JPS58157881A - Ultraviolet light absorber composition in form of aqueous dispersion - Google Patents

Abstract

PURPOSE:The titled composition, prepared by dispersing 2,2'-dihydroxy-4,4'-dimethoxybenzophenone in water as fine particles, and having improved dispersion stability and good suitablity to materials for polyester fiber, etc. CONSTITUTION:A composition obtained by suspending 2,2'-dihydroxy-4,4'-dimethoxybenzophenone as an active component in a mixture solution consisting of water and a suitable amount of a nonionic surfactant, preferably of polyethylene glycol alkyl phenyl ether type, or anionic surfactant, e.g. of an alkylbenzenesulfonic acid type, introducing glass beads thereinto, agitating the resultant mixture vigorously, and removing the glass beads.

Description

[Detailed description of the invention] More specifically, the present invention relates to an aqueous dispersion of an ultraviolet absorbent composition comprising mechanically atomized 2,2'-dihydroxy-4,4'-dimethoxypenzophenone as an active ingredient.

It is well known that ultraviolet absorbers are used to protect organic substrates in general, and materials made of synthetic polymers in particular, from the effects of light, and many compounds have already been provided. Typical examples of these compounds include benzophenone derivatives, benzotriazole derivatives, cyanacrylate derivatives, and the like.

Conventionally, the above-mentioned ultraviolet absorbers were processed by
(2) a method of copolymerizing an ultraviolet absorber having a functional group that can be incorporated into the polymer;
It has been applied by methods such as forming a molded article such as a zero-knit fabric or film and then coating the surface of the molded article, or (2) treating the molded article with an organic solvent solution containing an ultraviolet absorber.

However, in method (2), the molecules of the ultraviolet absorber used do not bond with the molecules of the polymer, and because the molecules are very small compared to the polymer, they often precipitate on the surface of the fiber or film, causing their properties to deteriorate. This causes significant deterioration.

In method (2), the above-mentioned drawbacks are overcome because the polymer and the ultraviolet absorber are bonded together, but since the polymer is often exposed to high temperatures during formation, the active ingredient may undergo thermal decomposition. It is inevitable that this will have an unfavorable effect on the physical and chemical properties of the electrolyte itself. In addition, methods (■) and (■) have the advantage of not damaging the properties of the polymer, but on the other hand,
It is extremely difficult to apply or process uniformly, and furthermore, it has the disadvantage of poor durability because the active ingredients come off due to various mechanical treatments after coating. Furthermore, there are cases in which a UV absorber is dissolved in a suitable organic solvent and then suspended in water containing a surfactant, but such suspensions are generally The particles are extremely coarse and non-uniform, and therefore uniform and good effects cannot be obtained when used, and the dispersion stability of the suspension itself is also poor.

The inventors have discovered that fibrous materials (
For example, when applying ultraviolet absorbers to polyester fiber materials in particular, we thought that the above disadvantages could be overcome if the active ingredients could be directly made into fine aqueous dispersions without using organic solvents. When we tried to disperse the absorbent into fine particles in water and examined their properties such as dispersion stability and dyeability, we found that only 2,2'-dihydroxy-4,4'-dimethoxybenzophenone was found to have an extremely small amount of dispersion. It has been found that particles have excellent dispersion stability and good adaptability to synthetic polymers, especially synthetic fiber materials (e.g., especially polyester fiber materials),
This has led to the present invention. That is, the present invention is an aqueous dispersion-like ultraviolet absorbent composition prepared by mechanically atomizing 2,2'-dihydroxy-4,4'-dimethoxybenzophenone as an active ingredient.

For atomization and dispersion of the active ingredient, known mechanical devices or methods used for this purpose can be applied.

For example, the active ingredient can be suspended in a mixture of water and a coupled nonionic surfactant or anionic surfactant, or a mixture of the two, and glass beads can be added to the suspension and vigorously stirred. will be achieved.

The concentration of the active ingredient in the aqueous dispersion of the present invention is preferably about 5 to 30% (heavy wrinkles) of the entire dispersion, and the amount of surfactant used at this time is 0% of the amount of the active ingredient. ,1
About 1.2 times is preferable.

