JPH05125668A - Fiber product and its production - Google Patents

Abstract

PURPOSE:To obtain a fiber product showing excellent durability and ultraviolet absorbing effects by sticking ferulic acid and its derivative to a fibrous material. CONSTITUTION:A fibrous material, e.g. natural fibers such as animal or plant fibers, regenerated fibers, semisynthetic fibers, polypropylene or spandex is immersed in a solution obtained by dissolving ferulic acid and its derivative in a water-soluble organic solvent such as dioxane or acetonitrile and diluting the solution with water and ferulic acid and its derivative are stuck to the fibrous material to give a fiber product having excellent ultraviolet absorbing effects and not causing change of color. Synthetic fiber such as acrylic fiber or urethane fiber may be cited as the fibrous material and use of dimethyloldihydroxyethyleneurea besides ferulic acid and its derivative improves washing resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a textile product having an ultraviolet absorbing effect and a method for producing the same.

[0002]

2. Description of the Related Art Textile products have been subjected to various special processes in accordance with diversification of consumers' demands. In particular, recently, in textile products such as clothing for women's blouses, sportswear, etc., which are worn in places exposed to the sun for a long time, the sunburn caused by ultraviolet rays is reduced and the generation of stains and freckles is reduced. There are even those that have been subjected to UV protection to make them.

Conventionally, as a fiber product which has been subjected to an ultraviolet ray prevention treatment, a benzophenone type ultraviolet ray absorbent is fixed to a fiber material (base cloth) such as cloth, or a metal having an ultraviolet ray absorbing effect such as titanium oxide or zinc oxide. For example, an oxide is fixed to a fiber material through a polymer binder.

[0004]

However, there are the following problems with these textile products that have been subjected to the ultraviolet ray prevention treatment. That is, in the former textile products, the benzophenone-based UV absorber has a strong UV absorbing ability and is excellent in the initial UV absorbing effect, but the washing durability can be easily improved in the manufacturing process. There is no problem in terms of washing durability because no auxiliary agent etc. has been found. In addition, yellowing due to heat is also large, and especially when trying to fix the fiber material in the state of being sulfonated into an aqueous solution, the sulfonated material for water-solubilization causes the fiber material to brown due to heat during processing. There is also a problem to say.

On the other hand, the latter fiber product can be obtained by treating the fiber material by the coating method with the use of an acrylic binder or the like. However, in the processing by the padding method, the sedimentation of particles occurs in the pad bath. It is not possible to obtain a product having a uniform UV protection effect. Therefore, it cannot be used for a fiber product that cannot be obtained by the padding method.

In view of such circumstances, it is an object of the present invention to provide a novel fiber product which has been subjected to a novel ultraviolet ray prevention treatment and a method for producing the same, which can solve the above problems.

[0007]

In order to achieve such an object, the present invention according to claim 1 provides that at least one of ferulic acid and its derivative is fixed to a fiber material. The main feature is textile products. In the above structure, ferulic acid and its derivative are represented by the following formula,

[0008]

[Chemical 1]

(Wherein R is hydrogen, linear alkyl group, cyclic alkyl group, branched alkyl group, polycyclic alkyl group, alkenyl group, aryl group, alkali metal, alkaline earth metal, quaternary ammonium, amine It represents any of the). Examples of the fiber material include natural fibers such as cotton and hemp silk wool, recycled fibers such as rayon and acetate, polypropylene, and synthetic fibers such as spandex. Examples of the shape include woven fabric, knitted fabric, yarn, and non-woven fabric. Those that can be continuously processed are desirable.

Ferulic acid is present in a small amount in vegetable oils and fats, and most of them are present as esters having 30 to 31 carbon atoms.
The ultraviolet absorption region has a maximum absorption around 320 nm, but if it is fixed to a fiber material, it will have a practical absorption region up to 350 nm due to its strong ultraviolet absorption ability, which is the direct skin of the UV-B region. It extends to the UV-A range, which is said to promote the influence on It is also an important compound as a pharmaceutical intermediate having bactericidal, antiseptic and rancidity-preventing ability.

