JPH08239648A - Ultraviolet absorber - Google Patents

Abstract

PURPOSE: To obtain an ultraviolet absorber improved in ultraviolet absorbing and intercepting properties by intercalating an aromatic ultraviolet absorber among the layers of a synthetic mica. CONSTITUTION: At least one member selected from among ethyl p- aminobenzoate, octyl p-methoxycinnamate and 2-hydroxy-4- methoxybenzophenone, etc., each of which has a molecular weight of about 500 is used as the aromatic ultraviolet absorber. About 1-50wt.% this absorber is mixed with a flaky synthetic mica represented by, for example, the formula: NaMg2.5 (Si4 O10 )F2 and having a particle diameter of about 100μm, and the mixture is heated to about 60-300 deg.C, desirably 150-200 deg.C for about 5-60min under agitation in a nitrogen stream. The heated mixture is cooled by introducing it into water, ground and screened to obtain an ultraviolet absorber composed of the synthetic mica and the ultraviolet abosrber intercalated among the layers of the mica and being excellent in the ability to absorb the entire ultraviolet region of a wavelength of <=400nm including UV-A, UV-B, and UV-C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an ultraviolet absorber.

[0002]

2. Description of the Related Art Conventionally, as an ultraviolet absorbing or blocking agent,
It is roughly classified into an organic compound type that absorbs ultraviolet rays and a metal oxide type that reflects ultraviolet rays such as zinc oxide and titanium oxide. These ultraviolet absorbers or blockers are incorporated in cosmetics, quasi drugs, etc. for the purpose of preventing erythema, sunburn, blackening, premature aging of the skin, and organic polymers such as plastics and rubber. It is also compounded in various organic polymer materials for the purpose of preventing deterioration of the material by ultraviolet rays.

However, among these conventional ultraviolet absorbers or blockers, organic compounds are short-lived because they are easily decomposed by ultraviolet rays, and are compounded in cosmetics and quasi drugs. In that case, it is easily absorbed from the skin and is irritating to the skin. As a side effect, there are problems such as an allergic reaction and an inflammatory reaction. Further, metal oxides, for example, when incorporated into cosmetics, quasi-drugs, etc., have poor transparency and feeling in use, poor sustainability, and have side effects such as irritation and inflammatory reaction. There are still problems with regular use.

[0004]

The main object of the present invention is to:
It can effectively absorb or block ultraviolet rays in the whole area, is stable for a long time, does not react with other materials, has little absorbability from the skin or irritation to the skin, for example, inflammatory reaction, irritative reaction, etc. It is an object of the present invention to provide an ultraviolet absorber which has no side effects and is excellent in transparency and feeling of use.

[0005]

Means for Solving the Problems As a result of intensive studies in view of the problems of the prior art as described above, the present inventor has found that a compound in which an aromatic ultraviolet absorber is intercalated between layers of synthetic mica, That is, it was found that a compound in which an aromatic UV absorber is inserted between the layers of the synthetic mica crystal having a layered structure can provide a UV absorber capable of achieving the above-mentioned object, and the present invention is completed here. Came to do.

That is, the present invention relates to a UV absorber obtained by intercalating an aromatic UV absorber between layers of synthetic mica.

