JPH0713127B2 - UV reflective material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel ultraviolet reflecting material, and more specifically,
The particle size useful as a UV-reflecting organic filling material is about 0.00
It relates to a UV-reflecting material containing resin particles of 5 to 100 microns.

(Prior Art) Conventionally, various resin moldings or coating films are easily deteriorated by ultraviolet rays in the sunlight, and therefore white pigments and various ultraviolet reflective or absorbing agents are added to prevent deterioration by these ultraviolet rays. Agents have been added to them. In addition, coloring materials with various white pigments are used for camouflage on ice and snow fields.

(Problems to be Solved by the Invention) The white pigments described above, for example, inorganic white pigments such as titanium dioxide and zinc oxide have a property of absorbing most of the irradiated ultraviolet rays and hardly reflecting the ultraviolet rays. It is less effective in preventing deterioration of various base materials, and for camouflage, it is ineffective for ultraviolet detectors and the like because it has poor ultraviolet reflectivity as compared to ice and snow.

On the other hand, inorganic particles such as alumina, magnesium oxide, magnesium carbonate, barium sulfate, and zircon are used for processing textiles, plastics, etc. for the purpose of reflecting ultraviolet rays, but the whiteness is insufficient, Therefore, it has various drawbacks in practical use, such as being difficult to disperse in a resin or having a large specific gravity. Therefore, in the prior art, it is the fact that almost no additive that is white and has high ultraviolet reflectivity is known.

The present inventors have solved the drawbacks of the prior art as described above, and as a result of detailed research to obtain a white material having high ultraviolet reflectivity, such as a resin molded product, a condensable triazine-based low-molecular compound, Cured resin particles in a specific particle size range consisting of their initial condensates or their polymers have excellent ultraviolet reflectivity, low specific gravity and excellent dispersibility in a dispersion medium such as a synthetic resin. The present invention has been completed by finding that a white material having high ultraviolet reflectivity can be obtained by incorporating it into various base materials such as paints and paints.

(Means for Solving the Problems) That is, the present invention provides a fine particle having a particle size of 0.005 to 100 microns obtained by curing a condensable triazine-containing low molecular weight compound and / or an initial condensate thereof or a polymer thereof. It is an ultraviolet-reflecting material containing resin particles.

Explaining the present invention in detail, the ultraviolet-reflecting resin particles used in the present invention and mainly characterizing the present invention include a condensable triazine low-molecular compound and / or an initial condensate thereof or a polymer thereof, A condensable triazine low-molecular compound used for the production of such resin particles, an initial condensate thereof or a polymer thereof, which is obtained by curing by a usual method, is a conventionally known triazine-based amino. A compound having a methylol group such as a methylol compound, an alkoxy compound, a halogenomethylated compound and the like, various derivatives modified with a methylol group, and a triazine-based amino compound are used.

The triazine-based amino compound is preferably a 1,3,5-triazine-based amino compound, and examples thereof include melamine (2,4,6-triamino-1,3,5-s-triazine),
Ammeline (2,4-diamino-6-hydroxy-1,3,5-
s-triazine), ammelide (2-monoamino-4,
6-dihydroxy-1,3,5-s-triazine), benzoguanamine (2,4-diamino-6-phenyl-1,3,5-s-)
Triazine), Astoguanamine (2,4-diamino-6)
-Methyl-1,3,5-s-triazine), formoguanamine (2,4-diamino-6-hydroxy-1,3,5-s-triazine) and the like are used.

In the above, melamine and benzoguanamine are the most preferred triazine-based amino compounds. Therefore, the most preferable compound as the condensable triazine low-molecular compound and the initial condensate thereof is a methylol melamine having 2 to 6 methylol groups and an alkoxymethyl derivative thereof, a methylol benzoguanamine having 2 to 4 methylol groups and a compound thereof. Alkoxymethyl derivatives and their initial condensates.

Particularly preferred are amino acid-modified methylolaminotriazine compounds or alkoxymethylaminotriazine compounds and their initial condensates,
For example, the amino acid-modified methylolmelamine obtained by using melamine is obtained by reacting methylolmelamine with, for example, about 0.05 to 3 mol of amino acid per mol of methylolmelamine during or after the production of methylolmelamine. .