The aqueous dispersion of the present invention thus obtained has excellent dispersion stability, and when applied to synthetic polymers, the degree of fixation and
Its fastness to washing is high, and since it does not use organic solvents, it can avoid harmful effects such as odor and toxicity caused by organic solvents. Furthermore, since there is no powder scattering property, a good working environment can be maintained during use, which is advantageous in terms of safety and health for workers.

Furthermore, it is easy to transport by pipe, and it can be easily diluted with water to a desired concentration, which is advantageous for saving labor.

Examples of nonionic surfactants that can be used in the present invention include polyethylene glycol alkyl phenyl ether, polyethylene glycol alkyl ether,
;l) Ethylene glycol fatty e ester type, polypropylene glycol polyethylene glycol ether type,
Examples include polyethylene glycol sorbitan fatty rttj ester, norbitan ester, and among these, Haho IJ ethylene glycol alkyl phenyl ether is relatively preferred. Examples of anionic surfactants include higher fatty acids, linear higher alcohol sulfate esters, side chain higher alcohol sulfate esters, alkylbenzene sulfonic acids, sulfosuccinic acid alkyl esters, and condensation of naphthalene sulfonic acid and formalin. Examples include product systems.

When producing the aqueous dispersion of the present invention, for example, protective colloid agents, metal sequestering agents,
Preservatives and other known additives may be added.

The particles of the aqueous dispersion of the present invention are treated (maximum particle size 1 μm or less) and uniform, and therefore have extremely good dispersion stability. The particle size and dispersion stability of an aqueous dispersion obtained according to the production example of an aqueous dispersion of the present invention described below and an aqueous dispersion having different active ingredients produced similarly were as shown in the table below.

When the active ingredient of the strained composition of the present invention was dissolved in acetone and dissolved in water containing a surfactant, the particle state of the resulting aqueous suspension was observed under a microscope. It is a suspension with poor dispersion stability in which crystals are observed and the active ingredient starts to precipitate almost immediately when the suspension is allowed to stand still, and is different from the fine and uniform aqueous dispersion of the composition of the present invention. were so uneven that there was no need to compare them.

The aqueous dispersion of the present invention has excellent dyeability and washing fastness for textile products made of synthetic polymers, especially polyester textile products. This is a characteristic of the aqueous dispersion of the present invention that is not found in the other ultraviolet absorbers mentioned above.

Therefore, the aqueous dispersion of the present invention can be used under the usual dyeing conditions for polyester textile products, such as carrier dyeing using a suitable carrier, high temperature and high pressure dyeing.

Alternatively, a thermosol dyeing method or the like can be applied.

For this reason, these dyes can be added at appropriate concentrations to the dye bath at the same time as dyeing, and this not only improves the light resistance of the dyed product by about 1 to 2 grades on the blue scale.
It is possible to prevent the deterioration of the fiber itself due to ultraviolet rays.

Furthermore, the aqueous dispersion of the present invention can also be used by being added to a resin processing bath.

The aqueous dispersion (or active ingredient) of the present invention can be mixed with other aqueous dispersion-like compositions such as dyes, pigments, paints, etc., and the present invention The active ingredient is added and this is atomized to produce dye,
It can also be an aqueous dispersion composition of pigments and paints.

The appropriate concentration of the aqueous dispersion of the present invention can be varied within a wide range, but for example, when the object to be treated is a textile product, it is about 0.1 to 10%, preferably 1 to 1%, based on the weight of the fiber.
The optimum concentration is preferably determined by preliminary experiments, although it is approximately 10%.

Examples of production and use of the aqueous dispersion of the present invention will be described below.

Production Example 1] 502 2,2'-dihydroxy-4,4'-dimethoxy/benzophenone bulk powder was mixed with 112 polyethylene glycol alkyl phenyl ether surfactant and 20
A diameter of 1 to 0 is suspended in a solution of 0
Approximately 200 pieces of 1.5 m glass beads were charged and atomized and dispersed for approximately 48 hours using a high stirrer HI-25 (manufactured by Tokyo Rika Kikai ■) at a rotational speed of 700 r, p, m. Next, the glass beads were removed, and 50 t of 10% PVA (incompletely saponified PVA) was added as a protective colloid, further diluted with water to a total weight of 500f, and stirred well until uniform.

