JPH05179568A - Fiber treating agent for protecting ultraviolet ray and woven fabric subjected to ultraviolet ray-protecting treatment - Google Patents

Abstract

PURPOSE:To obtain a fiber treating agent for protection of ultraviolet rays capable of readily carrying ultraviolet protecting treatment to fibers, excellent in ultraviolet protecting effect as well as retaining property of the effect and simultaneously having no adverse effect on fluorescence excitation phenomenon of fluorescent dyes. CONSTITUTION:A water soluble resin or emulsion resin for fiber treatment such as acrylic, glyoxal based, silicone based, urethane based, melamine based or fluorine based resin is blended with fine-particle metal oxide having 0.01-0.1mum average particle diameter (e.g. fine-particle titanium dioxide) of 3-65 pts.wt. based on 100 pts.wt. solid content of the resin to provide the objective fiber treating agent for protection of ultraviolet rays.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet ray preventing fiber treating agent which imparts an ultraviolet ray preventing function to fibers.

[0002]

2. Description of the Related Art Ultraviolet rays in sun rays (generally 1 to 380)
UV-A waves that belong to the near-ultraviolet region (300 nm or more) of the electromagnetic wave in the wavelength range of nm) darken the skin, cause spots and freckles, promote skin aging, and , UV-B waves are known to adversely affect the skin, such as causing the skin to swell red, burning, and causing water bubbles.

Therefore, in cosmetics, various products for preventing ultraviolet rays have been developed so far.
Recently, it has been demanded that textile products such as clothes retain the function of preventing ultraviolet rays, and products for preventing ultraviolet rays have begun to be developed.

As means for imparting an ultraviolet ray preventing function to such a textile product, light reflecting ceramics or an ultraviolet ray absorbent is kneaded in the spinning stage, or the ultraviolet ray absorbent is adsorbed on the fiber surface, or the ultraviolet ray absorbent is used. Is dispersed in a resin and the surface of the fiber is coated therewith (for example, “processing technology”, Vol. Two
6, No. 10 (1991), p649].

[0005]

However, the ultraviolet absorbers that have been used so far are organic ultraviolet absorbers such as benzotriazole-based, salicylic acid-based, and benzophenone-based ultraviolet absorbers. There is a problem that the effect is lost or coloring due to deterioration is caused.

Further, when the light-reflecting ceramics are kneaded at the spinning stage, the light-reflecting ceramics have poor dispersibility, so that a special master batch for improving the dispersibility is required, or yarn breakage occurs. There was a problem.

The present invention solves the above-mentioned problems in the prior art, makes it possible to easily carry out an anti-ultraviolet ray treatment on a fiber, has an excellent anti-ultraviolet ray effect, and is excellent in its durability. The purpose is to provide.

[0008]

The present invention has an average particle diameter of 0.0 based on 100 parts by weight of the solid content of a water-soluble resin or emulsion resin which is usually used for resin processing of fibers.
By blending 3 to 65 parts by weight of 1 to 0.1 μm of fine particulate metal oxide to form a fiber treatment agent for ultraviolet protection,
The above object is achieved.

That is, the fiber treatment agent for preventing ultraviolet rays of the present invention is prepared by preparing a treatment solution diluted to an appropriate concentration as described in detail later, and immersing a woven cloth in the treatment solution to form a woven cloth. Since it is possible to carry out anti-UV treatment such as, it is possible to easily carry out anti-UV treatment without the need for a special master batch like when kneading light-reflecting ceramics. Since it has an excellent ultraviolet ray blocking effect, an excellent ultraviolet ray preventing effect can be obtained, and since the particulate metal oxide is an inorganic substance, the resistance to deterioration is far superior to that of an organic ultraviolet absorber, Excellent durability of UV protection effect.

As the emulsion resin used in the preparation of the fiber treatment agent for preventing ultraviolet rays of the present invention, for example, an acrylic resin (for example, trade name: Primal T) is used.
R-49, manufactured by Nippon Acrylic Chemical Co., Ltd., glyoxal-based resin (for example, trade name: Euramine T-TS-10,
Mitsui Toatsu Chemical Co., Ltd., silicone resin (for example, product name: Light Silicone R-550N, Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), urethane resin (for example, product name: Elastron MF-9, Daiichi Kogyo Seiyaku Co., Ltd.) Manufactured), melamine-based resin (for example, trade name: Sumitex Resin M-6, manufactured by Sumitomo Chemical Co., Ltd.), fluorine-based resin (for example, trade name: Eras Guard 200, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like are suitable. It is mentioned as a thing.

