JPS6099186A - High molecular weight ultraviolet absorber and cosmetic containing the same - Google Patents

Abstract

PURPOSE:To provide a novel high molecular weight ultraviolet absorber, having improved safety, and capable of controlling the light absorbence and the solvent, by using glycidol, an alkylene oxide and an ultraviolet absorber as raw materials. CONSTITUTION:The objective high molecular weight ultraviolet absorber is the compound of formula Xl-Ym-Zn [X is group of formula I or formula II; Y is CH2CH2O, CH2CH(CH3)O, CH2CH(C2H5)O or CH2CH2CH2CH2O; Z is group of formula III (R1 and R2 are H or OH) or formula IV (A is carboxyl, -COOH, alkoxycarbonyl, -COOCH3, -COOC2H5, -COOC3H7, acetyl, or -COCH3); 3<=l<=200; 0<=m<=200; 2<=n<=200]. USE:Additive for beauty wash, milky lotion, cream, face powder, foundation, ointment, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel ultraviolet fat absorber and a cosmetic containing the same, more specifically, a copolymer of an ultraviolet absorber and glycidolpe or an alkylene oxide in addition thereto. This paper relates to a new high molecular weight ultraviolet absorber and its application to chemical raw materials.

Usually, sunburn occurs when sunlight 111 and ultraviolet rays act beyond the physiological limits of I. It is known as santan.

In general, the intensity of onset and subsequent course vary depending on the intensity and amount of ultraviolet rays received by the skin, but first, the symptoms are hyperemia of the capillaries within the skin, followed by swelling due to swelling, and erythema accompanied by chickenpox ( sampan). After a few days, the inflammation subsides, the erythema disappears, and melanin pigments are deposited within the skin, resulting in tanning.

Depending on the wavelength, ultraviolet rays can be classified into short wavelength ultraviolet rays (UV-C) of 280 nm or less, 2E30 to 32 Dnm.
Mid-wavelength ultraviolet region (UV-B), 320-400nm
(7) Although classified as long-wavelength ultraviolet light (UV-A), ultraviolet light of 290 nm or less is normally absorbed by the ozone layer, the atmosphere, etc. and does not reach the earth's surface, so ultraviolet light of 290 to 400 nm
The ultraviolet rays (UV-B and UV-A) of 290 to 520 nm are biologically important, and of these, the ultraviolet rays of 290 to 520 nm (UV-B) mainly cause acute erythematous effects (sampane).
It is related to erythematous ultraviolet rays, and is also called 320-400
Ultraviolet rays in the nanometer range (UV to A) promote blackening (suntan) and are therefore called UV rays in the blackening region. Therefore, it is essential that the ultraviolet absorber has a filtering effect on ultraviolet rays of at least 290 to 320 nm, and if necessary, it is also required to absorb ultraviolet rays of 620 to 400 nm.

As is well known, benzophenone thread compounds, p-aminoamzoic acid compounds, p-aminoacetophenone thread compounds, etc. have excellent ultraviolet absorption ability, and have extremely thick absorption ranging from 280 nm to 35 (JnmK). Along with various derivatives, it is used as a primary stabilizer for plastics, fibers, etc.
It has also been used in the cosmetics field to prevent skin irritation and sunburn caused by sunlight, and to photostabilize ingredients such as pigments and fragrances.

However, these derivatives and many of the derivatives derived from them are originally fat A'fase 1-, and the direction of conversion is also aimed at increasing fat solubility. Some of the water-bathable derivatives, which are important factors in their use in cosmetics, are ethylene oxide adducts to p-aminoacetophenone or 2-hydroxy-4-methoxybenzophenone-5-sulfonate (commonly known as Suriso-Ronzon). Except for the representative anionic derivatives, they were all the same. Moreover, even these water-soluble derivatives have safety problems such as a decrease in absorbance due to an increase in molecular weight and an effect on the skin, and cannot be said to be sufficient.

In view of this current situation, the present inventors have discovered that water solubility can be achieved by introducing glyceryl groups into various ultraviolet absorbers by adding glycidol, etc.
・Ultraviolet, outer 1, and ray absorbers [- have already been proposed (Unexamined Japanese Patent Publication No. 5
No. 8-109454 and JP-A No. 5EI-11053'5
issue). However, even in the above method, water solubility can be achieved only when 2 molar additions or more are added, and considering the presence of 1 molar adduct by-products (water-insoluble) that are inevitable in synthesis, it is more efficient or economical. Something was wrong.

