JP3138758B2 - Cellulose fiber excellent in ultraviolet blocking effect and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cellulose fiber having an excellent effect of blocking ultraviolet rays and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, an increase in ultraviolet rays of sunlight due to destruction of the ozone layer has become a problem worldwide, and there is an increasing demand for imparting an ultraviolet absorbing ability to textiles. Unlike synthetic fibers, which can be kneaded with UV absorbers in the fibers, even if cotton products made of cellulose are provided with UV absorbing ability, at present, only a method of coating the surface of the product with the UV absorber is known. Not. Thus, in the cotton product obtained by this method, by repeating washing, it is inevitable that the ultraviolet absorbent is easily detached from the surface of the cotton product, and an excellent ultraviolet absorbing ability that meets the above-mentioned demand is obtained. It has been extremely difficult to provide a cotton product that can be held for a long period of time.

[0003]

Means for Solving the Problems The present inventors have intensively studied to provide a cellulose fiber capable of maintaining excellent ultraviolet absorbing ability for a long period of time. As a result, it has been found that a desired cellulose fiber can be obtained by causing an ester of an aliphatic polyhydric alcohol represented by the following general formula (1), a carboxylated hydroxyphenylbenzotriazole and a polycarboxylic acid to act on the cellulose fiber. . The present invention has been completed based on such findings.

That is, the present invention provides a compound represented by the general formula

[0005]

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[Wherein, R represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a halogen atom. X has 1 to 1 carbon atoms
2 represents an alkylene group. Y represents a polyhydric alcohol residue. l represents 0 or 1, m represents an integer of 1 to 10, and n represents 1 or 2. A cellulose fiber obtained by reacting an ester of an aliphatic polyhydric alcohol represented by the formula (1) with a carboxylated hydroxyphenylbenzotriazole and a polycarboxylic acid, and an aliphatic polyhydric alcohol represented by the above general formula (1) And an ester of carboxylated hydroxyphenylbenzotriazole and a polycarboxylic acid on a cellulose fiber.

In the present invention, it is an essential requirement that the aliphatic polyhydric alcohol represented by the general formula (1) and the ester of a carboxylated hydroxyphenylbenzotriazole and a polycarboxylic acid act on cellulose fibers. is there. It is impossible to achieve the intended object of the present invention only by treating the cellulose fiber with the ester alone without using a polycarboxylic acid (see Comparative Example 1 described later).

[0008] The cellulose fibers in the present invention include cotton, hemp, rayon and blended fibers containing these fibers, and products made of these fibers include woven fabrics, knits and nonwoven fabrics.

In the present invention, one component acting on the cellulose fiber is an ester of an aliphatic polyhydric alcohol and a carboxylated hydroxyphenylbenzotriazole.

The carboxylated hydroxyphenylbenzotriazole, which is one of the components constituting the above ester, is
A compound having a skeleton of benzotriazole substituted with an aromatic ring having a phenolic hydroxyl group and a carboxyl group, and is represented by the following general formula (2).

[0011]

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Wherein R, X, l and n are as defined above. ]
Also, as the aliphatic or alicyclic polyhydric alcohol which is another component constituting the ester, conventionally known alcohols can be widely used. As the aliphatic polyhydric alcohol, specifically, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol,
Decanediol, dodecanediol, neopentyl glycol, methylpentanediol, trimethylpentanediol, diethylene glycol, triethylene glycol, a polymer of ethylene oxide, a polymer of dipropylene glycol, tripropylene glycol, a polymer of propylene oxide, a polymer of 1,2-butylene oxide Polymers, diols such as polytetramethylene glycol, glycerin, trimethylolethane, trimethylolpropane,
Pentaerythritol, dipentaerythritol, diglycerin, triglycerin, polyglycerin, reducing sugars such as xylitol, sorbitol, mannitol, erythritol, monosaccharides such as xylose, sorbose, arabinose, ribose, erythrose, galactose, lactose, and sucrose And disaccharides such as maltose. Specific examples of the alicyclic polyhydric alcohol include cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, spiroglycol, and the like, and geometric isomers thereof. Among the above polyhydric alcohols, ethylene glycol is preferred for use for the purpose of increasing the content of the carboxylated hydroxyphenylbenzotriazole component.