The amino acid preferably used in the above means a compound having a sulfone group or a carboxylic acid group at the same time as an amino group in the molecule, for example, sulfamic acid, glycine,
Any other amino acid such as α-, β-, γ- may be used. Further, homopolymers of unsaturated methyloltriazine compounds such as acrylamidomethylene (tetramethylol) melamine and their derivatives such as alkyl ethers, and these and other vinyl monomers or (meth)
Copolymers with acrylic monomers are likewise used.

Further, as a polyol component, a hydroxyalkylaminotriazine-based compound such as a reaction product of tri- or hexamethylol melamine or cyanuric chloride and mono- or diethanolamine is used as a polyol component, and conventionally known di- or polyisocyanate is cured by a urethane bond. Things can also be mentioned.

Further, those which are co-condensed with these may be used in combination as long as the intended function of the present invention is not impaired.

Examples thereof include methylol, alkoxymethyl, and halogenomethyl derivatives of the following compounds.

Urea, thiourea, ethylene urea, glyoxal monourein, glyoxal monourein, triazone, uron, burette, guanidine, biguanide, dicyanamide, adipic amide, phthalic amide, salicylamide, phenol, 4,4-dihydroxydiphenyl -2,2-Propane, hexamethylenediamine, aniline, dimethylaniline, p-toluenesulfoamide, alkyl carbamate, hydroxyethyl carbamate and other compounds; other vinyl monomers such as polyamide, polyurea, polyurethane, polyacrylamide and acrylamide Alternatively, it is a copolymer with acrylic acid esters and the like.

The UV-reflecting resin particles used in the present invention are obtained by curing the condensable triazine-based low-molecular compound and / or the initial condensate thereof as described above. By preparing an aqueous solution of a triazine-based low molecular compound and / or an initial condensate thereof and acidifying the pH of the aqueous solution, preferably to about pH 4 to 6, the above-mentioned condensable triazine-based low molecular compound or The precondensates are polycondensed with each other to give water-insoluble resin particles.

A particularly preferred method is to produce a condensable triazine-based low molecular compound and / or an initial condensate thereof as described above in an aqueous medium, preferably by modifying with an amino acid,
By preparing an aqueous solution having a concentration of about 5 to 40% by weight, dropping the aqueous solution into an acidic aqueous solution, and stirring vigorously
Fine resin particles with a size of 0.005 to 100 microns are produced. By adjusting the dropping speed and stirring speed, and the pH and temperature of the dropping liquid and acidic aqueous solution, the particle size can be adjusted to 0.00
It can be freely prepared in the range of 5 to 100 microns.

Further, by adding an acid to an aqueous solution of the above-mentioned condensable triazine small-diameter compound and / or an initial condensate thereof, the pH of the mixed solution is finally made acidic, preferably 4 to 6 In this case, the bulk resin is ground by a ball mill, sand mill or other known grinding means to obtain a particle size of 0.005 to 1
00 micron resin particles can be obtained. Further, after drying the above-mentioned bulk resin, dry pulverization with various pulverizers can obtain resin particles having a particle size of 0.005 to 100 microns.

According to a detailed study by the present inventor, the cured resin particles as described above have a reduced UV reflectivity when the particle size is smaller than 0.005 micron, and when the particle size exceeds 100 micron, synthetic resin, paint, ink or the like. It has been found that it becomes difficult to uniformly disperse the above into the substrate, and the ultraviolet reflectivity is lower than the amount used.

Resin particles used in the present invention produced as described above are white, solvent resistance, light resistance, heat resistance, water resistance,
It has good chemical resistance and can be sufficiently used as a white pigment or a filler for various base materials.

The ultraviolet reflective material of the present invention comprises the above resin particles and a carrier material. Here, the carrier material in the present invention refers to a binder resin which is conventionally used in pigment printing, printing ink, paint, etc., and synthetic fibers such as acetyl cellulose, vinylon, polyester,
When polyamide, polypropylene or the like is undiluted with the resin particles, these synthetic fibers are also included in the carrier material of the present invention. Further, using the resin particles, synthetic resins such as those described above, and other thermoplastic or thermosetting resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polycarbonate, polyimide, phenol resin, urea resin, and melamine resin. When a film, a sheet or other various colored molded products are obtained by coloring in white, these thermoplastic and thermosetting synthetic resins are also included in the carrier material of the present invention.