Therefore, the present inventors conducted research to obtain even better ultraviolet absorbers, and as a result, they combined these ultraviolet absorbers with glycidol, and added alkylene oxide as needed.
It has been discovered that copolymerization of one or three components can improve safety due to high molecular weight, control absorbance, and even change the solubility itself from water-soluble to tametanol-soluble. , which completed the present invention.

The present invention (general formula (1) % formula % ( Any one or a mixture of two or more of the following, Z is the following ■ or ): Δ (However, A is carboxyl jl, : -COOH,
7ru:1xycarbonyl group: -ccocb3. -c○
0C2)15, -COOC5H7, acetyl group knee C0
C) (Represents 3) Also, t, m, and n each represent the number of added moles i, 1.3≦t≦200.0≦m≦200.2≦
n≦200. The present invention relates to a polymeric ultraviolet absorber represented by the following formula, and further relates to a cosmetic containing one or more of the above-mentioned polymeric ultraviolet absorbers.

Regarding the raw material components forming the high molecular weight ultraviolet absorber of the present invention, firstly, glycidol is used as the X component, thereby making it water-soluble.

Next, as the Y component, ethylene oxide, propylene oxide, and 1,2-butylene oxa.

i[ or more are selected and used from alkylene oxides such as tetramethylene oxide (T) and tetramethylene oxide (T) IF). The alkylene oxide is used here for two purposes. One is the control function of dissolved PM properties from water-soluble to ethanol-soluble, and this is closely related to the number of carbon atoms, the presence or absence of branching, etc.

Another feature is the molecular weight control function.

When polymerization is carried out without using alkylene oxide, the degree of polymerization generally reaches a plateau at the average molecular zi ooo to 3000, although there is some variation depending on the noodles of the ultraviolet 1Ii91 absorber. By using these together, the degree of polymerization is dramatically accelerated.

Furthermore, as the two components, benzophenone compounds such as 2,4-dihydroxybenzophenone, 2,2',4-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, p- Aminobenzoic acid and its derivatives (methyl,
Various ultraviolet absorbing agents such as ethyl (ethyl, furovir), p-aminoacetophenone, etc., can be mentioned, but it is very difficult to use this substance directly as a polymerization component. In practice, p-
A glycidylimino group or a glycidyl ether group is introduced into the amino group for aminobenzoic acid-based and p-aminoacetophenone threads, or the hydroxyl group at the 4-position in benzophenone threads, and used for polymerization as a synthetic intermediate component. Although it is possible to polymerize the synthetic intermediate alone by thermal polymerization or other appropriate polymerization methods, the resulting polymer generally becomes a resin and becomes insoluble and infusible.

In the present invention, the desired high-molecular-weight ultraviolet absorber is obtained by random addition polymerization of the above-mentioned two components X, Z, and Y component as necessary. The number of added moles t, m, and n is 3 (t(200
,0(m<,200.2≦n≦2DC, and the average molecular weight is preferably in the range of 1,000 to 20,000.

Here, regarding the characteristic point of the present invention, in the above composition range, by changing the plugs and composition ratio of the glyceryl group moiety and the alkyl ether group moiety, the solubility of the obtained compound can be changed to water-soluble. This means that it can be varied in a variety of ways, from ethanol to ethanol solubility. For example, when ethylene oxide and brobylene oxide are used as alkylene oxide, they are water-soluble in a wide range of composition ratios, whereas when 1,2-butylene oxide and tetramethylene oxide (THP) are used, When I was there,
? The composition ratio of glyceryl groups and alkyl ether groups in the polymerized product, when the ratio of alkyl ether group/glyceryl group is 1 or less, it is water soluble, when it is 2 or more, it is ethanol soluble, and when it is in the range of 1 to 2, it absorbs ultraviolet rays. Depending on the type of agent, it tends to be water-soluble or ethanol-soluble. Since it is possible to arbitrarily change the solubility in this way, it becomes possible to provide a desired polymer TJ ultraviolet absorber depending on the product form in which it is used.

The high molecular weight ultraviolet absorber of the present invention, for example, in the case of benzophenone-based storage, is a pale yellow transparent highly viscous liquid substance with a wavelength range of 280 to 290 nm (UV-B) and a range of 320 nm.
~330 nm (UV-A) The absorption maximum is in the 9fi region, and p-aminobenzoic acid-based monomers and p-aminoacetophenone-based polymers are transparent, pale yellow to reddish brown, highly viscous liquid substances, and have a wavelength of 310 nm. It exhibits light absorption characteristics with maximum absorption near 340 nm (p-amine benzoic acid type) and 340 nm (p-aminoacetophenone type).

