JPS5955893A - Protenin derivative containing grafted ultraviolet ray absorptive group, manufacture and composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention tri) provides a protein iIt i) that has been chemically modified to contain a fund of UV ILII grafted onto a protein molecule 611.
This protein of the present invention V, 1 also has H on the body! ■The production method of derivatives, and this poem i, Q body full activity ('l:'l
A composition for the total treatment of skin and hair and protection from photochemical deterioration, containing as qJ+ a valuable cosmetic property for the treatment of hair.
Many protein 'IL1 hydrolysates containing I'l are already known. Furthermore, it is also known to craft molecular threads that have an effect on UV light on synthetic polymer buttons.
Jk polymer +; i, harmful sunlight to the skin 11ζ
4.9 i/l of cosmetic compositions that remove water. However, these polymers are commonly used in conventional cosmetic solutions due to their viscosity, the hardness of the film they form, and their UV absorption properties. It was found that the force is relatively low (this means that the composition containing them should not be 11.11.11.11 in the history). The purpose of the present invention is to provide a chemically treated skin protector that can be used as a skin treatment product and as a skin protection product against the wide shadow of ultraviolet rays. It is to provide the raw fish) 'r'l, 9/If'', ultraviolet tI-'
Chains of natural polymers are used as carriers for crafting molecules that can be removed.Therefore, this can be used for skin and hair, processing effects and grafting due to the presence of protein chains. 41 of this molecule
Protection due to existence, j! y, ) 1 pot and 2 il( 411 points are obtained.In addition, the protective skin lIq formed on the skin
The compositions containing these products are flexible enough! It is more comfortable to use a sun protection composition containing a synthetic polymer with l″j nine-dimensional grafts 1θ1.
t-I photoIIL protein 1j) (L'
It can be seen that +u'rl is large. These dJ protein 11゛; sex protein l! t is a conventional cosmetic medium Ij4. Therefore, the present invention is suitable for materials with a molecular weight of about 500 to 50,000.
and the following general formula % formula % [In this formula, Y is a group of molecules that absorb ultraviolet rays,
P□ and P2 are groups of protein negative derivatives that are not acylated and not chemically modified by nucleophilic order j7III or substitution, and e e M is derived from H1 alkali metal or magnesium. cation, or N (R2)4 (wherein the group R2
U, which may be the same or different, represents a hydrogen atom or a hydroxyalkyl group or alkyl group containing up to 41f/i+ carbon atoms, and Q is the 419 constituent amino acid of protein. The alkyl group and aryl group 'ilζ are aralkyl groups, and T is 0 or N.
It represents li, or it represents fJ, S when the tanno-crystalline substance contains all the cysteine, and z 1 or group 80; 1M (in the formula, the cation Ml has the same color as above) or 5R3 (in the formula, 1 and 3 are (formula, in which p ij: is an integer from 0 to 5't, R41
j is a hydrogen atom or an alkyl group having up to 14 carbon atoms, and It5 is or (1 in formula 5) 14. A total of 2 to 10 carbon 161 atoms? (I1 if, 6': "j and t branched alkylene porridge" mowashi, fil! ion M (IJ t:j: has the same fishy taste as above, the group It
6tJ: a hydrogen atom or an alkyl group f having up to 4 carbon atoms, which may be repeated or different;
f, j hydroxyalkyl group? i? Is EtJ halogen [00,R8O,-'l or Jj
-J1 (indicates an association) of hydrocarbons containing 1 to 10 carbon atoms in SO''4.
It is derived from the 13A group + 1 amino acid of the protein 'f1, and has the same 11 amino acids as above, and is monosubstituted by ``u, l; , diti, 7. (, the amino group represented by the formula, q +, l: I from l to 51
+rll uncle, but NLZ Karin e middle 803M also r, J-8l, kei, washiki f
s, q Must be YJ-1 and protein protein 1 must contain cystine, single (1'l A is 170 of protein inducer,
L4 represents percent, 111th place B t, U
Protein Ipj ii δ41, body's O~15 isotope weight above percent total table vs. 11, to do 4? Il'ke body and-! Chemically, the thickness of the protein derivative production represented by the barring style (iris) on the protein derivative that has been chemically That is, the underlying protein '#4 G, t keratin,
It may be derived from a material source of II+II origin selected from 111° consisting of gelatin, albumin from egg white, blood albumin, casein and lactalbumin; Keratin is a substance contained in the group consisting of hair, wool, horn, fur, mineral bristles, and feathers.
