JPH07197310A - UV shielding agent for fiber blending - Google Patents

Abstract

PURPOSE:To obtain a ultraviolet rays-shielding agent for blending into fiber, free from lowering of ultraviolet rays-shielding effect, having good dispersibility to fibers and without impairing characteristics of fibers themselves. CONSTITUTION:This ultraviolet rays-shielding agent for blending into fibers consists of composite particles having a coated layer of at least one kind of metal oxide selected from a group composed of titanium, iron, lead, zirconium, vanadium, cerium, yttrium on fine particles used as a core.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an ultraviolet shielding agent,
More specifically, the present invention relates to an ultraviolet ray shielding agent for blending fibers, which comprises composite particles having a coating layer of a specific metal oxide on core fine particles.

[0002]

2. Description of the Related Art Heretofore, various synthetic fibers such as polyamide and polyester have been devised for improving water absorption and texture. At present, as one of the synthetic fibers having improved water absorption, light weight, and good texture, for example, a hollow fiber having a hollow inside can be cited. However, the hollow fiber has a drawback that it is inferior in ultraviolet ray shielding effect to a non-hollow fiber having the same fiber cross-sectional area. As the hollowness is increased to improve the water absorption capacity and the weight is reduced, the amount of ultraviolet rays shielded by the fiber itself is decreased. On the other hand, if the fabric is made thick to shield the ultraviolet rays, the lightness is impaired, which causes problems such as being undesirable. This problem also applies to fibers other than hollow fibers. Therefore, in order to absorb or reflect ultraviolet rays without impairing the lightness, it is performed to add an ultraviolet absorber such as benzotriazole or benzophenone or an ultraviolet shielding agent such as titanium oxide, talc or kaolin to the fiber. However, although the above-mentioned ultraviolet absorber has a certain degree of ultraviolet absorbing effect, when added in a high concentration, it may be discolored or deteriorated by sunlight, and its decomposition product may cause skin damage. Further, since the ultraviolet shielding agent has poor dispersibility, it cannot be uniformly blended in the fiber, which causes problems such as yarn breakage during fiber processing and reduction in fiber strength.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a UV-screening agent for blending fibers, which does not deteriorate the UV-screening effect, has good dispersibility in the fiber, and does not impair the properties of the fiber itself. To provide.

[0004]

The object of the present invention is to provide titanium, iron, lead, zirconium, vanadium,
Achieved by an ultraviolet shielding agent for blending fibers, comprising composite particles having a coating layer of at least one metal oxide selected from the group consisting of cerium and yttrium (hereinafter referred to as “specific metal oxide”) To be done.

The present invention will be described in detail below. The core fine particles used in the present invention are not particularly limited as long as they are organic compounds, various polymers or natural polymers can be used, and specifically, polystyrene, polystyrene, polymethylmethacrylate, polyethylene,
Polymers such as polypropylene, polyimide, polyamide, polyvinyl chloride, polyvinylidene chloride, polyurethane, polycarbonate, fluororesin, polyester elastomers, polyamide elastomers, styrene elastomers, butadiene elastomers, etc., or a copolymerizable monomer. Copolymers of copolymers (including crosslinkable monomers such as divinylbenzene and ethylene glycol dimethacrylate); cellulose, natural rubber, etc., and one or more of these core fine particles can be mentioned. Can be used in combination. Further, the shape of the core fine particles is not limited to the true spherical shape, but may be irregular shaped particles such as flat particles having concave portions and rod-like particles having a major axis and a minor axis.

Specific metal oxides used for coating the core fine particles include titanium, iron, lead, zirconium, vanadium,
At least one metal oxide selected from the group consisting of cerium and yttrium is preferable, but it is preferably a composite particle in which titanium oxide and another specific metal oxide are combined, and particularly titanium oxide in the specific metal oxide. Is 30
It is preferably about 95% by weight.