In the ultraviolet absorbent of the present invention, the synthetic mica is not particularly limited, and various known synthetic mica can be used. Examples of such synthetic mica include Na tetrasilicic mica [NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ ], Na
Or Li teniolite [(Na, Li) Mg ₂ Li (S
i ₄ O ₁₀ ) F ₂ ], Na or Li hectorite [(N
a, Li) _1/3 Mg _8/3 Li _1/3 (Si ₄ O ₁₀ ) F ₂ ]
In addition to synthetic mica having a composition such as that of JP-A-58-1937
No. 9, nickel, cobalt, manganese, titanium,
Synthetic mica containing 1 to 20% by weight of vanadium and barium in terms of oxide, JP-A-3-8
General formula described in No. 712: Ce _{x KY} Mg ₃ Fe _z Al
_1-z Si ₃ O ₁₀ F ₂ (where X, Y, and Z are 0.05 ≦
X ≦ 0.25, 0.25 ≦ Y ≦ 0.85, 0.10 ≦ Z
Selected from the range of ≦ 1.00), Te, Bi, P described in JP-A-3-33179.
b, Ce, Fe, Mo, Nb, W, Sb, Sn and Zn
An element selected from the group consisting of 1 to 30 in terms of oxide
Synthetic mica containing by weight% Te, Bi, Pb, Ce, F
e, Mo, Nb, W, Sb, Sn, V, Mn, Ni, C
Examples thereof include synthetic mica containing 1 to 30% by weight in terms of oxide of two or more elements selected from the group consisting of o, Zn and Ti, and particularly Na tetrasilicic mica [NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ ] and the like are preferable.

In the present invention, the use of such synthetic mica facilitates the formation of the following intercalation compound with an aromatic ultraviolet absorber.

In the present invention, various aromatic UV absorbers known in the art can be used, for example, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, Benzophenone derivatives such as dihydroxydimethoxybenzophenone, 2,4-dihydroxybenzophenone and tetrahydroxybenzophenone; paraaminobenzoic acid such as paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, amyl paradimethylaminobenzoate and octyl paradimethylaminobenzoate. Acid derivative; ethyl paramethoxycinnamate, isopropyl paramethoxycinnamate, octyl paramethoxycinnamate, 2-ethoxyethyl paramethoxycinnamate, mono-2-ethylhexadiparamethoxycinnamate Methoxycinnamic acid derivatives such as glyceryl; octyl salicylate, phenyl salicylate,
Salicylic acid derivatives such as homomenthyl salicylate, dipropylene glycol salicylate, ethylene glycol salicylate, myristyl salicylate, and methyl salicylate; urocanic acid derivatives such as urocanic acid and ethyl urocanate; 4-tert-butyl-4′-methoxydibenzoylmethane; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole; methyl anthranilate and the like can be exemplified. In the present invention, these aromatic ultraviolet absorbers can be used alone or in combination of two or more.

In the present invention, among the above-mentioned aromatic ultraviolet absorbers, those having a molecular weight of about 500 or less are preferable from the viewpoint of easy intercalation into synthetic mica.

In the present invention, the aromatic ultraviolet absorber preferably used is a benzophenone derivative, a paraaminobenzoic acid derivative, a methoxycinnamic acid derivative or the like.
Particularly preferred are hydroxy-4-methoxybenzophenone, ethyl paraaminobenzoate, octyl paramethoxycinnamate and the like.

The ultraviolet absorber of the present invention is the above synthetic mica in which an aromatic ultraviolet absorber is intercalated. In this way, by adopting a structure in which an aromatic UV absorber is intercalated in synthetic mica, the UV blocking function of the synthetic mica and the UV absorbing function of the aromatic UV absorber are combined, and the wavelength In the UV-A, UV-B, and UV-C UV region of 400 nm or less, an extremely excellent UV absorption or blocking function, which has not been obtained in the past, can be obtained. Also, by intercalating the aromatic UV absorber between the layers of synthetic mica,
Absorption of aromatic UV absorbers from the skin and direct irritation to the skin due to aromatic UV absorbers is prevented, and for example, inflammatory reactions, allergic reactions and other side effects become extremely safe and highly safe. Furthermore, the decomposition of the aromatic ultraviolet absorber due to ultraviolet rays is prevented, and the ultraviolet absorbing function can be stably exhibited for a long period of time. In addition, since the aromatic ultraviolet absorber is stably present between the layers of the synthetic mica, the aromatic ultraviolet absorber does not elute, and thus it may be mixed in various compositions such as cosmetics and paints. It does not react with the base, and the deterioration of the ultraviolet absorption function does not occur. Furthermore, the ultraviolet absorber having such a constitution has good transparency, and does not leave whiteness on the skin even when blended in cosmetics,
It has an excellent finished condition, and also spreads well on the skin, giving it an excellent feeling in use.