I can do it. (In addition, it is a protein consisting of soybean, groundnut and cottonseed.)
1"C: It may be derived from a substance originating from a substance that is exposed.Furthermore, this protein bamboo derivative V"1, after grafting an ultraviolet absorbing group to M) after storing potassium water. It may be a chemically modified protein hydrolyzate. If the chemically modified protein represented by the formula (1) 'j'l i'i,'l conductor group 7 or less, that is, u', f((' !Is not 1.1 or more] 2-11 (class alkoxyno,
(by i+'4 i@(is cinnamoyl group, varadialkylaminobenzoyl group, zarythyloylnor, placed (<+5) or (is 1 in the aromatic nucleus)
If'(
4114 Sal, Z't (Also, J, ) A carboxylic acid group derived from benzylidene camphor, substituted by a sulfo group at the 10th carbon atom of camphor, and an acyl group derived from a sulfonic acid. It is ethyl sulfonyl, 1〆f, J: Q, or sulfonyl group derived from isophthalylyl-camphor group or terephthalylidene-camphor group,
2-arylbenzimidazole, 2-arylbenzofuran, 2-arylbenzoxazole, 2-arylbenzotriazole and 2-7arylindole]+'l complex 172 type absorbent +'tl
An acyl group or a sulfonyl group derived from a carboxylic acid or a sulfonic acid derived from μ sulfone 11, an acyl group or a sulfonyl group derived from a sulfonic acid derived from an absorbent yielding to hydroxybenzophenones, 1)' l+! '(
Acyl 41 (, 11't') derived from absorbent made of carboxysilmarin tilt, which has been converted to monophenyl cyanoacrylate, either unconverted or 11'ζ substituted in the U aromatic nucleus. t', an acyl group derived from a single-acting agent of diphenylcyanoacrylic 414, and unsubstituted or ill 1 (+i・1 or more hydroxyl 1 (also t', lower alkoxy yarn or
Consists of an acyl group or a sulfonyl group derived from an absorbent made of dibenzoylmethane, which is substituted by an alkyl two! Four chemically modified proteins belonging to PK, l, t,
For Y -fj-r samurai, θ'r' ”L t, < is based on the following, (it = 11% C1l: (, CI
') or ψCI (3 la 113).
The molecule l'l of the Q conductor (is 5,000 to 30,00
It would be nice if it were 0. Similarly, if Z represents S)ζ23 gold, then the formula fly
) Oyo U (■) ni oitep (J, ni', r t L,
<'t is 0, and 1ζ4 is or is a hydrogen atom. The present invention also provides that, firstly, if you are at ease, f1 is set so that the molecules of the hydrolyzate ■1; hydrolytic force ゛t by firIY element, +(L2), one or more compounds corresponding to the following formula (in this formula, , 7.II + moisture 111
By reacting with all or part of the amino group, alcohol group (boomey) L group of tanno-kuri a which has not been hydrolyzed or has been hydrolyzed, Also, r,,t) Ultraviolet i,'i! ”
<If the absorbing group is grafted and 203 has aminono'-, which can still react after chemical grafting of the UV-absorbing group, then the following formula) 4 (In the formula, Xlr halogen atom gold represents, R4,
琐 and p have the meanings listed above 1-. ．． it7
carries out the N-'fulkylation reaction with an alkylating agent compatible with one of the hydrogen atoms or (alkylno with up to 4 carbon atoms, L represents), and fourthly, if necessary is, and the protein used is 1'
When the rice contains cystine, (i) the r'til notation treatment is carried out to reduce the disulfide of the protein 11 (all or part of the grain, tri > -80
117.1; optionally after this oxidation, the 1"+'2-80311 group is converted into a salt thereof, or -: i7 and -5 (11) of the protein subjected to the above treatment. Cystino, ′, : All or − of the disulfide bridges of
QH(p, '+YJ element to become a thiol group, after this element Ij'l m, i layer:: (Ila), (Il
la), (IVa) and (W'a) "XJ
The present invention relates to a process for producing a chemically modified protein 'ala Vf form of formula +11, which is characterized in that the S-alkylation is carried out by an alkylating agent with R5. The method for producing the present protein ql derivative consists of these sequential steps, that is, if necessary, the first step is power 11 water decomposition, ?
1. 2 steps of IL-based grafting, 3rd step if necessary.