A stable aqueous dispersion composition containing 10% by weight of active ingredient was thus obtained.

In this example, even if a polypropylene glycol polyethylene glycol ether type or a polyethylene glycol sorbitan fatty acid ester type surfactant is used instead of the polyethylene glycol alkyl phenyl ether type surfactant, the same stable aqueous dispersion can be obtained. A composition was obtained. A similar aqueous dispersion composition can also be produced using a mixture of nonionic and anionic active agents consisting of polyethylene glycol alkyl phenyl ether system 10f and condensation product 12 of naphthalene sulfonic acid and formalin. Ta.

Usage example 1] [Carrier dyeing bath treatment of Tetoron yarn] o, 1f/l
A polyethylene glycol alkyl phenyl ether type nonionic activator was added to water at about 60°C to a concentration of 5 f/l, and glacial acetic acid was added to adjust the pH of the dye bath to 5 to 6. Adjust accordingly. Then, in this, disperse dye for polyester [
For example, C, 1, Diaperse Blue 64)
and the aqueous dispersion-like ultraviolet absorber composition of the present invention (
10 weight percent) is added so that the amount is 3.0% (based on the weight of the fiber). Put Tetoron thread into this dye bath,
After raising the temperature of the dye bath to the boiling point in 1 minute, dyeing is continued at the same temperature for 60 to 90 minutes. Then, after slow cooling, it was washed with water, washed for 20 minutes in a bath containing 0.5% (heavy duty) caustic soda and 1.0% (by weight) nonionic surfactant at about 80°C, and further washed at 60°C for about Rinse with water for 15 minutes and dry. The light fastness of the thus obtained dyed product was found to be improved by about 1 grade on the blue scale compared to that dyed in the same manner using a dye bath not containing the ultraviolet absorbent composition of the present invention.

Usage example 2] [Carrier dyeing bath treatment of Tetron/rayon blended fabric] Tetron/rayon i-spun fabric (70/30) Woα52
/l of a polyethylene glycol alkyl phenyl ether type nonionic activator at 50 to 55°C, and the orthophenylphenol type carrier was added to the bath at 50 to 55°C.
Add so that it becomes 0f/l. Then C,I Dire
Add ct Red 224 (direct dye) to a concentration of 2.0% (based on fiber weight) and dye for about 10 minutes. 15
The pH of the dye bath is adjusted to 17.0-75 by adding monosodium phosphate (monohydrate) to 5.0y7t within 20 minutes. Then C, 1, Disperse Red
152 (disperse dye for polyester) and the ultraviolet absorbent composition of the present invention at 2.0% each (based on the weight of the fiber)
The temperature of the dye bath is raised to the boiling point in 45 minutes. After dyeing the tetron side at the same temperature until the desired density is reached, 20% (based on the fiber weight) of common salt is added to fix the color on the rayon side. Thereafter, the water is removed, the temperature of the dye bath is lowered, and the dye is washed and dried in a conventional manner.

The light fastness of the thus obtained dyed product was found to be improved by about 1 grade on the blue scale compared to that dyed in the same manner using a dye bath that does not contain the ultraviolet absorber composition of the present invention.

Usage Example 3] [High-temperature dyeing bath treatment of Tetron plain woven fabric] In a 60°C bath containing 12/l of an alkyl sulfate ester type anionic activator, 1. Disperse Red 221 (disperse dye for polyester) and the ultraviolet absorber composition of the present invention (10 layers) were added at a concentration of 30% (based on the fiber weight), and acetic acid was added to adjust the pH to 5.0-5. 5
Adjust to.