The method for fixing ferulic acid and its derivative to the fiber material is not particularly limited, but since the fiber material is mostly treated in the water during the production process of the fiber product, ferulic acid and its derivative are desired. Aqueous solution to a concentration, using this solution padding method,
Treatment by a coating method, an exhaust method, a spray method or the like is preferable. It should be noted that the sodium salt of ferulic acid is 7
Dissolves about%, but cannot be used when the solution becomes acidic.

The amount of ferulic acid and its derivatives attached is
Although not particularly limited, 0.0001 relative to the weight of the fiber material
˜1%, preferably 0.005 to 0.1%. In addition to ferulic acid and its derivatives, other drugs can be used in combination. Examples of the above-mentioned concomitant drug include dimethylol urea, dimethylol dihydroxyethylene urea, dihydroxy ethylene urea, methylol melamine, etc. Examples thereof include a texture modifier, a fluorine-based oil repellent, an antibacterial insecticide, a flameproofing agent, an antistatic agent, a dye and the like. Although the range of use of the concomitant drug is not limited, when ferulic acid is used, the combined use with a cationic polymer tends to deteriorate the stability of the compounded liquid because ferulic acid is weakly anionic.

Further, if a resin such as an acrylic, urethane, isocyanate, or epoxy polymer and a resin such as dimethylol urea or methylol melamine is used in combination, the washing durability is improved, and especially dimethylol dihydroxy is observed. The use of ethylene urea, methylol melamine, etc. and an acidic catalyst significantly improves durability. The amount of the above resin used is 1 to 15% in the bath in the case of padding treatment.
It is preferably 3 to 10%. Further, the treatment method by exhaustion imparts good durability to synthetic fibers such as polyester and nylon, and the amount used is 0.
01-0.05% (OWF) is preferable.

On the other hand, the invention of claim 2 is a fiber product in which a ferulic acid solution having a desired concentration is fixed to a fiber material by one method selected from the group consisting of a padding method, a coating method, a spray method and an exhaust method. The manufacturing method of
After dissolving ferulic acid in a predetermined water-soluble organic solvent,
The gist is a method for producing a textile product, which is characterized by diluting this solution with water to a desired concentration.

In the above structure, the water-soluble organic solvent is not particularly limited, but examples thereof include dioxane, acetonitrile, tetrahydrofuran and the like, and these can be used alone or in combination.

[0016]

According to the structure of the above-mentioned claim 1, the ferulic acid and its derivatives fixed to the fiber material are not only 280-320 nm (UV-B) irradiated on the fiber product but also around 350 nm on the longer wavelength side. Absorbs UV rays and prevents the UV rays from reaching the skin protected by the textile. Further, the durability is improved by using an acrylic-based, urethane-based, isocyanate-based, epoxy-based polymer, or a resin such as dimethylol urea or methylol melamine in combination.

On the other hand, according to the constitution of claim 2, the solubility of ferulic acid is readily soluble in hot water, but only slightly in cold water, and even if a small amount of alcohol solvent is added, the solubility is almost zero. Although recrystallization still occurs, a high concentration aqueous solution can be obtained by first dissolving it in a water-soluble organic solvent such as dioxane, acetonitrile, or tetrahydrofuran.

[0018]

The present invention will be described in more detail with reference to the following examples. All “%” in the formulation and “part” in the text shall be weight standards. (Example 1) Preparation liquids 1 to 5 shown in Table 1 were prepared, and cotton wire width 3 was soaked in the pad bath, squeezed to a squeezing ratio of 70% with a mangle, and then 1 using a baking machine.
The sample was heat-treated at 60 ° C. for 1 minute and 30 seconds, and the ultraviolet transmittance of the sample was measured using the ultraviolet absorption effect measuring method described below. The results are shown in Table 1 together with the measurement results of the blank cloth (represented by 0 in the table).
It was shown to. The blank cloth was measured by passing the same kind of cloth through water. Ultraviolet absorption effect measuring method Measuring instrument: Autograph spectrophotometer UV-3101PC60 Using a integrating sphere (manufactured by Shimadzu Corporation) A sample cloth was placed on the optical path entrance side of the integrating sphere to measure the transmittance. Air was used as a blank and the transmittance was 100%. Measurement area is 250-450
nm.