In the present invention, as a method for coating the surface of the core fine particles with the specific metal oxide, for example, a hydrolysis method,
Various methods such as mechanical method and vacuum method can be adopted. In the hydrolysis method, the core fine particles are uniformly dispersed in an aqueous solution of a hydrolyzable metal salt and / or metal alkoxide, and then at room temperature or while being heated to a temperature of 40 ° C. or higher,
If necessary, in the presence of carbonate ions having a source of urea, carbonic acid or the like, a hydrolysis reaction is caused to form a basic metal carbonate on the core fine particles, followed by alkali treatment at room temperature, or by air treatment. It is a method of converting into a specific metal oxide by heating to 200 to 300 ° C. in the atmosphere. here,
The amount of the hydrolyzable metal salt and / or the metal alkoxide used per 1 liter of the hydrolysis reaction solution is 0.01 to 1
00 millimole is preferable, and 0.1 to 100 millimole is more preferable. The mechanical method is to put the metal and / or metal alkoxide and the core fine particles into a mixer or a crusher having high-speed rotating blades or rotating arms such as a Henschel mixer, a hybridizer, and an Ong mill, and then 200 to 1
20,000 rpm, preferably 1,000-8,000
rpm for 1 to 120 minutes, preferably 3 to 30
This is a method of coating the core fine particles with a metal and / or a metal oxide by stirring at high speed for a minute, usually at room temperature with heating or cooling if necessary. The vacuum method is usually a vacuum deposition, sputtering or ion plating for 1 to 30 minutes while vibrating the core fine particles to be treated at a vacuum degree of 10 ^{−5 to 2} Pa using a metal and / or a metal oxide as a deposition source or a target. This is a method of processing. When a metal is coated, it can be converted into a metal oxide by heating at 100 to 300 ° C. in oxygen or air after the above treatment.

When coating the metal oxide,
The surface of the core fine particles may be hydrophilized by a physical method (for example, irradiation with short wavelength ultraviolet rays, plasma treatment, etc.) or a chemical method (for example, hydrolysis, introduction of a polar group) and then coated by the above method.

The average particle size of the composite particles obtained as described above is usually 0.01 to 10 μm for practical use, and preferably 0.02 to 5 μm. 0.01μ
When it is less than m, the cohesiveness between particles becomes strong, and it is not possible to obtain homogeneous composite particles, and when it exceeds 10 μm,
The spinnability of the fiber mixed with this may become poor, and there is a possibility that yarn breakage may occur or the texture and strength of the fiber may be impaired. Further, the thickness of the coating layer of the specific metal oxide with respect to the outer diameter of the composite particles is preferably 0.1 to 90%, more preferably 1 to 80%.

Use of composite particles when the composite particles thus obtained are blended with fibers (for example, synthetic fibers such as polyamide fibers (6-nylon, 6,6-nylon, etc.), polyester fibers, polyurethane fibers, etc.) The amount is 1 fiber
0.5 to 30 parts by weight with respect to 00 parts by weight,
It is preferably 1 to 20 parts by weight. If the amount of the composite particles used is less than 0.5 part by weight, a sufficient ultraviolet ray shielding effect cannot be obtained, and if it exceeds 30 parts by weight, the spinnability may be poor or the strength of the fibers may be reduced. When the conventionally used inorganic particles such as titanium oxide are blended, if the blending amount exceeds 5 parts by weight, spinnability is affected, but the composite particles of the present invention have excellent dispersibility.
Even if added up to parts by weight, the spinnability is not affected. When a large amount is blended, it is preferable to use core fine particles having a composition corresponding to the fibers to be blended. That is, it is preferable to use composite particles in which an acrylic polymer is used as core fine particles for the acrylic fiber, and to use composite particles in which a polyamide polymer such as nylon 6 is used as the core fine particles for the polyamide fiber.

When the ultraviolet shielding agent of the present invention is blended with the fiber, other components usually blended with the fiber can be blended appropriately as needed. For example, a small amount of organic ultraviolet absorber is added to express higher shielding properties, a flame retardant, a plasticizer, an antibacterial agent, a deodorant, an optical brightener,
Additives such as stabilizers may be contained.

[0012]

EXAMPLES The present invention will be described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Light resistance test: The fiber stock solution was stretched at 20 ° C. in a 65% by weight dimethylformamide aqueous solution while being spun, washed with water, dried and densified, and wet-heat treated at 120 ° C. The obtained fiber was made into a non-woven fabric (100 g / m
² , thickness 1 mm), and a light resistance test was performed according to JIS L-0842.

UV transmittance; 360 nm and 305 for the nonwoven fabric before the light resistance test and 96 hours after the test.
UV transmittance of nm is Hitachi spectrophotometer u-34
00 was used for measurement.