Step N-alkylation and if necessary 61!
4 steps n! 82, 3 and 4V consisting of S-alkylation to converted or reduced
If you do all of this, the manufacturing saw method +■1 factory can be replaced.
Normal r+:'! /Jll water decomposition or known protein hydrolase (broteinase PSF 2019'
, glonase, trypsin, papain, etc.). ) J11 water splitting process is plI and 11? , the element/group ff+j ratio changes to 3 depending on the enzyme used. N j:'τ method (1z2 on 1''n r, I, in particular, consists of acylation, and its target is not hydrolyzed or also &;t7J11 is hydrolyzed) The reactivity of the alcohol, on the thiol moiety, is the acyl group derived from one or more L molecules that yields one purple i-ray, and the acyl groups are V, nulfonyl, J, j,', '
i,. Acylated iL normal °
j' in the presence of alkaline a's, /I') - chloride, especially acid chloride, is carried out every month. River (the third way to use V is culm 111, if it is done, if!, the formula (II a), (llll
a), (IVa) and (N'a,) by an alkylating agent corresponding to one of them. The N-alkylating agent used (formula X,
Those corresponding to -CO□-C021-4 (X. and the taste of MG9 are as described above) are advantageous. A preferred N-alkylating agent is monochloroacetic acid. The fourth step of the reaction, if carried out, is the oxidation of the disulfide bonds of the cystine groups of the protein, or the disulfide bridges of the protein, with a conventional type of reducing agent such as an alkali metal salt of thioglycolate or a solution of ammonium thioglycolate. I earned it by redeeming it in advance by -S
It can consist either of S-alkylation of the H group. After the disulfide bridges of the cystine groups of the protein have been cleaved, they can be converted to cystic acid groups by oxidizing the treated protein. The oxidation is preferably carried out in an acidic medium with an oxidizing agent such as hydrogen peroxide or a peracid. If necessary, the 1803H group is converted into its salt following oxidation. S-alkylation is carried out by the above formulas (Ila), (llla),
Preferred alkylating agents and particularly preferred alkylating agents are those indicated in the case of N-alkylation. , grafted onto a proteinaceous derivative/:, 1)° 4'l of the rostrum: 1'3)'(,l"il'r: il
'I'm kidding.・f〃wat, if Y is not ii'i', Benzoylno 1(:, -Lilythi [Jylno 1(, Benzylidene-Carbonyl 12-mata(, 1, 1, derived from sulfone rRA6 '8. A, carboxylic acid or e (sulfone 1 wave acyl group derived from e, acyl group derived from the absorbent prepared by J.
This compound θ knee 11 is 280 to 32. Onm wavelength (l'j, lA -c:)Y; k absorption f le. If Y is derived from terephthalylidene-camphor group >K-
J is a nulfonyl group, 2-arylbenztriazole or hydroxypenzophenone is an 'AN6 syl group, monophenylcyanoacrylic i fc+, L is an acyl group derived from an absorbent made from diphenylcyanoacrylic 474. In particular, the compounds generally absorb light in the wavelength range of 320 to 380 nm. If Y is not converted or f is 11′1”
Dibenzoylmethane being converted? If it does not represent an acyl group derived from the absorbent of 7'i structure, the present compound Ej
: generally absorbs light at wavelengths of 300 to 380 nm (4).
[1] Containing at least one compound represented by formula (1) of 44, it is used as a composition for protecting the human epidermis.
8) A cosmetic Jl composition for use as a sunburn composition. The present invention aims to treat all parts of natural and sensitive hair and protect it from photochemical deterioration.For this purpose, in a suitable carrier, It relates to a composition containing at least one compound of the formula Il. "Sensitized hair" refers to hair that has been subjected to perming, color fastening or whitening.