The method of intercalating the aromatic UV absorber with the synthetic mica is not particularly limited, and various conventionally known intercalating methods can be applied. For example, the synthetic mica and the aromatic UV absorber may be mixed in the presence or absence of a solvent such as chloroform or ethanol, but preferably in the absence of a solvent, at about 60 to 300 ° C., preferably 100. To about 200 ° C., more preferably about 150 to 200 ° C., at a temperature between the melting point and the decomposition temperature of the aromatic ultraviolet absorber used,
It may be heated for about 5 to 60 minutes, preferably about 5 to 30 minutes with stirring. The synthetic mica is usually in the form of fine flakes, and the size thereof is not particularly limited, and those having an appropriate size can be used as appropriate, but since the intercalation is easy, the particle size is Of about 100 μm or less may be selected and used, and a particle size of about 5 to 20 μm is preferable.

The ratio between the synthetic mica and the aromatic UV absorber is not particularly limited, and may be appropriately adjusted within the range of the amount by which the aromatic UV absorber is stably intercalated between the layers of the synthetic mica. However, it is usually appropriate that the amount of the aromatic ultraviolet absorber is about 1 to 50% by weight, preferably about 5 to 40% by weight, based on the weight of the synthetic mica.

When a synthetic mica in which an aromatic UV absorber is intercalated, that is, the UV absorber of the present invention is blended into various compositions, the blending method can be appropriately selected according to the purpose of use. However, for example, they can be blended in various states such as powder or a compression molded product thereof. When blending in powder form, it may be pulverized by an appropriate method, if necessary.

The ultraviolet absorbent of the present invention can be used by being blended with, for example, cosmetics, quasi drugs and the like. As specific examples of such cosmetics, sunscreen agents are mainly mentioned, but as other specific examples, for example,
Cosmetics for washing shampoos, body shampoos, etc .; creams, emulsions, makeup creams, cosmetic oils,
Basic cosmetics such as packs; foundation cosmetics such as foundation, lipstick, blusher, eyeliner, mascara, eye shadow, nail polish, white powder; hair cosmetics such as hair styling, hair nourishing, hair dyeing; bath agents, whitening agents , Rinse, acne preparation, hair remover and the like.

Examples of the forms of these cosmetics and quasi drugs include liquids, oils, lotions, liniments, oily ointment bases, O / W hydrophilic ointments and W / O water absorbing ointments. Examples thereof include emulsion ointment bases, water-soluble ointment bases, pasta agents, plasters, patches, creams, emulsions, etc., but are not limited thereto. These forms of cosmetics and quasi-drugs can be prepared according to a conventional method,
A wide variety of materials known in the art can be widely used for the preparation.

For example, as a base for cosmetics or quasi drugs, an oily base may be used alone or in combination of two or more, and a water-soluble base may be used alone or in combination. The above can be mixed and used. As these bases, specifically,
Peanut oil, sesame oil, soybean oil, safflower oil, avocado oil, sunflower oil, corn oil, rapeseed oil, menzi oil, castor oil, camellia oil, coconut oil, olive oil, poppy oil, cacao oil, beef tallow, lard, wool fat. Oils and fats such as; oils and fats modified by chemical changes such as hydrogenation; mineral oils such as petrolatum, paraffin, silicon oil, squalane; isopropyl myristate, N-butyl myristate, isopropyl linoleate , Propylricinolate, isopropylricinolate, isobutylricinolate, heptylricinolate, diethyl sebacate,
Diisopropyl adipate, cetyl alcohol, stearyl alcohol, white beeswax, gallow, tree wax,
Higher fatty acid esters such as lanolin, carnauba wax and shellac wax, higher fatty acid alcohols and waxes; higher fatty acids such as stearic acid, oleic acid and palmitic acid; monosaturated or unsaturated fatty acids having 12 to 18 carbon atoms,
A mixture of di and triglycerides; ethylene glycol,
Polyhydric alcohols such as polyethylene glycol, propylene glycol, polypropylene glycol, glycerin, batyl alcohol, pentaerythritol, sorbitol, mannitol; gums such as gum arabic, benzoin gum, guaiac butter, tragacanth gum; gelatin, starch, casein, dextrin, pectin , Natural water-soluble polymers such as pectin sodium, sodium alginate, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, nitrocellulose, crystalline cellulose; polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, sodium polyacrylate, carboxy Synthetic water solubility of vinyl polymer, polyethyleneimine, etc. Child; nonionic, anionic, zwitterionic, surfactants cationic and the like; ethanol, can be exemplified isopropanol, and water.