The average particle size used in the present invention is 0.0
As the fine particle metal oxide having a particle size of 1 to 0.1 μm, for example, fine particles of a white metal oxide such as titanium dioxide, zirconium oxide, zinc oxide, aluminum oxide, silicon oxide and antimony oxide are preferably used. Particularly, fine particles of titanium dioxide or zinc oxide are preferable.

Further, in order to improve dispersibility, light resistance and the like, a material obtained by coating the surface of the above-mentioned fine particle metal oxide with alumina, silica, titania, zirconium or the like can be preferably used.

In the present invention, it is necessary that the fine particle metal oxide has an average particle diameter of 0.01 to 0.1 μm. This is because it is necessary that the particulate metal oxide transmits visible light with a long wavelength, is not colored and is transparent without hiding power, and also reflects and absorbs ultraviolet light with a short wavelength to block ultraviolet light. This is because it is necessary to have an action.

That is, when the average particle size of the fine particulate metal oxide is smaller than 0.01 μm, the ultraviolet shielding effect is small, and the average particle size of the fine particulate metal oxide is 0.
When it is larger than 1 μm, visible light also begins to be reflected and becomes opaque.

In the UV-preventing fiber treating agent of the present invention, the average particle diameter is 0.01 to 0.01 with respect to 100 parts by weight of the solid content of the water-soluble resin or emulsion resin for fiber processing.
It is necessary to mix 3 to 65 parts by weight of the particulate metal oxide of 0.1 μm, and it is particularly preferable to mix 8 to 45 parts by weight.

When the amount of the finely divided metal oxide compounded is less than 3 parts by weight with respect to 100 parts by weight of the resin solid content,
There is little effect of imparting an ultraviolet protection function to the fiber,
Further, the compounding amount of the above-mentioned fine particulate metal oxide is resin solid content 1
When it is more than 65 parts by weight with respect to 00 parts by weight, the texture of the fibers treated with the fiber treatment agent for preventing ultraviolet rays becomes poor, and the adhesion state of the fine particle metal oxide to the fibers also becomes poor.

The fiber treatment agent for preventing ultraviolet rays of the present invention can be applied to both natural fibers and artificial fibers. Examples of the natural fiber include cotton, silk, hemp, and wool. Examples of artificial fibers include nylon, polyester, acrylic, vinylon, polypropylene and other synthetic fibers, viscose rayon and other recycled fibers, and acetate and other semi-synthetic fibers.

The form of the fiber during the treatment may be the fiber itself, a fiber product such as a filament, a yarn,
It may be a woven fabric, a non-woven fabric, a knitted fabric, or a fiber finished product such as a blouse, sportswear, stockings, or a fabric of parasol. However, usually, in view of workability at the time of processing, the filament, the thread, the woven fabric and the like are processed, and after the processing, a desired finished product is finished if necessary.

As described above, the fiber treatment agent for preventing ultraviolet rays of the present invention can easily perform an ultraviolet ray preventing treatment on a fiber, has an excellent ultraviolet ray preventing effect, and is excellent in its sustainability. A particular advantage over the UV absorber is that it does not eliminate the fluorescence excitation phenomenon of the fluorescent dye.

Explaining this in detail, a fluorescent dye is usually used to improve the whiteness of the woven cloth. Fluorescent white is most preferred for summer clothing, which requires the most protection from ultraviolet rays.

When fluorescent treatment is performed using a fluorescent white dye,
When a conventional organic UV absorber is used, for example, “processing technology”, Vol. 20, No. 10 (199
1), as described on page 651, the fluorescence excitation phenomenon is completely eliminated, and the desired whiteness cannot be obtained.

However, in the case of the ultraviolet ray treating fiber treating agent of the present invention, the particulate metal oxide does not adversely affect the fluorescent dye, and the above-mentioned fluorescence excitation phenomenon does not disappear. Therefore, by post-processing a woven fabric or the like treated with a fluorescent white dye with the agent for treating ultraviolet rays of the present invention, it is possible to achieve both an ultraviolet ray preventing effect and an improvement in whiteness. Woven fabrics are not only white, but also red,
Although it is dyed with blue, yellow, etc., or a pattern is designed, since the fiber treatment agent for ultraviolet ray prevention of the present invention has a particle diameter of the fine particle metal oxide to be used is shorter than the wavelength of visible light, It is transparent to visible light and does not cause the so-called fog phenomenon in which the color or pattern of the woven fabric becomes whitish.