Therefore, one example of the ultraviolet reflective material of the present invention corresponds to the one using the above resin particles in place of the conventional pigment or filler in liquid materials such as conventional pigment printing agents, printing inks and paints. In the same manner as in the prior art, the resin particles are added in an amount of about 0.1 to 100 parts by weight in the liquid material.
It is generally used at a ratio of 50 parts by weight. The carrier material is generally used in an amount of 1 to 30 parts by weight, and the medium is used in an amount of 10 to 95 parts by weight.

In another example, in the synthetic fiber or the resin molded product, the resin particles are contained in the fiber or the molded product in an amount such that the fiber or the molded product can be colored substantially white, for example, 0.1 to 30% by weight. It is common.

The ultraviolet reflecting material of the present invention as described above is a liquid material as described above, or a white colored fiber or a resin molded product as described above, both of which are conventionally known pigment printing agents,
It can be obtained by the same method as the method for producing a paint or printing ink, the method for coloring an undiluted solution, or the method for coloring and molding a synthetic resin.

Incidentally, in the above, it is natural that the ultraviolet-reflecting resin particles as described above may be used alone, or may be used in combination with other colored pigments, etc.
Colored ultraviolet reflective materials of various hues can be obtained.

(Operation / Effect) The ultraviolet reflection material of the present invention as described above can be used in the same manner as conventional pigment printing agents, paints, and printing inks, and is useful for printing woven and non-woven fabrics, coating various articles, and printing. , Gives a white coloration, and the ultraviolet reflectivity of these white articles is
The value is remarkably higher than that of a colored product using a conventional white pigment.

The same applies to the case where the ultraviolet reflective material of the present invention is a colored fiber or a molded product, and a fiber or a molded product having similar ultraviolet reflectivity is provided.

Therefore, the ultraviolet ray reflective material of the present invention is remarkably improved in various kinds of deterioration resistance to ultraviolet rays.

Also, for military use, in areas with a lot of snow, white camouflage is applied to various facilities so that it cannot be distinguished from ice and snow on the ground, but these camouflages are performed using materials containing conventional white pigments. In this case, although a sufficient camouflage effect can be visually obtained, an ultraviolet detector or the like is easily detected because the ultraviolet reflectance of snow or ice and the ultraviolet reflectance of the white pigment used are significantly different. Although the camouflage effect was low, the UV-reflecting material of the present invention has a high UV-reflecting property similar to that of ice and snow fields. Therefore, when the UV-reflecting material of the present invention is used for camouflage, precise UV detection can be performed. An excellent camouflage effect that cannot be detected even with a container can be achieved.

Further, the ultraviolet-reflecting material of the present invention, unlike the conventional material containing ultraviolet-reflecting inorganic particles, since the resin particles are organic substances, they are very excellent in dispersion in synthetic resins and paints, and also inorganic particles. Since its specific gravity is very small as compared with the above, various problems due to the high specific gravity of conventional inorganic particles have been solved.

Next, the present invention will be described more specifically with reference to Reference Examples and Examples. In the text, “part” or “%” is based on weight unless otherwise specified.

Reference Example 1 40 parts of melamine, 100 parts of 35% formalin, 20 parts of methanol and 28 parts of water were mixed and stirred, and the temperature was raised to 80 ° C. to dissolve it colorless and transparent. Next, this solution is cooled to 45 ° C., 2.8 parts of sulfamic acid is added and reacted, one drop after the reaction is dropped into water and the reaction is continued until those initial condensates are precipitated, and then 20% aqueous sodium hydroxide solution is added. 5.8 parts and methanol 2
The reaction was terminated by adding 0 part. 20 parts of this resin solution
Dissolved in a part of water and used as a dropping solution.

200 parts of the above dropping solution is added dropwise to 2,000 parts of water at 50 ° C. with stirring. After dropping, raise the temperature to 90 ° C and adjust the pH of the solution to 4.0-
The mixture was adjusted to 6.0, stirred at 90 ° C. for 1 hour, filtered, washed with water, and dried at 100 ° C. to obtain fine ultraviolet-reflecting resin particles used in the present invention.