In the production of the above cosmetics and quasi drugs, if necessary, various known cosmetic bases or bases used for quasi drugs such as excipients, binders, lubricants, etc. Agents, disintegrants and the like can be used, and if necessary, various oils, fats, waxes, hydrocarbons, fatty acids, higher alcohols, ester oils, oils such as metal soaps, etc. within a range not impairing the effects of the present invention. Raw materials, animal and plant extracts, vitamins, hormones, pharmaceuticals such as amino acids, surfactants, pigments, dyes, pigments, fragrances, preservatives, bactericides, moisturizers, thickeners, antioxidants, metals In addition to the ion sequestering agent and the pH adjusting agent, various known components and additives can be appropriately combined and used. In addition to the ultraviolet absorbent of the present invention, other ultraviolet absorbents, ultraviolet scattering agents, etc. can be added.

When the ultraviolet absorbent of the present invention is used by being blended with cosmetics or quasi drugs, the amount thereof is not particularly limited as long as it can exert the effect as an ultraviolet absorbent, Specifically, it may be appropriately adjusted depending on the type of cosmetics or quasi drugs. When used as cosmetics,
Usually, the cosmetics are used as they are, or 0.
It is suitable to add 1% by weight or more, and it is 0.1 to 90.
It is preferable to blend the composition in an amount of about wt%. When used as a quasi drug, it is usually used as a quasi drug, or
It is suitable to add 0.1% by weight or more to the total amount of quasi-drugs, preferably about 5 to 30% by weight.

Further, the ultraviolet absorbent of the present invention is incorporated into a composition containing an organic polymer material such as a synthetic resin molded product, a rubber product, and a paint to prevent the organic polymer material from being deteriorated by ultraviolet rays. It can also be used for the purpose. When blended in these compositions, the blending amount of the ultraviolet absorber is not particularly limited, as long as it is an amount capable of exerting an effect as the ultraviolet absorber, if appropriately adjusted depending on the type of composition. Although it is good, usually, in the total amount of the organic polymer material-containing composition, 0.
It is preferably about 1 to 30% by weight.

[0022]

EFFECT OF THE INVENTION The ultraviolet absorber of the present invention has been hitherto obtained in the entire ultraviolet region of about 400 nm or less by combining the ultraviolet shielding function of the synthetic mica and the ultraviolet absorbing function of the aromatic ultraviolet absorber. It has an extremely excellent UV absorption or blocking function that never existed, and prevents absorption of aromatic UV absorbers from the skin and direct irritation to the skin due to aromatic UV absorbers, resulting in inflammatory reactions and allergic reactions. It is highly safe with very few side effects. In addition, decomposition of aromatic UV absorbers by UV rays is prevented, and since aromatic UV absorbers do not elute, they do not react with other bases and exhibit stable UV absorbing function for a long period of time. You can Furthermore, it has good transparency, and when blended in a cosmetic or the like, it has an excellent finished state and a good feeling in use.

[0023]

EXAMPLES The present invention will be described in more detail with reference to production examples and examples.