The fiber treatment agent for preventing ultraviolet rays according to the present invention has a solid content of 100 of the above-mentioned water-soluble resin or emulsion resin.
It is prepared by adding 3 to 65 parts by weight of a fine particle metal oxide having an average particle diameter of 0.01 to 0.1 μm to the parts by weight and dispersing. In that case, an anionic activator, a cationic activator, a nonionic activator or the like may be added as a dispersant, if necessary, in order to improve the dispersion stability. However,
When adding an activator, it is desirable to consider the liquidity of the resin so as not to cause coagulation, and when the fiber is not subjected to fluorescence treatment, an ultraviolet absorber may be used in combination. ..

The specific means for treating the fibers with the fiber treatment agent for preventing ultraviolet rays of the present invention is as follows, using a case where a woven fabric is used as the fibers.

First, a treatment solution is prepared by diluting the ultraviolet ray treating fiber treatment agent of the present invention with water to a concentration of about 30 to 200 g / l, and a woven fabric is usually added to the treatment solution for about 1 to 60 seconds. After dipping, the squeezing ratio is set to about 60 to 90%, followed by drying and curing (baking). And, in the above treatment, when diluted with water, the amount of the particulate metal oxide is 1 to 20 g / l.
It is preferable that the concentration be about the same.

[0026]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples.

Examples 1 to 5 and Comparative Examples 1 to 3 Resins shown below and finely divided metal oxides were blended in the compositions shown in Table 1 to prepare the ultraviolet ray treating fiber treatment agents of Examples 1 to 5, The test cloth (cotton broad No. 40) was subjected to UV protection treatment. In addition, the compounding amounts shown in Table 1 are all parts by weight, and the resin amount is shown by the solid content.

Resin: Primal TR49 (trade name, acrylic resin, resin concentration 50% by weight, manufactured by Nippon Acrylic Chemical Co., Ltd.)

Particulate metal oxide: MT-500B (trade name, titanium dioxide, average particle size 0.035 μm, manufactured by Teika)

As Comparative Example 1, the case where no ultraviolet ray protection treatment was carried out was selected, and in Comparative Example 2, treatment was carried out only with the resin, and Comparative Example 3
Was selected for treatment with a treatment liquid prepared by adding a conventional organic UV absorber to water. UV absorber is Sunguard T40
(Trade name, benzotriazole type, manufactured by Senka Co., Ltd.) is used, and this ultraviolet absorber is also added to the treatment liquid of Example 5. The concentration of the treatment liquid in Table 1 shows the concentration of the ultraviolet ray preventing fiber treatment agent in the treatment liquid in which the test cloth is dipped.

[0031]

[Table 1]

Treatment and Test Method Cotton broad No. 40 was used as a test cloth, and the test cloth was dipped in each of the treatment solutions shown in Table 1 at 25 ° C. for 10 seconds, and after the immersion, was squeezed with a mangle (rubber roller). The rate was set to about 70%, dried at 100 ° C. for 3 minutes, and then cured at 130 ° C. for 1 minute.

The transmittance of the test cloth after the above treatment was measured with a self-recording spectrophotometer model U-3410 manufactured by Hitachi. Table 2 shows the transmittances in the wavelength range of 290 to 420 nm including a part of ultraviolet rays and visible rays.

[0034]

[Table 2]

As shown in Table 2, Examples 1 to 5 of the present invention
Is a wavelength of 380 nm in the ultraviolet region as compared with Comparative Examples 1 to 3.
The following transmittance was small, and the ultraviolet ray preventing effect was excellent.

In Example 5, the conventional organic UV absorber was also used, but no particular synergistic effect was observed.

Examples 6 to 7 and Comparative Examples 4 to 6 Cotton broad 40, which had been fluorescent-treated with a fluorescent white dye, was treated with a fiber treatment agent for ultraviolet protection, and its ultraviolet protection effect and fluorescent whiteness were examined.

The composition of the fluorescent treatment, the fiber treatment agent for ultraviolet protection, the ultraviolet protection treatment, the test method and the results are as follows.

Fluorescent treatment Test cloth: cotton broad 40 Fluorescent white dye: MiKephor BSconc. (Product name, manufactured by Mitsui Toatsu Dye Co., Ltd.)

MiKephor BSconc. 1% by weight aqueous solution was prepared, and cotton broad 40 was made to have a bath ratio of 1:30, and was immersed at 40 ° C. for 30 minutes for fluorescent treatment.