The Tetoron plain woven fabric is immersed in this dye bath (bath ratio 1:30).
After processing for about 15 minutes, the temperature of the dye bath is raised to 100°C in 20 minutes, and then to 120-130°C in 40 minutes. After dyeing at the same temperature for 60 to 90 minutes, it is slowly cooled and washed with water. Then 80 to 85
After processing at ℃ for 10 minutes, it is washed with water and dried.

The light fastness of the dyed product thus obtained was improved by about Y11 grade on the blue scale compared to that of the dyed product treated in the same manner with a dye bath not containing the ultraviolet absorber composition of the present invention.

Use example 4] [Thermosol dyeing bath treatment of Tetron plain woven fabric] C, 1,
A mixed dispersion consisting of 20 t/l of Disperse Yellow 54 (disperse dye for Tetron) and 20 f/L of the ultraviolet absorber composition of the present invention was padded onto a Tetron plain woven fabric, and the squeezing rate was 75% (
Squeeze the material so that the fiber weight is 1) and pre-dry it at 100°C for 3 minutes. This was then dry heat treated at 180°C for 30 seconds to fix the dye and ultraviolet absorber to the fibers, and then heated at 70°C for 50 minutes in a soaping bath containing 22/l of a polyethylene glycol alkyl phenyl ether nonionic activator.
Treat for minutes, wash with water, and dry.

The light fastness of the dyed product thus obtained was improved by about 1 grade on the blue scale compared to a dyed product treated in the same manner with a dye bath not containing the ultraviolet absorber composition of the present invention.

Usage example 5] [Thermosol dyeing bath treatment of Tetoron/cotton blend fabric] Dye used: C, 1, Disperse V for Tetoron
iolet 28 for cotton C, 1, Vat Violet
11. Add 10% each of disperse dye for Tetoron and vat dye for cotton to water containing 7t of polyethylene glycol alkyl phenyl ether activator. Further, the ultraviolet absorbent composition of the present invention is added thereto at a concentration of 20 f/l, and this dye solution is padded onto a Tetoron/cotton (65/35) blended fabric. . Squeeze with a mangle so that the squeezing rate is 80% (weight against fiber),
After pre-drying at 100°C for 3 minutes, dry heat treatment is performed at 180°C for 30 seconds to fix the dye and ultraviolet absorber to the fibers. Then 5 f/l hydrosulfide and 5
After padding with a solution consisting of f/l caustic soda and steaming for about 15 minutes to a squeezing rate of 80% (to fiber heavy weight), 1 t/l of a polyethylene glycol alkyl phenyl ether activator was applied. The bath ratio is 1 for a liquid containing
:30.Soap at 70°C for 10 minutes, then wash with water and dry.

The light fastness of the thus obtained dyed product was improved by Y11 grade on the blue scale compared to that of a dyed product treated in the same manner with a dye bath not containing the ultraviolet absorbent composition of the present invention.

Usage example 6] [Two-bath dyeing resin processing of Tetoron/cotton blend fabric] Dye used: C, 1, Reactive R for cotton
C, 1, Disperse Re for ed 2 Tetron
d 60 First, the cotton side of the Tetoron/cotton (65/35) blend fabric was dyed with C, 1, Reactive Red 2 at 2% (heavy needles to fiber) according to the usual dyeing method for reactive dyes, and then soaped. Wash with water. Next, this dyed cloth was padded with a dyeing solution consisting of the following composition of the ultraviolet absorber composition of the present invention: 20 glyoxal resin liquid 120 magnesium chloride resin catalyst 40, and the squeezing rate was 80% (pair fiber weight *) Squeeze and pre-dry at 100°C for 3 minutes. Further, this is subjected to a dry heat treatment at 180° C. for 30 seconds, and then soaped to remove unfixed dye and resin, washed with water, and dried.

The light fastness of the thus obtained dyed product was improved by about 1 grade compared to that of a dyed product treated in the same manner using a dyeing solution that does not contain the ultraviolet absorbent composition of the present invention.

Agent: 1) Akira Agent Ryo Hagi Hara -

Claims (1)

[Claims] 2,2'-dihydroxy-4,4'- as active ingredient
An aqueous dispersion-like ultraviolet absorbent composition comprising mechanically atomized dimethquine penzophenone.