Example 1 As a synthetic mica, sodium type tetrafluorosilicon mica: N
a [Mg _2.5 Si ₄ O ₁₀ F ₂ ] ・ 2H ₂ O (Na-TS
-S10% sol, manufactured by Topy Industries, Ltd., and ethyl paraaminobenzoate (E
BA, manufactured by Wako Pure Chemical Industries, Ltd. or 2-hydroxy-4-methoxybenzophenone (OB, manufactured by Sigma) was used to prepare the ultraviolet absorbent of the present invention by the following method.

(1) Powdering of Synthetic Mica The sol type synthetic mica was powdered by the following method.

First, about 50 ml of synthetic mica sol and about 450 ml of ultrapure water were added to a 500 ml beaker and stirred with a glass rod, followed by centrifugation at 2000 rpm for 10 minutes, and the supernatant was discarded. After repeating this operation 6 times, about 200 ml of ultrapure water was added to the precipitated synthetic mica to resuspend it, and pleated filtration was performed.

The residue thus obtained was dried in a microwave oven, collected from a filter paper, pulverized in a mortar, and the material passed through an 80-mesh sieve was further dried in a dryer at 150 ° C. The water content of this synthetic mica is measured by the Karl Fischer method (measuring device: MK-A
II, manufactured by Kyoto Electronics Manufacturing Co., Ltd.), and the water content was 5% or less.

(2) Intercalation of aromatic UV absorbers Ethyl paraaminobenzoate (EBA) or 2-hydroxy-4-methoxybenzophenone (OB) passed through an 80-mesh screen and powdered synthesis by the above method. Mix well with mica in various mixing ratios, fill a glass test tube with about 200 mg of the mixture, and under a nitrogen stream, drive lock bath (dry block bath, AL-500 type, Sonics)
(Manufactured by Corporation). Immediately thereafter, the mixture was cooled in ice, crushed in a mortar and then passed through an 80 mesh sieve to obtain a sample in which EBA or OB was intercalated in synthetic mica.

The sample obtained by such a method was subjected to X-ray diffraction by the following method.

(3) X-ray Diffraction Method A sample is added little by little to the sample-filled portion of the glass sample plate, and the sample is pressed by the glass plate.
A 0 mg sample was filled so that the sample surface was flush with the glass plate. The powder X-ray diffractometer (M03X-HF,
(Made by Mac Science Co., Ltd.) was horizontally set, and X-ray diffraction was performed under the following conditions.

[Measurement conditions] CrKα, λ = 2.29 angstrom Tube voltage: 40.0 kV Tube current: 30.0 mA Sampling width: 0.02 deg Scanning speed: 4.00 deg / min Scanning range: 2θ = 2 35 degree (4) X-ray diffraction result Among samples obtained by using EBA as an aromatic ultraviolet absorber (hereinafter referred to as "EBA-synthetic mica"), 1
An X-ray diffraction diagram before and after the heat treatment of the sample obtained by performing the heat treatment at 80 ° C. for 15 minutes is shown in FIG. 1, and the sample obtained by using OB as the aromatic ultraviolet absorber (hereinafter, referred to as “OB-synthesis”). 2) shows X-ray diffraction patterns before and after heat treatment of a sample obtained by heat treatment under the same conditions.
Further, FIG. 1 also shows an X-ray diffraction diagram before and after the heat treatment when only EBA was heat-treated, and FIG. 2 also shows an X-ray diffraction diagram before and after the heat treatment when only OB was heat-treated.

As is clear from the above results, when only EBA or OB was heat-treated, a peak appeared at the same position as before the heat treatment, so that EBA and OB were each recrystallized. It could be confirmed. Also, EBA-
Regarding the synthetic mica and the OB-synthetic mica, a new peak appeared around d = 1.9 nm after the heat treatment, and the d value increased from 1.2 nm to 1.9 nm. It was confirmed that the intercalation distance between EBA and synthetic mica and the intercalation compound between OB and synthetic mica were formed, respectively.