This property p is as follows for p-aminoandzoic acid polymers:
It has an effective filtering effect against ultraviolet rays in the erythema region,
It has been shown that p-aminoacetophenone polymers are effective against ultraviolet rays in the blackening region, and benzophenone polymers are effective against both, making them extremely useful for sunscreen applications.

These various polymers are blended in the form of lotions, emulsions, creams, white powders, foundations, cartilage, etc., and can be particularly advantageously used in water-based products, as well as for photostabilizing pigments, fragrances, sunscreens, etc. used. In addition, the blending concentration at this time is generally about 0.01 to 60% based on the base, but the optimum concentration depends on the type of base, whether or not it is used in combination with other UV absorbers/cutting agents, and the purpose of use. It is practical to choose the concentration.

In the polymeric UV absorber polymer according to the present invention, first, as a first step, epichlorohydrin is added to various UV absorbers, and then glycidyl imine or dalicidyl ether (synthetic intermediate) is synthesized by alkaline saponification. . Historically, in two steps, polymerization is performed using two to five components of glycidol, a synthetic intermediate, and optionally alkylene oxide in the presence of a catalyst.

Examples of synthesis of the polymer of the present invention are shown below.

Synthesis example 1. 2. 4-dibenzophenone compound (Et, oHO 1 bath) 2,4-dihydroxybenzophenone 214P (
1mot), epichlorohydrin 370f (4mot)
I put it in. The mixture was heated to 100° C. in an oil bath without stirring, and granular sodium hydroxide was added in 6 portions over 2 hours. Thereafter, the mixture was stirred at the same temperature for 2 hours, and after cooling, the precipitated salt was separated.

The q solution was concentrated and crystallized from ethanol to give 2-hydroxybenzophenone-4-gly/zyl diether as m,
It was obtained as pale yellow needle-like crystals with p, 103-104°C. The obtained crystal 5.49 (0.02 mob) was 300-6
Place in a diluted flask, dissolve in 100% of tetrahydrofuran, and add 0.1 m of boron hexafluoride modified thyl ether complex.
Added l. Add 50rn of glycidol 14 and El to this.
1 of diluted with tetrahydrofuran was added dropwise over 1 hour, and the reaction was further allowed to proceed at room temperature for 1 hour. Unreacted tetrahydrofuran was distilled off to obtain Compound 1 as a pale yellow viscous product.

Optical properties of O polymer and average molecular near-ultraviolet absorption λmax (EtOH) 290 nm, filter 24
nm (See Figure 1) Infrared absorption 3370c7n-+ OH stretching vibration 294
0crn1 and 288DCIn-' CH,.

1625crn-' C= On 1260crn-' = C-0-C antisymmetric stretching 1100
crn"COi'4aa;4tJt700m" Pensen cough extra-plane modified cough () Molecular weight measurement by PC (Puru Ruff'!N1L) ζ=
9000 Coa Example 2. 2,4-dihydroxybenzophenone thread polymer (water η" soluble) Stirrer, cooler, dropping funnel J) ν: 200
2-Hydroxybenzophenone-4-glycidolethe #5 shown in Synthesis Example 1 was added to a six-bottle flask of m1.
．． 49 (0.02 mot), add 20 tnl of dioxane and dissolve, hexafluoride pome, ethyl ether! Fa
(40,4- was added, and the temperature was raised to 70°C. Glycidol 14.El was added to this for 30 minutes, and the reaction was then carried out at 70°C for 1 hour. Dioxane was distilled off, and the mixture 1 was pale yellow. It was obtained as a viscous liquid.

Optical information of 011 compound and average molecular UV absorption λ
max (MeOH) 290nm, 324nm (see Figure 2) Infrared absorption 3370 crn -' O-H stretching vibration 2940o+
+-" and 288 Don-" C-11 stretching vibration 16
25cr++-1C=O stretching vibration 1260crn-1=C-0-C antisymmetrical stretching R1δ110
0crn-1C-O stretched rope vibration 700crn-' Molecular weight measurement by pensene nuclear out-of-plane bending OPC (pullulan conversion) = 2000 Synthesis example 6 Ethyl PABA thread polymer (water soluble) Stirrer, cooler, dropping funnel Pour ethyl PABA 825'/ (0.5 mot) into the 1t third flask you took and add dichloromethane 400m/! Add and dissolve, and then add 5 ml of boron hexafluoride trineider complex.

added. While stirring, 47 f (0.5 mot) of epichlorohydrin was added dropwise at 40° C. or below over 1 hour.

