JPH05214673A - Uv absorber for hydrophobic fiber - Google Patents

Abstract

PURPOSE:To obtain the subject UV absorber suitable for application to a hydrophobic fiber, excellent in UV absorbing effect, low in yellowing and exhibiting an excellent washing fastness by blending specified UV absorbers. CONSTITUTION:A UV absorber composed of a compound represented by formula I (R1 is H or OH; R2 is H, OH or CH3; R3 is H, OH or CH3) and/or a compound expressed by formula II (R4 is H or Cl; R5 is H or t-C4H9) and useful for application to a hydrophobic fiber is dispersed, e.g. by using an anionic or nonionic surfactant. A polyester- or polyamide-based fiber is subjected to exhaustion dyeing treatment at the ordinary temperature by using the obtained dispersion, thus obtaining the objective hydrophobic fiber excellent in UV absorbing effect and washing fastness and low in yellowing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet absorber suitable for hydrophobic fibers, especially polyester and polyamide fibers.

[0002]

2. Description of the Related Art In recent years, it has been said that chlorofluorocarbon has been used in large quantities in the world, and as a result, the ozone layer of the earth has been destroyed and ultraviolet rays harmful to the human body have increased. Prolonged exposure to UV light will damage the skin, causing erythema and blistering. In addition, melamine formation is promoted and the skin becomes black. Further, when repeatedly exposed to ultraviolet rays, collagen fibers in the subcutaneous tissue are destroyed, generation of fine lines, pigmentation such as spots and freckles, and aging of the skin are promoted. Furthermore, there is a risk of skin cancer with long-term irradiation.
In the ultraviolet rays contained in the sun rays, the wavelength that causes acute inflammation particularly to human skin is about 280 to 32.
It is a 0 nm medium wave beam (UVB). About 320-400n
m long wave light (UVA) oxidizes the reduced melamine of the epidermis and directly causes sunburn. Most of ultraviolet rays (UVC) with a short wavelength of 280 nm or less are absorbed in the atmosphere, and the amount reaching the ground surface is small, but for the skin, U
As harmful as VB.

Therefore, attempts to prevent these ultraviolet rays have been made in cosmetics and the like, and have recently been applied to clothing. As such an ultraviolet absorber, dimethylaminobenzoic acid esters, salicylic acid esters, cinnamic acid esters, cyanoacrylic acid esters, benzophenone-based compounds, benzotriazole-based compounds and the like are known. Currently for the purpose of applying
For example, for polyester, an ultraviolet absorber originally intended to improve the light resistance of a dyed polyester fiber and an aqueous dispersion thereof [see, for example, JP-A-60-59185 2-
(2'-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-benzotriazole] has been used. Further, in the case of nylon fiber, the light resistance improver of the dyed fiber is generally a copper metal compound or the like as found in JP-B-59-44434, and the so-called ultraviolet absorbing effect is small, Attempts have been made to use light resistance improvers for dyed polyester fibers.

[0004]

However, when it is used for the purpose of producing an ultraviolet absorbing fiber, it has not only the ultraviolet absorbing effect but also the ease of processing into a fiber, that is, the affinity of the ultraviolet absorbent with the fiber, Important factors are low yellowing and texture change due to treatment, good washing resistance, cost and safety. The light resistance of the dyed textiles is often good if it is not particularly impaired, and is required for the purpose of diversion of the light resistance improver of the textile dyed, or mere diversion of the UV absorber used in cosmetics from the viewpoint of safety. At present, they are not satisfied because they have different physical properties and performance.

Therefore, an object of the present invention is to provide an ultraviolet absorber suitable for producing an ultraviolet absorbing fiber having improved physical properties as described above.

[0006]

That is, the ultraviolet absorbent for hydrophobic fibers according to the present invention comprises a compound represented by the following formula (1) and / or a compound represented by the following formula (2). Characterized by:

[Chemical 3] (However, R ₁ = -H, -OH; R ₂ = -H, -OH,-
_{CH 3; R 3 = -H,} -OH, a -CH ₃₎

[Chemical 4] (However, R ₄ = -H, -Cl; R ₅ = -H, -t-C ₄ H
₉ )

In the present invention, the above formula (1) or formula
Any compound represented by (2) can be used, but preferably 2,4-dihydroxybenzophenone,
2-hydroxy-4-methoxybenzophenone, 2,2 '
-Dihydroxybenzophenone, 2,2 ', 4-trihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4'-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone,
2,4'-dihydroxy-4-methoxybenzophenone,
2,2 ', 4,4'-tetrahydroxybenzophenone, 2,
2 ', 4'-trihydroxy-4-methoxybenzophenone, 2-hydroxy-4'-methoxybenzophenone,
2,4-dihydroxy-4′-methoxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2- (2'-hydroxy-5'-methylphenyl)-
Benzotriazole, 2- (2'-hydroxy-3'-t
-Butyl-5'-methylphenyl) -benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5
-Chlorobenzotriazole, 2- (2'-hydroxy-
3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole is preferable, and 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxybenzophenone and 2 are more preferable. , 2 ', 4-trihydroxybenzophenone, 2,
4'-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4'-methoxybenzophenone, 2- (2'-hydroxy-5 '-Methylphenyl) -benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-
Chlorobenzotriazole is good.