Preferably, the compound of formula +1) is present in the composition of the invention in a proportion of 5 to 15 weight percent based on the total Tlj tri of the composition. Further, the compound is dissolved in a solvent selected from the group consisting of water, lower monoalcohols or polyols, and aqueous alcohol solutions. Particularly preferred mono- or polyalcohols are chosen from ethanol, isogopanol, 7"robylene glycol and glycerol. The compositions according to the invention may be provided in the various forms normally used for compositions of this type. In particular, this composition 47
/I can be provided as a solution in the form of a lotion of various thickening degrees, as an emulsion in the form of a cream or milk or in the form of a jelly, and can be packaged in an aerosol can. The subject-matter compositions of the present invention intended for protecting or treating the skin contain cosmetic adjuvants commonly used in compositions of this type, such as thickeners, softeners, humectants,
superfatting agents, emollients, humectants, surfactants, preservatives, anti-foaming agents, fragrances, oils, waxes, pigments and (also I)
d) It may contain colorants or any other ingredients commonly used in cosmetics. One aspect of the present invention provides that, in addition to the compound represented by formula (1), a fatty alcohol, a polyoxyethylated or polyglycerolated fatty alcohol, a fatty acid ester, a fatty acid triglyceride, a fatty acid, or lanolin can be used in the presence of water. emulsions in the form of protective creams or milks containing natural or synthetic oils or waxes. Another embodiment is a lotion, such as an oil-alcoholic lotion based on a lower alcohol (e.g., ethanol), or a glycol (e.g., globylene glycol), and/or a polyol (e.g., glycerol) and a fatty acid ester or fatty acid triglyceride. Become. 1. Aqueous-alcoholic lotions based on the above-mentioned low alcohol content and water can also be removed. The cosmetic composition of the invention may be an oil-alcoholic gel comprising, in the presence of an oil, one or more lower alcohols such as ethanol, propylene glycol, glycerol and a thickener. If the composition according to the invention is used as a sunscreen cosmetic composition, the composition comprises at least one compound of formula (1), but optionally υUV-B radiation or UV- Other sun stimulants specific for A-rays and compatible with the compound can be used in conjunction with the compound. In this way it is possible to obtain a formulation that removes all of the UV-B radiation and [JV-A i. A further subject of the invention consists of compositions intended for the protection or treatment of natural or sensitized hair. These compositions rL1 Shampoo, before shampoo-
Afterwards, the 0.00-glue should be applied to the body before coloring or bleaching, and on the body before perming. Rakushi type lotion, jelly or emulsion, styling lotion or treatment lotion, flow drying lotion, setting lotion, hair lacquer, box f? : It can take the form of a composition for perming, coloring or bleaching hair. These compositions contain, in addition to the compound of the formula Electrolytic TI, organic solvent, silicone derivative, oil, wax, grease inhibitor,
The composition itself or may contain pigments and/or colorants which serve to color the hair, and any other ingredients commonly used in the hair field. When constituting compositions or shampoos, these consist essentially of at least one anionic, nonionic or amphoteric surfactant or mixtures thereof in an aqueous medium, as well as a compound of formula (1). It is characterized by containing. Shampoos may also contain various adjuvants, such as cationic surfactants, colorants, preservatives, thickeners, foam stabilizers, synergists, emollients, electrolytes, sequestrants, one or more cosmetic resins, fragrances. , natural substances, oils and any other adjuvants used in shampoos. In this C) shampoo, surfactant 1f+
1. l'7il"'+1!, l:t", -111! to 2
~50% by weight, as examples of nonionic surfactant agents, such as monoalcohols, diols, alkylphenols, amides, diglycolamides and glycidol, and synthesis products such as French Patent No. 2,091,5162,
:12B, 7 (i3 No. OLD 1.4'17
* (Non-ionic field book 1' (cut,
-t-L/'ff polyoxyethylated or IJ,
Polyglycerolized, 1 with 8 to 181 carbon atoms
IiT Rib i+'r %: If lI? R rib alcohol, alkylphenol ethylene side oxidation Fk-containing, ethylene oxide 7
[Do]゛Rohil/Nkaheshito and cojR Master! Of course, ethylene-4 oxide. L hip r J birenogisido and lI
iT ribalcoalcohol synthesis, hoIJ, t = 1'
Schedirenated fatty amide; 1, Lyokine-edylenated fatty amine, ethanolol-7 MiI', /' IJ