Reference Example 2 50 parts of an 80% aqueous solution of methylated methylol melamine resin
After diluting and dissolving in 40 parts of 40% aqueous methanol solution, 2 parts of sulfamic acid was added to the solution and reacted at 45 to 50 ° C. for 20 minutes, and then neutralized by adding 5 parts of 20% aqueous sodium hydroxide solution. After cooling, 10 parts of methanol was added to terminate the reaction to obtain a solution of the initial condensate. This solution had a solids content of about 40% and remained clear when diluted with water.

15 parts of the above resin solution was diluted with 100 parts of water to obtain a dropping solution. 200 parts of this dropping solution is added dropwise to 2,000 parts of water at 50 ° C. with stirring. After the dropping, raise the temperature to 90 ° C and adjust the pH of the solution to 4.0.
It was adjusted to ˜6.0, stirred at 90 ° C. for 1 hour, filtered, washed with water, and dried at 100 ° C. to obtain fine UV-reflecting resin particles used in the present invention.

Reference Example 3 2 parts of sulfamic acid were added to 90 parts of a 50% methanol aqueous solution containing 20 parts of methylol melamine and 20 parts of methylated melrol melamine, and after reacting at 45 to 50 ° C. for 10 minutes, 20%
The reaction was terminated by adding 5 parts of an aqueous sodium hydroxide solution. The reaction solution had a solid content of about 40% and remained a clear solution even when diluted with water.

15 parts of the above resin solution was diluted with 100 parts of water to obtain a dropping solution. 200 parts of this dropping solution is added dropwise to 2,000 parts of water at 50 ° C. with stirring. After the completion of dropping, raise the temperature to 90 ° C and adjust the pH of the solution to 4.0-
The mixture was adjusted to 6.0, stirred at 90 ° C for 1 hour, filtered, washed with water, and dried at 100 ° C to obtain fine ultraviolet-reflecting resin particles used in the present invention.

Reference Example 4 40 parts of melamine, 100 parts of 35% formalin, 20 parts of methanol and 28 parts of water are mixed and stirred, and the temperature is raised to 80 ° C. to be transparent,
Then, this solution is cooled to 45 ° C., 2.5 parts of glycine is added and reacted, and the reaction is carried out until the formation of an initial condensate thereof. Then, 5.8 parts of 20% sodium hydroxide aqueous solution and 20 parts of methanol are added and stirred to terminate the reaction. This solution was doubled with water and 400 parts of the solution was added at pH 5.6-6.0 to 90 parts.
Drop it into 1,500 parts of water at ℃ with vigorous stirring, cure at 90 ℃ for 1 hour, filter and dry to 0.1-0.2
The UV-reflecting resin particles used in the present invention having a particle size of micron were obtained.

Example 1 25 parts of the UV-reflecting resin particles obtained in Reference Examples 1 to 4, 100 parts of vinyl chloride resin, 70 parts of DOA and 3 parts of Na-Zn soap were kneaded by a roll mill to prepare a vinyl chloride resin sol. Was coated evenly on a Tetoron / cotton blended fabric to a thickness of 0.3 mm and heat-cured at 200 ° C. for 10 minutes to prepare a white sheet. The ultraviolet reflectance of this white sheet was measured with a Hitachi 330 type self-recording spectrophotometer (measurement: reflection integrating sphere). Each of the white sheets showed a good reflectance with respect to ultraviolet rays of several wavelengths.

As a comparative example, 85 parts of barium sulfate was blended in place of 25 parts of the above-mentioned UV-reflecting resin particles, and the UV reflectance of a sheet prepared by the same method was measured under the same conditions.

Example 2 30 parts of the UV-reflecting resin particles obtained in Reference Examples 1 to 4 and 100 parts of a 15% acrylic rubber toluene solution were kneaded, and 70 parts of toluene was further added to the polyester base cloth to have a thickness of 0.05 mm. It was applied evenly and dried to form a white sheet.

This white sheet was measured with a Hitachi 330 type self-recording spectrophotometer (measurement: reflection integrating sphere) in the same manner as in Example 1 above. This white sheet had an excellent reflectance with respect to ultraviolet rays of several wavelengths.

The measurement results of Example 1 and Example 2 are shown in Table 1 below.

Claims (1)

[Claims] 1. A condensable triazine low-molecular compound and /
An ultraviolet-reflecting material characterized by containing fine resin particles having a particle size of 0.005 to 100 μm obtained by curing an initial condensation product thereof or a polymer thereof.