[0013] Among the above esters, from the viewpoint of availability, the general formula

[0014]

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[Wherein k represents an integer of 1 to 20]. And mixtures of polyethylene glycol monoesters and diesters.

The amount of the ester used varies depending on the type of the ester used, and cannot be determined unconditionally.
The content of carboxylated hydroxyphenylbenzotriazole is usually 0.0
The ester is preferably used in an amount of from 0.01 to 10% by weight, preferably from 0.01 to 5% by weight. If the amount of the corresponding ester used is less than 0.001% by weight, the desired ultraviolet ray blocking effect tends to be not expected. On the other hand, if the ester is used in an amount of more than 10% by weight, the ultraviolet ray blocking effect is not so improved. Not economic.

The polycarboxylic acids used in the present invention include linear aliphatic polycarboxylic acids, branched aliphatic polycarboxylic acids, alicyclic polycarboxylic acids, and aromatic polycarboxylic acids. May have a hydroxyl group, a halogen atom, a carbonyl group, a carbon-carbon double bond, or the like. Specific examples of such polycarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, speric acid, azelaic acid, sebacic acid and the like, and their branched carboxylic acids, maleic acid, fumaric acid, and cyclohexanedicarboxylic acid. Acids and their positional isomers, alicyclic dibasic acids such as tetrahydrophthalic acid and nadic acid, tricarballylic acid, aconitic acid, tribasic acids such as methylcyclohexentricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, Tetrabasic acids such as tetrahydrofurantetracarboxylic acid, ene adducts of methyltetrahydrophthalic acid and maleic acid, hydroxy fatty acids such as malic acid, tartaric acid and citric acid, trimellitic acid, pyromellitic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid Acid, diphenylsulfo It can be exemplified aromatic polycarboxylic acids such as tetracarboxylic acid. Of these polycarboxylic acids, butanetetracarboxylic acid is most suitable.

The amount of the polycarboxylic acid used is as follows:
Although it depends on the type of polycarboxylic acid used and cannot be said unconditionally, the polycarboxylic acid is usually used in an amount of 0.1 to 30% by weight, preferably 0.5 to 10% by weight, based on the cellulose fiber to be processed. Good to use. When the amount of the polycarboxylic acid used is less than 0.1% by weight, the effect of blocking the ultraviolet rays of the work cloth tends to be reduced by washing. Does not improve and is not economical.

As a solvent for allowing the above-mentioned substrate, that is, the above-mentioned ester and polycarboxylic acid to act on the cellulose fiber, an organic solvent can be used, but water is used as a solvent in consideration of safety and cost. Is preferred. If one of the substrates does not dissolve in water, a two-bath system in which cellulose fibers are immersed in one substrate-containing solution and then the fibers are immersed in another substrate-containing solution may be employed. A one-bath method in which a liquid in which a substrate is emulsified or solubilized with a surfactant is prepared, and cellulose fibers are immersed in the liquid is more preferable. Here, as the surfactant, conventionally known surfactants can be widely used as long as they are active in an acidic aqueous solution.Examples thereof include an ethylene oxide adduct of an alkylphenol, an ethylene oxide adduct of a higher alcohol, an alkylbenzene sulfonate, an alkyl sulfate, and an alkyl sulfate. Examples include betaines, sorbitan fatty acid esters and ethylene oxide adducts thereof, fatty acid monoglycerides and ethylene oxide adducts thereof, and castor oil or hydrogenated castor oil ethylene oxide adducts. In the present invention, it is stable for a long time in an acidic aqueous solution,
In addition, ethylene oxide adducts of alkylphenols and ethylene oxide adducts of higher alcohols, which are hardly affected by alkalis or salts for pH adjustment, described below are particularly preferred.

The concentration of the polycarboxylic acid or the concentration of the ester in the above-mentioned liquid (processing liquid) may be set to a concentration calculated from the squeezing rate of the processing liquid and the required supported amount.