The ultraviolet absorbent of the present invention has the above formula.
It is preferable to use one or more compounds represented by formula (1) and one or more compounds represented by formula (2) in combination, and in particular, formulas (1) :( 2) = 1: 9 to When it is 9: 1, a good effect is obtained, and most preferably the formula (1) :( 2) = 1: 5 to 5 :.
1 is good.

The ultraviolet absorbent of the present invention can be used for hydrophobic fibers in order to impart ultraviolet absorbing ability to the hydrophobic fibers, and in this case, 0.0% for the hydrophobic fibers.
The treatment may be carried out with an aqueous dispersion which is present in an amount of 1% by weight or more, preferably 0.1-5% by weight.

When the ultraviolet absorbent of the present invention is 0.01% by weight or more based on the hydrophobic fiber, sufficiently effective performance can be obtained, and there is no particular upper limit, and a high content can be used. Even if it exceeds the weight%, the effect is not so much improved, so from the point of industrial suitability, 0.1 to 5 weight% is preferable. Further, the concentration of the ultraviolet absorber aqueous dispersion does not affect the effect of using the ultraviolet absorber of the present invention, and the amount of the ultraviolet absorber is good as long as it is low or high. Can be used for

The aqueous dispersion of the ultraviolet absorber may be produced by a conventionally known method, for example, water, an ultraviolet absorber, a dispersant, a protective colloid agent, a thickener and the like are mixed and pulverized by a sand mill, a ball mill, a colloid mill or the like. A wet milling method of forcibly stirring together with steel balls, glass beads and the like in the machine is suitable, and it is preferable to use an aqueous dispersion having an average particle size of 5 μm or less.

The dispersant is not particularly limited, and conventionally known ones can be used. For example, a sulfonic acid type anionic surfactant, a phosphoric acid ester type surfactant, a polycarboxylic acid type surfactant, a polyoxyalkylene type non-surfactant. Examples thereof include ionic surfactants.

A cationic surfactant may be used if necessary, for example, in combination with an ultraviolet absorber other than the ultraviolet absorber of the present invention.

As the sulphonic acid type anionic surfactant, a formaldehyde condensate of naphthalene sulfonic acid,
Examples thereof include formaldehyde condensate of phenol sulfonic acid, formaldehyde condensate of cresol sulfonic acid, lignin sulfonic acid, alkylbenzene sulfonic acid, alkylnaphthalene sulfonic acid, and sulfosuccinic acid ester.

As the polyoxyalkylene type nonionic surfactant, higher alcohol alkylene oxide adduct, alkylphenol alkylene oxide adduct,
Examples thereof include fatty acid alkylene oxide adducts, propylene oxide / ethylene oxide copolymers, sorbitan fatty acid esters, and glycerin fatty acid esters.

Examples of the protective colloid agent and the thickener include carboxymethyl cellulose, polyvinyl alcohol, hydroxypropyl cellulose and the like.

There are roughly two methods for treating hydrophobic fibers with an aqueous dispersion of an ultraviolet absorbent, and one is to immerse the hydrophobic fibers in the aqueous dispersion of an ultraviolet absorbent and to absorb it over a certain period of time. The so-called exhaustion method in which the ultraviolet absorbent is supported on the hydrophobic fiber by exhaustion, and the other is to dip the hydrophobic fiber in the aqueous dispersion of the ultraviolet absorbent or spray the aqueous dispersion of the ultraviolet absorbent on the hydrophobic fiber. This is a so-called pad method in which the hydrophobic fiber is made to absorb the aqueous dispersion of the ultraviolet absorber and held, and then the ultraviolet absorber is forcibly supported on the hydrophobic fiber by heat treatment.

The dipping in the exhaust method requires raising the temperature of the liquid or prolonging the dipping time when the affinity between the ultraviolet absorbent and the hydrophobic fiber is low, but in the pad method the ultraviolet absorbent is used. This point is good because it is forcibly supported regardless of the affinity between the hydrophobic fiber and the hydrophobic fiber.