Included are Cole's Ili Ding 11Jj rl Nisdel, the flit IIJ month'I reester of nlubitol, the Ilif rib varnish of sucrose, and the lycoside alkyl ether, alone and if necessary with a nonionic surfactant. Anionic surfactants which can be used in particular are alkyl sulfates, oxyethylated alkyls selected from alkali metal salts, ammonium salts, amine (at or amino alcohol salts) of the following compounds: Sulfates, alkylamidosulfates and oxyethylenated alkylamidosulfates, polyoxyethylenated alkylaryl sulfates and monoglyceride sulfates, -alkyl sulfonates, alkylamides sulfonates, alkylaryl sulfonates and α - olefin sulfosuccinates, mono-alkyl sulfosuccinates, oxyethylenated alkyl-sulfosuccinates, and alkylamido-sulfosuccinates, - alkyl sulfosuccinamates, - alkyl sulfoacetates and alkylbo-liglycerol carboxy -alkyl taurade, and oxyethylenated alkyl phosphate, monoalkyl sarcosinate, alkyl polypebutidate, alkylamide polypebutidate, alkyl isethionate and alkyl taurade, (alkyl group of all the above compounds) shall contain 12-18 carbon atoms), and acids derived from fatty acids such as oleic acid, ricinoleic acid, palmitic HL and stearic acid, copra oil or hydrogenated cozola oil, and the formula % formula % (the formula in which the substituent Alk corresponds to a straight chain having 12 to 18 carbon atoms, and n is an integer from 5 to 15. Any anionic surfactant 1r-1 agent can also be used;
(Examples of ampholytic active agents include, inter alia, algylaminomonoglobionates and alkylaminodiprobionates of betaines, such as N-alkylbetaines, N-alkylsulfobetaines and N-alkylamidobetaines, Examples of compounds include alkylimidacillins, and asparagine derivatives. The alkyl groups in these surfactants preferably have 22 or fewer carbon atoms. John, setting lotion or styling lotion tri consists of treatment lotion
Well, these are generally water-based, alcoholic and water-based.
In the alcoholic solution, in addition to the compound represented by formula (1), at least one cationic, anionic,
Non-ionic or non-ionic polymers or mixtures thereof generally 0.1 to 10% by weight, preferably 4%
If it is 0.1 to 3M per cent, it contains an anti-foaming agent. This composition is a wash-off type lotion (called a rinse).
When forming a shampoo, they are applied before or after whitening, before or after perming, before or after shampooing, or in between two shampoos, and then washed off after a four-step interval. These compositions may contain aqueous or water-alcoholic solutions, emulsions, containing or without surfactants.
Or it may be a jelly. These compositions can also be pressure filled into aerosol cans. The surfactants that can be used in the formulation are essentially the non-ionic or cationic surfactants mentioned above in one case of shampoo composition 1, especially monoalcohols or alpha-dioic surfactants. A condensation product of glycidol with alkylphenol, amide, diglycolamide, etc.
ItT groups having from 7 to 21 carbon atoms or mixtures thereof, in which the aliphatic chain may contain ether groups, thimeether groups and hydroxymethylene groups, r being a subsequent opening from 1 to 101; (In this formula, R9 represents an alkyl group, an alkenyl group, or an alkylaryl group, and S represents a standard value varying from 1 to 10.) The compound represented by the formula % formula % (in this formula R□. contains or does not contain one or more 01-1 groups, and 8 to 3011i1
an aliphatic group having 1 carbon atom, and t is 1 to 5
The compound represented by is an integer or decimal number up to . Also used are polyoxyethylenated or polyglycerolated fatty alcohols, alkylphenols or acids having 8 to 18 carbon atoms in the fatty chain, most commonly containing 2 to 15 moles of ethylene oxide. I can do it. The concentration of surfactant may vary from 0.1 to 10%, preferably 1-10%, and from 5 to 7 weight percent. Nonionic, cationic, anionic or amphoteric polymers and, if necessary, anionic or amphoteric surfactants can be added to these compositions. When the composition is in the form of an emulsion, it may be non-ionic or anionic. Nonionic emulsions consist primarily of mixtures of oil and/or fatty alcohols with polyoxyethylenated fatty alcohols, such as polyoxyethylenated stearyl or cetyl-stearyl alcohol, in the presence of water. Cationic surfactants or cationic polymers can be added to these emulsions. The ionic milk candle liquid is made from soap and contains an anionic or a nonionic compound represented by formula (1). When the compositions are in the form of a jelly, they contain a thickening agent in the presence or absence of a medium. Thickeners used a) include sodium alginate, gum arabic, or cellulose derivatives such as methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose. The lotion may also be thickened by a mixture of polyethylene glycol and polyethylene glycol stearate or distearade, or by a mixture of phosphate esters and amides. The concentration of thickener is 0.5~