It is desirable that the pH of the aqueous solution in which the polycarboxylic acid is dissolved is previously adjusted by adding an alkali or a salt. The pH range is usually 1 to 6, preferably 2
It is better to be within the range of ~ 5. When the pH of the solution is higher than the above range, the ultraviolet blocking effect tends to be significantly reduced by washing. On the other hand, when the pH of the solution is lower than the above range, a decrease in fiber strength due to hydrolysis of cellulose tends to be unavoidable. Is not preferred. As the alkali or salts used, sodium hydroxide,
Sodium bicarbonate, sodium borate, sodium metaborate, sodium silicate, sodium metasilicate, sodium phosphate, sodium metaphosphate, sodium polyphosphate, sodium pyrophosphate, sodium phosphite, sodium hypophosphite, sodium formate, Sodium acetate and the like. In place of the above alkali or salts of sodium, potassium, ammonium and the like, and salts of volatile lower amines such as methylamine, dimethylamine, trimethylamine and triethylamine can also be used. These may be used alone or in combination of two or more.

The amount of the alkali or salt used varies depending on the amount and type of the polycarboxylic acid dissolved and cannot be specified unconditionally. However, the concentration of the processing solution is usually preferably 0.1 to 10% by weight. The surfactant may be used in such an amount that the ester, which is one component of the substrate, can be stably dispersed in water, and is usually used in an acidic aqueous solution in the range of 0.1 to 10% by weight.

In the present invention, the cellulose fibers to be treated are immersed in the treatment liquid prepared as described above, squeezed according to the required amount of support, dried, and heat-treated by a so-called pad-dry-cure method. It is desirable to treat the cellulose fibers.

The rate of penetration of the treatment liquid of the present invention into cellulose fibers is sufficiently high, and there is no particular limitation on the immersion time and bath temperature. Usually, the immersion time is 0.5 to 300 seconds and the bath temperature is 10
Performed at ４０40 ° C. The drawing differs depending on the product to be processed, and an appropriate drawing method and drawing ratio can be adopted for each.
Usually, it is preferable to set the aperture ratio at 40 to 200%.
The temperature for the subsequent drying is preferably about 40 to 150 ° C., and the drying time may be set appropriately according to the temperature. Further, the temperature of the heat treatment is usually 100 to 250C, preferably 120 to 200C, and the heat treatment time is about 30 seconds to 1 hour. If the conditions of the heat treatment are milder than the above, the UV blocking effect of the work cloth tends to be reduced by washing,
On the other hand, if the conditions are too severe, the cellulose fibers tend to be degraded, causing a decrease in strength and yellowing of the fibers.

The cloth processed as described above is further subjected to conventional means such as washing with water, soaping, and application of a fabric softener to obtain a desired product.

[0026]

According to the present invention, there is provided a cellulose fiber capable of maintaining excellent ultraviolet absorbing ability for a long period of time.

[0027]

The present invention will be further clarified with reference to the following examples and comparative examples.

Example 1 0.1% by weight of Tinuvin 213 (manufactured by Ciba-Geigy)
After immersing a scouring bleached and mercerized 100% cotton cloth (hereinafter referred to as "under bleaching processing") in the dissolved methanol solution, the squeezing rate was reduced to 100% with a mangle. 80 this cloth
After drying at 15 ° C. for 15 minutes, it was immersed in an aqueous solution of 5% by weight of 1,2,3,4-butanetetracarboxylic acid and 1.2% by weight of sodium carbonate, and the squeezing rate was 100% by mangle. The cloth was dried again at 80 ° C. for 15 minutes, and then dried at 180 ° C. for 90 minutes.
Heated for seconds.

The work cloth thus obtained is cut in half to obtain an L0 cloth, and the remaining cloth is cut using a tergot meter.
Washed twice to make L3 cloth. The detergent used was phosphorus-free, alkyl sulfate.

The UV blocking ability of the work cloths (L0 and L3) and the untreated cloth was measured by measuring the transmittance of UV light to scattered light by an integrating sphere. The results are shown in FIG. As is clear from FIG. 1, since the absorption in the harmful ultraviolet region of 280 to 360 nm was not eliminated by washing, it can be seen that the work cloth obtained as described above has excellent ultraviolet shielding ability over a long period of time.