Synthesis Example 1 200 g of ethyl acrylate, 100 g of polyfunctional urethane acrylate UA-101H (manufactured by Kyoeisha Co., Ltd.), 10 g of ethylene glycol dimethacrylate, 1 g of 2,2-azobis (2,4-dimethylvaleronitrile), sodium lauryl sulfate. 05g and 1500g of water are mixed,
5 hours at 40 ° C with stirring under nitrogen atmosphere, then 6
Polymerization was carried out at 5 ° C. for 5 hours and at 80 ° C. for 8 hours to obtain polymer particles. The average particle size of the polymer particles was 8 μm. 80 g of the obtained polymer particles and an average particle size of 0.05
20g of titanium oxide particles of μm and 1,500 at room temperature were used by using an OM Dizer (manufactured by Nara Machinery Co., Ltd.) with an internal volume of 4l.
After premixing at rpm for 3 minutes, another 7,500 rp
m for 5 minutes to obtain composite particles coated with titanium oxide (hereinafter referred to as “composite particle A”). Composite particle A
Had an average particle size of 8.24 μm.

Synthesis Example 2 80 g of the polymer particles obtained in Synthesis Example 1 and an average particle size of 0.
20 g of 02 μm zinc oxide particles were mixed and treated in the same manner as in Synthesis Example 1 to obtain composite particles coated with zinc oxide particles (hereinafter referred to as “composite particles B”). The average particle size of the composite particles B was 8.12 μm.

Synthesis Example 3 80 g of the polymer particles obtained in Synthesis Example 1 and an average particle size of 0.
5 μm of titanium oxide particles of 05 μm and average particle diameter of 0.0
15 g of 5 μm zirconium oxide was mixed and treated in the same manner as in Synthesis Example 1 to obtain composite particles coated with titanium oxide and zirconium oxide (hereinafter referred to as “composite particles C”). The average particle size of the composite particles C was 8.20 μm.

Example 1 Fiber resin in acrylic fiber stock solution (25% by weight solution of dimethylformamide) consisting of acrylonitrile / ethyl acrylate / sodium methacryl sulfonate = 93.3 / 5.5 / 1.2 (weight ratio) With respect to 100 parts by weight, a non-woven fabric obtained by using a fiber stock solution containing 5 parts by weight of the composite particles A obtained in Synthesis Example 1 was subjected to a light resistance test and an ultraviolet transmittance measurement. Further, the dispersibility of the composite particles A added to the fiber stock solution was observed using an electron microscope.

Comparative Example 1 Titanium oxide powder having an average particle diameter of 0.05 μm was used as fiber resin 1
A non-woven fabric obtained by using the same fiber stock solution as in Example 1 except that 1 part by weight was added to 00 parts by weight was subjected to a light resistance test and an ultraviolet transmittance measurement. In addition, the dispersibility of the titanium oxide powder added to the fiber stock solution was observed using an electron microscope.

Example 2 A non-woven fabric obtained by using the same fiber stock solution as in Example 1 except that the composite particles B obtained in Synthesis Example 2 were used instead of the composite particles A, and a light resistance test and an ultraviolet transmittance were performed. Was measured. Further, the dispersibility of the composite particles B added to the fiber stock solution was observed using an electron microscope.

Example 3 A non-woven fabric obtained by using the same fiber stock solution as in Example 1 except that the composite particles C obtained in Synthesis Example 3 were used instead of the composite particles A, and the light resistance test and the ultraviolet transmittance were performed. Was measured. In addition, the dispersibility of the composite particles C added to the fiber stock solution was observed using an electron microscope.

Comparative Example 2 A non-woven fabric obtained by using the same fiber stock solution as in Example 1 except that the composite particles were not blended was subjected to a light resistance test and an ultraviolet transmittance measurement.

The above results are summarized in Table 1.

[0023]

[Table 1]

[0024]

Industrial Applicability According to the present invention, there is provided a fiber-containing UV-screening agent which does not deteriorate the UV-screening effect, has good dispersibility in the fiber, and does not impair the properties of the fiber itself.

Claims (1)

[Claims] An ultraviolet shielding agent for blending fibers, comprising composite particles having a coating layer of at least one metal oxide selected from the group consisting of titanium, iron, lead, zirconium, vanadium, cerium and yttrium on core fine particles. .