Composition of UV-Preventing Fiber Treatment Agent Table 3 shows the composition. The resin, the particulate metal oxide and the ultraviolet absorber used are the same as those used in Example 1 and the like.

Comparative Example 4 shows a case in which the cotton broad cloth 40 which has been subjected to the fluorescent treatment is not subjected to any ultraviolet ray preventive treatment, and Comparative Example 5 has a conventional organic ultraviolet ray absorbent (Sunguard T40, mentioned above) in water. The case of treatment with the added treatment liquid is shown, and the comparative example 6 shows the case where the ultraviolet treatment is not applied to the cotton broad 40 before the fluorescence treatment.

[0043]

[Table 3]

UV Protection Treatment and Testing Method The cotton broad 40 treated with the above-mentioned fluorescence was used in Example 6 of Table 3.
~ 7 and the treatment solution described in Comparative Example 5 at 25 ℃ for 10 seconds, after dipping, with a mangle (rubber roller) to a squeezing ratio of about 70%, dried at 100 ℃ for 3 minutes, then at 130 ℃ for 1 minute. By curing, UV protection treatment was performed.

The reflectance of the cotton broad 40 which has been subjected to the ultraviolet ray prevention treatment as described above was measured with a 607 color analyzer manufactured by Hitachi Ltd. over a wavelength range of 380 to 780 nm. The reflectance in the wavelength range of 380 to 580 nm is shown in FIG.

In FIG. 1, Examples 6 to 7 and Comparative Example 4
Are shown on the same curve, because they showed almost the same reflection properties, making it impossible to show on another curve.

As shown in FIG. 1, Examples 6 to 7 of the present invention are shown.
Shows almost the same reflection characteristics as Comparative Example 4 which was only subjected to fluorescence treatment but not subjected to ultraviolet protection treatment, and Comparative Example 5 which was subjected to ultraviolet protection treatment with an organic ultraviolet absorber or Comparative Example 6 which was cotton broad 40 itself. Compared to, the visible part of 420-44
The reflectance in the vicinity of 0 nm was high, and the fluorescent whiteness was kept high even though the anti-ultraviolet treatment was performed.

Next, the above Examples 6 to 7 and Comparative Example 4
For cotton broad 40 of Nos. 6 to 6, the transmittance was measured in the same manner as in Example 1 and the like. Table 4 shows the transmittances at wavelengths of 290 to 420 nm.

[0049]

[Table 4]

As shown in Table 4, Examples 6 to 7 of the present invention are shown.
Has a wavelength of 380 nm in the ultraviolet region as compared with Comparative Examples 4 to 6.
The following transmittance was low, and the ultraviolet ray preventing effect was excellent.

[0051]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, it is possible to provide a fiber treatment agent for UV protection, which is easy to perform UV protection treatment on a fiber, has an excellent UV protection effect, and has excellent durability. It was

Further, since the fiber treatment agent for ultraviolet ray prevention of the present invention does not adversely affect the fluorescence excitation phenomenon of the fluorescent dye, the fiber treatment agent for ultraviolet ray prevention of the present invention can be applied to a woven cloth or the like which is fluorescently treated with a fluorescent white dye. By carrying out the ultraviolet ray prevention treatment with, it is possible to achieve both the addition of the ultraviolet ray preventing function and the improvement of the fluorescent whiteness.

[Brief description of drawings]

FIG. 1 is a diagram showing visible light reflection characteristics of Examples 6 to 7 of the present invention and Comparative Examples 4 to 6.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location D06P 5/00 DBA 9160-4H 104 9160-4H (72) Inventor Yasuaki Kumagai Nishikonishi Nishi, Okayama City, Okayama Prefecture 1072 Teika Co., Ltd. Okayama Laboratory (72) Inventor Noriyuki Tanno 1-347, Funamachi, Taisho-ku, Osaka City Teika Co., Ltd.

Claims (3)

[Claims] 1. A solid content 1 of a water-soluble resin or emulsion resin for fiber processing such as acrylic, glyoxal, silicone, urethane, melamine, and fluorine.
3 to 65 parts by weight of a particulate metal oxide having an average particle diameter of 0.01 to 0.1 μm is blended with 100 parts by weight of an ultraviolet ray preventing fiber treating agent. 2. The fiber treatment agent for ultraviolet protection according to claim 1, wherein the metal oxide is titanium dioxide and / or zinc oxide. 3. A fiber cloth having an anti-ultraviolet function, characterized in that a fiber cloth treated with a fluorescent dye is treated with the fiber treatment agent for ultraviolet light protection according to claim 1.