On the other hand, there are disadvantages such as limited equipment, and it is desirable to be able to process even by an exhaust method which can be processed by an ordinary batch dyeing machine. In the exhaustion method, the degree of affinity between the ultraviolet absorber and the hydrophobic fiber greatly affects the ultraviolet absorption effect, washing resistance, etc., and the conventional ultraviolet absorber has a low affinity with the hydrophobic fiber. It was necessary to take measures such as lengthening the immersion time and raising the liquid temperature.
However, raising the temperature of the liquid has the adverse effect of increasing the working time and cost as well as lowering the dyeing fastness, and there has been a demand for treatment at low temperatures.

When the ultraviolet absorbent of the present invention is used, the hydrophobic fiber can be treated at a high liquid temperature, and at the same time, it can be treated at room temperature to take advantage of the exhaust method.

That is, the exhaustion treatment of the hydrophobic fiber using the ultraviolet absorbent of the present invention is from room temperature to 180 ° C., preferably 2
It is effective to exhaust and process at 0 to 150 ° C.

The UV absorber of the present invention can be used even if it is used in the pad method without impairing the effect.
It can be used in the same manner as the conventional method. In the case of the pad method,
The amount of the ultraviolet absorber with respect to the above-mentioned hydrophobic fiber is the amount of the ultraviolet absorber in the aqueous dispersion to which the fibers are attached.
Incidentally, when the ultraviolet absorbent of the present invention is used, unlike the conventional pad method, if the aqueous dispersion is held for a certain amount of time as in the exhaust method after absorbing the liquid, the hydrophobic fiber is absorbed by the ultraviolet rays without heat treatment. It is also possible to carry an agent.

The ultraviolet absorbent of the present invention can be applied to hydrophobic fibers in general, and is particularly effective for polyester and nylon, particularly nylon, but not limited thereto. Further, it is also applicable to a blended fiber composed of these hydrophobic fibers and affinity fibers such as cellulosic fibers.

Further, for example, butyl methoxydibenzoylmethane having UVA absorption may be used in combination within a range that does not impair the effects of the present invention.

[0025]

EXAMPLES The present invention will be further described below with reference to examples. Examples 1 to 7 30 parts of each of the ultraviolet absorbers shown in Tables 1 and 2 were mixed with 5 parts of sodium alkylnaphthalene sulfonate, 0.2 part of carboxymethyl cellulose and 64.8 parts of water, and pulverized with a horizontal continuous wet disperser. An aqueous dispersion having an average particle size of 0.6 to 1.0 μm was obtained.

The fibers were treated under the conditions shown in FIG. The UV absorption effect of the treated cloth is UV manufactured by Shimadzu
The light transmittance was measured and evaluated by a -220 type self-recording spectrophotometer. The results are shown in transmittance at 340 nm. The smaller the value, the better the effect. The yellowing due to the treatment was evaluated by measuring the whiteness of the Hunter using an SZ-Σ80 type spectrocolorimeter manufactured by Nippon Denshoku Industries. This value means that the larger the value, the better the whiteness. Washing resistance is JIS L0844
(Test method for dyeing fastness to washing) Method A-2 (Soap 5
g / liter, 50 ° C, 30 minutes), wash 5 times,
It was calculated by the following formula. The washing resistance is described as having a relatively good ultraviolet absorption effect.

[0027]

[Equation 1] The results are shown in Tables 1 and 2.

Comparative Examples 1 to 9 The ultraviolet absorbers of Comparative Examples shown in Tables 1 and 2 were treated in the same manner as in Examples. The results are shown in Tables 1 and 2.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

EFFECT OF THE INVENTION The ultraviolet absorbent of the present invention has an excellent ultraviolet absorption effect, little yellowing, and good washing resistance. Further, even if the exhaust temperature is low, it is adsorbed on the fibers, that is, it has a high affinity with the fibers, and there is almost no change in texture because no binder is used. In addition, the ultraviolet absorbent of the present invention is also highly safe since it contains cosmetic raw materials listed in the standard of cosmetic raw materials, and is excellent as an ultraviolet absorbent for hydrophobic fibers.

[Brief description of drawings]

FIG. 1 illustrates a method of treating a fiber with an ultraviolet absorbent in Examples and Comparative Examples.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location D06P 1/651 7306-4H 3/24 Z 7306-4H 3/52 Z 7306-4H

Claims (1)

[Claims] 1. An ultraviolet absorbent for hydrophobic fibers, which comprises a compound represented by the following formula (1) and / or a compound represented by the following formula (2). [Chemical 1] (However, R ₁ = -H, -OH; R ₂ = -H, -OH,-
CH ₃ ; R ₃ = -H, -OH, -CH ₃ ) (However, R ₄ = -H, -Cl; R ₅ = -H, -t-C ₄ H
₉ )