-times washed fabrics Performance was investigated as follows.

[0047] A 10 x 10 cm sample of each of the above fabrics was placed in a 600 ml Erlenmeyer flask and the flask was tightly capped. Next, a gas or liquid containing a malodorous compound at a certain concentration was injected from the top of the flask using a microsyringe and allowed to stand for 60 minutes. After injection, the liquid malodorous compound was heated and evaporated with a hot air gun, and then left to stand. The same gas or liquid was injected into the flask without dough and left for 60 minutes. Gas concentration measurement after standing was performed using a Kitagawa gas detection tube.

Injection conditions for malodorous compound; ammonia: 10
20ml of 35% ammonia water in a 0ml Erlenmeyer flask
It was heated and ammonia gas was generated. Collect the gas at the top of the flask with a gastight syringe and collect 0.2ml.
Injected.

Isovaleric acid: 0.5 μl of isovaleric acid was injected with a microsyringe and evaporated by heating.

The removal rate of malodorous compounds was determined by the following formula.

[0051]

[Math 1]

The deodorizing abilities of the fabrics of each example, the fabrics of each comparative example, and the untreated fabrics were measured before and after washing, and the results are shown in Table 1. Further, Table 2 shows the content of the gripping metal compound before and after washing the fabrics of each example.

[0053]

[Table 1]

[0054]

[Table 2]

[Antibacterial performance evaluation] Examples 1-2 and 6-8
The antibacterial performance of the fabrics obtained in Example 1 and Comparative Examples 1 to 2 and 6 to 8 was examined using the following test method.

Test strain: Staphylococcus aureus
lococcus aureus IAM1208
2) Test method: Halo test method is AATCC TE
According to ST METHOD 90.

[0057] Bacteria count was measured using AATCC TEST.
According to METHOD 100.

[0058] The results of the halo test are shown in Table 3, and the results of the bacterial count measurement are shown in Table 4.

[0059]

[Table 3]

[0060]

[Table 4]

[Evaluation of UV protection performance] The UV protection effects of the fabric obtained in Example 4 and the fabric obtained in Comparative Example 4 were evaluated by the following method. That is, as a UV light source, short wavelength,
Long wavelength switching type ultraviolet hand lamp UV-GL-58
(manufactured by San Gabriel U.S.A.), and placed an ultraviolet intensity meter (UM-1, manufactured by Minolta Camera) with the sensor portion covered with a measuring cloth directly under the lamp to measure the intensity of ultraviolet light passing through the fabric. . The UV sensors used were UM-36 for long wavelengths and UM-25 for short wavelengths, and the transmitted intensity in each wavelength range was measured. Transmittance (%) was calculated using the following formula.

[0062]

[Math 2]

The results obtained are shown in Table 5.

[0064]

[Table 5]

[Evaluation of heat storage performance] The heat storage effect of the fabric obtained in Example 4 and the fabric obtained in Comparative Example 4 was evaluated by the following method. That is, each fabric was placed in a constant temperature room at 20°C and 60% Rh, and a photographic film was placed at a distance of 1.5 m from the fabric.
A 00W white electric lamp was placed and irradiated with light. Five minutes after the start of irradiation, the surface temperature of the fabric on the opposite side to the irradiated surface was measured using an infrared non-contact surface thermometer. The results are shown in Table 6.

[0066]

[Table 6]

Claims (2)

[Claims] 1. A natural cellulose fiber comprising a water-insoluble inorganic metal compound held inside the cellulose fiber. 2. A method for producing natural cellulose fibers containing a water-insoluble inorganic metal compound, which comprises introducing metal ions into the interior of the cellulose fibers and then converting the metal ions into the form of a water-insoluble inorganic metal compound.