Thereafter, it was stirred at 50°C for 12 hours, dichloromethane was distilled off, and then crystallized from chloroform to give m, N-(2-hydroxy-3-chloropropyl)-ethyl PABA.
It was obtained as white crystals of p, 1o6-1o4°C. then 50
Calcium hydroxide 8.99 (0,1
2 mot) and 300 g of water were added and dispersed. A solution of the obtained crystal 15.5 P (0.06 mob) in 50 mA of tetrahydrofuran was poured into the solution, and the mixture was stirred at room temperature for 20 hours.

After that, excess calcium hydroxide was used, the oral fluid was extracted with ethyl acetate, the 6'r acid ethyl acetate layer was concentrated, and then crystallized using a needle to obtain ethyl glycidyl-p-aminobenzoate, m, p, 69 Obtained as white crystals at ~70°C. Next, 50 g of chloroform was placed in a 5-300 mJ flask equipped with a stirrer, a cooler, and a granite, and 0.5 g of boron hexafluoride-ether complex was added thereto. To this, ethyl glycidyl-p-aminobenzoate 67'p (0,05
mob), glycidol 16.42 ('0.'l 8
mot) dissolved in chloroform 100-
It was completed for 3 hours under M flow conditions. After the addition, the mixture was further stirred for 1 hour, the chloroborum layer was decanted, and the resulting precipitate (N compound) was taken out. Compound 1 was a reddish brown water-soluble viscous liquid.

○ Optical properties and average molecular weight of Oki 1 compound Ultraviolet absorption λmax (MeOH,) 309 nm (r5
j See Figure 3) Infrared absorption 3400t1n-' O-H stretching vibration 2950crn-1 and 2900c+++-' C-H
Stretching vibration 168Dc+++-' C=○Stretching vibration 129
0m-” Carorh-N (lii, vibration 110Dc
M-1C-0 stretching vibration 835c1n-' Benzene nucleus out-of-plane bending vibration GPC molecular weight 111: constant (pullulan tyn>) and 3oo.

Synthesis example 4. p-aminoacetophenone polymer (water soluble) P-aminoacetophenone 67, 59 (0
, 5mot), persalt gm zinc hexahydrate 1.649 (
0,005 mot), and 400 ml of dioxane was added to dissolve it. Shrimp chlorhydride y 47 V (0.5 mot) was added at 1 fJ for 1 hour at a temperature below 50°C while stirring.
Ten n2> was defeated. Thereafter, the mixture was stirred at 60°C for 48 hours (1), and after distilling off dioxane, it was fractionated with a silica gel column.
(2-Hydroxy-4-chloropropyl)-p-aminoacetophenone was obtained as white crystals, m, p, 79'-82°C. Next, put 8.99 mj of calcium hydroxide (0.12 mot) into a 500 mj beaker and add 300 mj' of water.
was added and dispersed. Crystals obtained from this 15.79
(0.06 mol) dissolved in 50% of tetrahydrofuran was poured into the mixture and stirred at room temperature for 20 hours. After that, 1 liter of calcium hydroxide was separated daily, extracted with oral fluid ethyl acetate, and extracted with DT'? After 4 sets of A ether, it was crystallized from ether to obtain glycidyl-p-aminoacetophenone as white crystals with a temperature of 92-93°C. Next, the 500 was equipped with a stirrer, cooler, and dropping funnel.
20 ml of propylene oxide was placed in a 3-bottle flask, and 05d was added to the hexafluoroboron titanium complex.

Add to this 12 g of glycidyl-p-aminoacetophenone.
(0,05mot), Glycidol 37 W (0,5mot)
w>l) was dissolved into propylene oxide 20-, hFr+ was removed in 1 hour, and the reaction was further allowed to proceed at room temperature for 1 hour. Unreacted propylene oxide was distilled off, and the polymerized product became a pale yellow viscous liquid, which was filtered off.

01 compound chemical properties and average molecular knowledge ultraviolet absorption λmax (MeO)] ) 567n11
1 (884V#1lQi) Infrared absorption 6400cm-' 0-) (iKayo1 transfer 2950cr
n-1 and 2900cm-' C-4i pl+ gi
Vibration 'l645cnr-1C-〇Stretching vibration 1290cm-' Carolr+, -b: Stretching vibration 1
100L:rn-' C-○ compression vibration 820o++-"
Molecular weight determined by pensene nuclear out-of-plane bending GPC: 11 ji + constant (pullulan equivalent) - 1.5,000 Next, in order to confirm the safety of the high molecular weight UV absorber of the present invention, an animal test (6 Angorauser P animals) was conducted.
Table 1 shows the resultant jets.