EXAMPLE 2 To an aqueous solution in which 5% by weight of 1,2,3,4-butanetetracarboxylic acid and 5% by weight of monosodium phosphate were dissolved, 0.2% by weight of tinuvin 213 and 9 mol of higher alcohol ethylene oxide were added. 4% by weight of the mixture was added, and the mixture was vigorously stirred to obtain an emulsion, which was used as a treatment liquid. Example 1
The same exposed cotton fabric as in Example 1 was immersed for 1 minute, and the squeezing rate was set to 100% using a mangle. The fabric was dried at 80 ° C. for 15 minutes and then heated at 180 ° C. for 90 seconds.

The work cloth thus obtained was cut in half to obtain an L0 cloth, and the rest was washed three times using a home washing machine to obtain an L3 cloth. The detergent used was phosphorus-free, alkyl sulfate.

The UV blocking ability of the work cloths (L0 and L3) and the untreated cloth was measured by measuring the transmittance of UV light to scattered light with an integrating sphere. The results are shown in FIG. As is apparent from FIG. 2, the absorption in the harmful ultraviolet region of 280 to 360 nm was not eliminated by washing, indicating that the work cloth obtained as described above has excellent ultraviolet shielding ability over a long period of time.

Example 3 A knitted cloth (smooth) was used as the test cloth, and the drawing ratio was 150%.
The treatment was carried out in the same manner as in Example 2 except for the above, and the ultraviolet absorbing ability was examined in the same manner.

FIG. 3 shows the results. As is clear from FIG. 3, the absorption in the harmful ultraviolet region of 280 to 360 nm was not eliminated by washing, indicating that the work cloth obtained as described above has an excellent ultraviolet shielding ability over a long period of time.

Comparative Example 1 The processing solution of Example 2 was treated in the same manner as in Example 2 except that 1,2,3,4-butanetetracarboxylic acid was not added, and the ultraviolet absorbing ability was examined in the same manner.

FIG. 4 shows the results. As is clear from FIG. 4, the absorption in the harmful ultraviolet region of 280 to 360 nm disappeared by washing, indicating that the processed cloth obtained above does not have a long-term ultraviolet shielding ability.

[Brief description of the drawings]

FIG. 1 is an ultraviolet absorption spectrum diagram of a treated cloth obtained in Example 1.

FIG. 2 is an ultraviolet absorption spectrum of the treated cloth obtained in Example 2.

FIG. 3 is an ultraviolet absorption spectrum diagram of a treated cloth obtained in Example 3.

FIG. 4 is an ultraviolet absorption spectrum of the treated cloth obtained in Comparative Example 1.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroshi Tsujimoto 1-1-1, Takasu-cho, Nishinomiya-shi, Hyogo Mukogawa Danchi No.2 Building 918 (72) Inventor Kango Fujitani 128 (72) Inventor Mikio Nakazawa 1-91, Iseda-Kida, Uji-city, Kyoto (72) Inventor Koichi Murai 4-6-6, Tenjin, Nagaokakyo-shi, Kyoto (56) References JP-A 1-282388 (JP, A JP-A-61-63786 (JP, A) JP-A-49-61070 (JP, A) JP-A-49-61068 (JP, A) Japanese Translation of PCT Application No. Sho 60-500137 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) D06M 13/358 D06M 13/192

Claims (2)

(57) [Claims] 1. A compound of the general formula [In the formula, R represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a halogen atom. X represents an alkylene group having 1 to 12 carbon atoms. Y represents a polyhydric alcohol residue. l represents 0 or 1, m represents an integer of 1 to 10, and n represents 1 or 2. Cellulose fibers obtained by reacting an ester of a polyhydric alcohol represented by the formula (1) with a carboxylated hydroxyphenylbenzotriazole and a polycarboxylic acid on the cellulose fibers. 2. A method for producing a cellulose fiber, wherein the aliphatic polyhydric alcohol according to claim 1 and an ester of a carboxylated hydroxyphenylbenzotriazole and a polycarboxylic acid are allowed to act on the cellulose fiber.