EBA-synthetic mica obtained by heat treatment at 60 ° C., which is lower than the melting point of EBA of 88 to 90 ° C., and at 130 ° C. and 180 ° C., which are temperatures above the melting point, for 15 minutes each. The X-ray diffraction pattern of is shown in FIG. In the sample heat-treated at 60 ° C, almost no peak due to the intercalation compound appeared, but the peaks at 130 ° C and 180 ° C
A peak due to the intercalation compound was observed in the sample heat-treated at ℃.

FIG. 4 shows an X-ray diffraction pattern of EBA-synthetic mica obtained by changing the compounding ratio of EBA to synthetic mica in the range of 5 to 40% by weight. EBA blending concentration is 5
In the case of wt%, no clear peak due to the intercalation compound was observed, but the intensity of the peak due to the intercalation compound increased as the compounding concentration was increased.

On the basis of the above X-ray diffraction results, the intensity ratio I ₂ / E _{2 of} the EBA-synthetic mica and the X-ray peak intensity I ₁ of the synthetic mica obtained at each heat treatment temperature, I ₂ /
The results of the relationship between I ₁ and the concentration of EBA compounded are shown in FIG. This result suggests that as the heating temperature increases, the rate of formation of the intercalation compound increases.

Example 2 In Example 1, the EBA-synthetic mica obtained by heat treatment at 180 ° C. for 15 minutes with the mixing ratio of EBA to synthetic mica being 20% by weight was used to measure the amount of ultraviolet ray transmission by the following method. . As a comparative sample, a synthetic mica alone,
The same measurement was performed on the EBA-synthetic mica mixture before heat treatment.

The sample for measurement was pulverized and then uniformly spread on a tape in a fixed amount, and a solar simulator 600 type (manufactured by Solarlight Company, Inc.) (xenon source) was used as a light source. The sample was irradiated with ultraviolet rays, and the intensity of transmitted light was measured for ultraviolet rays having a wavelength in the range of 290 nm to 420 nm using a spectroradiometer (USR-20B, manufactured by Ushio Inc.) as a detector. FIG. 6 shows the results.

From these results, it can be seen that the amount of ultraviolet ray transmission is extremely small when EBA-synthetic mica obtained by heat treatment at 180 ° C. for 15 minutes is used.

Production Example 1 A sunscreen cream having the following composition was prepared.

Glycerin monostearate 10 g UV absorber of the present invention 1) 5 g Stearic acid 5 g Stearyl alcohol 1 g Sesame oil 2 g Triethanolamine 1 g Glycerin 5 g Purified water Appropriate amount 100 g Note 1) In Example 1, mixing ratio of EBA to synthetic mica Of 20% by weight and EBA-synthetic mica obtained by heat treatment at 180 ° C. for 15 minutes Production Example 2 A sunscreen ointment having the following composition was prepared.

UV absorber of the present invention 2) 10 g stearic acid 6.3 g triethanolamine 0.8 g stearyl alcohol 4.5 g macrogol 1540 3.0 g methylparaben 0.2 g glycerin 10 g purified water suitable amount total 100 g Note 2) Example 1 OB-synthetic mica obtained by heat treatment at 180 ° C. for 15 minutes with OB mixed with synthetic mica at 20 wt%.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction diagram of EBA-synthetic mica before and after heat treatment.

FIG. 2 is an X-ray diffraction diagram of OB-synthetic mica before and after heat treatment.

FIG. 3 is an X-ray diffraction diagram of EBA-synthetic mica when the heat treatment temperature is changed.

FIG. 4 is an X-ray diffraction diagram of EBA-synthetic mica when the EBA blending concentration was changed.

FIG. 5 is a graph showing the relationship between the EBA blending concentration and the peak intensity ratio of X-ray diffraction for EBA-synthetic mica.

FIG. 6 is a graph showing UV transmission intensity for EBA-synthetic mica.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C08K 5/00 KAJ C08K 5/00 KAJ 7/00 KCJ 7/00 KCJ

Claims (1)

[Claims] 1. An ultraviolet absorber obtained by intercalating an aromatic ultraviolet absorber between layers of synthetic mica.