[0019]

[Table 1]

From Table 1, it can be seen that the cloth of this example can reduce the ultraviolet transmittance to about 1/4 in the range of 280 to 350 nm in comparison with the blank cloth. (Example 2) Preparation solutions 1 to 4 shown in Table 2 were prepared, and cotton wire width No. 3 was treated in the same manner as in Example 1, and the transmittance before and after washing was measured together with the blank cloth (represented by 0 in the table). The measurement was carried out in the same manner as above, and the results are shown in Table 3.

[0021]

[Table 2]

[0022]

[Table 3]

From Table 3, it is understood that the combined use of the dimethylol dihydroxyethylene urea resin and the acid catalyst improves the durability. (Example 3) 0.2 g of ferulic acid was dissolved in 200 g of water, and 5 g of polyester cloth and 5 nylon cloth were dissolved in this solution.
Each g was exhausted to fix ferulic acid. The processing conditions are an initial temperature of 40 ° C., a temperature increase of 3 ° C./min, and a final temperature of 100.
It was performed at 20 ° C. for 20 minutes. The transmittance of the obtained processed cloth before and after washing was measured in the same manner as in Example 1 together with the blank cloth (represented by 0 in the table), and the results are shown in Table 4.

[0024]

[Table 4]

From Table 4, in the case of polyester, a blank cloth was also found to have an ultraviolet ray-preventing effect, but it was found that the longer wavelength side was effectively absorbed, and the durability was good, and it was necessary to use a crosslinking agent in combination. I know there isn't one. (Example 4) 10 parts of cationic soft base, 3 parts of anionic soft base, 3 parts of nonionic soft base, 3 parts of nonionic stearic acid surfactant [ethylene oxide (EO) 20 mol adduct] 3 parts, Ferula A mixture of 2 parts of acid was melted at 90 ° C. and the internal temperature was kept at 90 ° C. using a propeller type stirrer.
The mixture was stirred for 15 minutes, 84 parts of hot water at 90 ° C. was added, and the mixture was stirred for 15 minutes to obtain an emulsion (A). A mixture of 1 to 3 shown in Table 5 was prepared from this emulsion (A) and water, and cotton wire width 3 was treated in the same manner as in Example 1 to obtain the ultraviolet transmittance before and after washing with a blank cloth (0 in the table). (Represented and treated with water) and measured in the same manner as in Example 1, and the results are shown in Table 5.

[0026]

[Table 5]

(Embodiment 5) Ferulic acid was mixed with a water-soluble organic solvent at a mixing ratio of 1 to 10 and dissolved.
Diluted to 0 times (weight), the stability of the solution such as cloudiness and recrystallization was compared, and the results are shown in Table 6.

[0028]

[Table 6]

It can be seen from Table 6 that a high concentration ferulic acid aqueous solution can be stably obtained by previously dissolving ferulic acid in a predetermined organic solvent.

[0030]

EFFECTS OF THE INVENTION Since the fiber product according to claim 1 is configured as described above, ferulic acid and its derivatives fixed to the fiber material are irradiated to the fiber product 280-280.
320 nm (UV-B) as well as 3 on the longer wavelength side
It absorbs UV light up to around 50 nm so that it does not reach the skin protected by the textile. Therefore, it is possible to reduce sunburn caused by ultraviolet rays and to reduce the generation of stains and freckles. In addition, by using ferulic acid and its derivatives in combination with a resin such as an acrylic, urethane, isocyanate, or epoxy polymer, dimethylol urea, or methylol melamine, washing durability can be improved and the effect can be maintained for a long time.

Further, it is possible to reduce the risk of yellowing during the heat treatment. On the other hand, since the method for producing a fiber product according to claim 2 is configured as described above, it is possible to obtain a stable treatment liquid having a high concentration, and to continuously perform other treatments of fibers performed in an aqueous system. A stable process can be performed.

Claims (2)

[Claims] 1. A fiber product in which at least one of ferulic acid and its derivative is fixed to a fiber material. 2. A method for producing a fiber product, wherein a ferulic acid solution having a desired concentration is fixed to a fiber material by one method selected from the group consisting of a padding method, a coating method, a spray method, and an exhaust method. A method for producing a fiber product, which comprises dissolving ferulic acid in a predetermined water-soluble organic solvent and then diluting the solution with water to a desired concentration.