The test method is as follows.

Test sales of skin dregs: Samples were applied once daily for 4 consecutive days to the backs of hair-removed Ancora rabbits (100% disease-free, 60%
, 10%) was administered transdermally, and the results were observed the next day. Note that water or ethanol was used as the diluting solvent 7.

Table 1: Skin dregs - secondary stinging test 10: Reaction -: No reaction It is extremely high.

Furthermore, Table 2 shows the effect of 4ν on the solubility of the unexploded four-corner molecular weight ultraviolet absorber by the ratio of the glyceryl group 2ts and the alkyl ether group.

[Raw materials] X component: Glycidol Yhνtr+=Tek; J-1-1/So7→Tono L'/ITII, r+\z component: 2-hydroxybenzopheno (synthetic intermediate) As shown in Table 2, the present invention The solubility of ultraviolet absorbers varies depending on the ratio of glyceryl group to alkyl ether group.For example, when an ethanol-soluble polymer is blended, water evaporates after ethanol evaporates on the skin. It is possible to make water-resistant cosmetics that form an insoluble film, and it is suitable for application to various formulation systems. A formulation example is shown below.

The blending ratio is 1ti parts.

Example 1. Hydrogen burn lotion (Santan River) ethanol 80 Propylene glycol 5.0 Hyalcymin o, i Polyoxyethylene (50) Hydrogenated castor 4 0.5 Citric acid 0.02 Sodium citrate 0.1 Methylparaben 0.05 Fragrance Sting 0.26 Water 86. .

Example 2 Sunscreen cream Stearic acid 4.5 Whale wax 65 Setanol 25 Lanolin 15 Myristic inpropyl 6.0 Squalane 4.5 Polyoxyethyl monostearate 45 Renruhytan Monostearin Tortoise sorbitan 1υ Propylene glycol 35 Butylparaben 0.2 Butylated hydroxytoluene 005 Fragrance phase 0.25 Water 500 Example 6. Water resistant sunscreen lotion ethanol
77.0 Polyoxyethylene (50) Ice packed castor 0.5 Oil Olive oil 0.1 Glycerin 0.5 Lipo-nucleic soda 0.1 Cationized cellulose 01 Fragrance 0.2 Water 11.5

[Brief explanation of the drawing]

FIG. 1 shows the ultraviolet absorption spectrum (F, tc+H) of the 2,4-dihydroxybenzophenone thread high molecular weight ultraviolet absorber (ethanol compatible) prepared in Synthesis Example 1. Figure 2 shows the ultraviolet absorption spectrum (MeOH) of the 2,4-dihydroxybenzophenone polymer 1L ultraviolet absorber (water soluble) produced in Synthesis Example 2. FIG. 3 shows the ultraviolet absorption spectrum (MeOH) of the ethyl PABA-based high molecular weight ultraviolet absorber (water-soluble) produced in Synthesis Example 6. FIG. 4 shows the ultraviolet absorption spectrum (MeOH) of the p-aminoacetophenone thread polymer produced in Synthesis Example 4, and the ultraviolet absorber (water bathable). Patent applicant: Pola Chemical Industries, Ltd. Absorbance

Claims (1)

[Claims] 1) A high molecular weight ultraviolet absorber represented by general formula (1). X-4-ZH(1), C) j2cH20, LJ(2CH(CH3)O, Cl
]2CB(C2115)0. CF12C! -120H2cH20 is one or a mixture of two or more, Z is the following ■ or ■; (However, R1 and R2 represent hydrogen or a hydroxyl group); (However, 7, A is a carboxyl group: -Coo)t , alkoxycarbonyl group: -coocPI3. -caoc
2s5゜-COOC3B7, acetyl group: -COCH
In addition, t, m, and n each represent the number of added moles, and 3<, t(,200,0(m<200.2<,
' n < 200. ] 2) 1 of the high molecular weight ultraviolet absorber represented by general formula (1)
Cosmetics containing more than one species. XJt-Yyou-Zh(I) Cl 20H20, CF2Cl(CH5)O1Cb2c
H(c2■+5)O. (J (2ct> 2 CH20H20 any 1
or a mixture of two or more, 2 is the following ■ or ■: (However, R1 and R2 represent hydrogen or a hydroxyl group); A (However, 7, A is a carboxyl group: -Coo)], an alkoxycarbonyl group: - COOCHro, -COOC
2H5. -COOC3H7, acetyl group: -COCIco3) Also, L, m, and n each represent the number of moles added,
5≦t≦200.0≦m≦200.2≦n<j200. ]