In order to provide a clearer understanding of the subject matter of the present invention, some of its embodiments are set forth below, but these are merely This is for illustrative purposes only and is not intended to limit the scope of the present invention.Example 1 Represented by formula (1), in which the proportion of unit B is 0 and the proportion of unit A is approximately 40% by weight. Ashi, M+ is H@
, and the unit has the formula (in this formula, Q is the alkyl group of the amino acid of keratin,
It represents an aryl group or an aralkyl group, and T is N1(-1
Production of a hydrolyzate having:
t and 860 d of water are introduced into the reactor. The mixture is heated under reflux for 8 hours and then filtered. lJ'#wo water 1
Dilute with 5t and separate the precipitate. The keratin thus obtained contains 60-80% water. Relative analysis of amine 11)' shows similar proportions in untreated chicken feathers and extracted keratin. In each case the proportion of cystine is of the order of 7% (between 6.5 and 7.5-0, depending on the starting material). 2nd step: Enzyme power of keratin (J water decomposition) The keratin obtained as shown in the above 1st step is used as a starting material. A suspension of 5 kg of keratin in 3.5 liters of softened water. Prepare the suspension and heat this suspension to 40°C. Add a 30% aqueous solution of sodium hydroxide to adjust pI to 8.6. Add proteinase "PSF 2019" 489 at once and mix. i3 hours 40t1℃; 6i11j'
Le. pI (U) is maintained at 8.4-8.6 by adding a weighted M% aqueous solution of sodium hydroxide.Then, the pH of the resulting solution is adjusted to 7.5 with concentrated hydrochloric acid, and the pH is adjusted to 95. Deactivate the enzyme by heating for 5 minutes at ℃.The mixture is quickly cooled to room temperature, centrifuged, the supernatant is treated with cellulose acetate, and the bath is lyophilized. This gives a water-soluble beige powder. 1.375 f i
obtain. Yield: 92 cm. 3rd step Grafting of molecules with light effect 20Shiho Adjust the temperature to 2℃ and charge fc2 into the reactor with the following materials: 1101 obtained in the 2nd step - water 2
50 cy”, -acetone 250α, and -sodium hydroxide 30'Jff part % concentration aqueous solution 10
cm (this results in pi-1rJ,,'9). Next, 3-benzylidene-camphor-41-sulfonyl chloride 82f (0.24 mol) is added in amounts > tJ over 1 hour. Keep pHr between 8,9 and 9.2. The reaction is complete when the 6 o'clock tune is turned on. Next, concentrated J acid 3
Add ocrn to bring the p)l of the solution to 2.5. 2 tons of water
When diluted with water, a gummy texture is obtained. This is separated by decantation for 19 minutes, taken up in 500 cm of water, and ground at 1 point until crystallization is complete. Separate the crystals and add water again
The mixture is made into a paste-like form in 100ml of water, washed twice with 400 J of water, crushed into fine pieces, dissolved in water with a pH of 7, and freeze-dried. This gives a beige powder 952. Yield 60%
. Example 2 Expressed by formula (1), unit A40 weight i and unit B2.5
Including heavy M and chi! C, M (9 represents Ho, unit A has the same formula as in example 1, unit B has the formula -5CH
Preparation of the Zt gold-containing hydrolyzate represented by 2COOI (5'7X). 1st step: Reduction of cystine to cysteine The product obtained at the end of Example 1 is used as the starting material. , stirred under nitrogen for 20 hours. The product obtained in Example 1, 421, 210 car' of water. A 95% yield solution of monothioglycolic acid, 3.1α3,
and -sodium hydroxide in an amount sufficient to bring the pHt to -9 to 9.5Second step: S-carboxymethylationTo the solution IVL obtained at the end of the first step of this example
2.3 f (0.13 mol)'t-addition. pn
The mixture was stirred at room temperature for 2 hours. Next, make this acidic to pn42-2.5, dilute with water, filter the precipitate once, wash with water until the pIl of the washing solution becomes 6, dissolve in water with pH 7, and freeze-dry the solution. . This gives a beige colored powder. Yield about 88 inches. Example 3 is represented by formula (1), contains 39% by weight of unit A and 3 double stitches of unit B, MQ represents Hot-, and A i is Example 1
7. has the same meaning as in and B has the meaning of formula 7. The solution obtained at the end of step 41 of F/L+2 is used as a starting material. l-dimethylethylammonio-3-
Acrylic F Midogropan Bromi F 34.5f (0,1
3 mol) Add the mixture to j+l of the mixture C at room temperature, pf
I9-9.5-C Stir for 4 hours. After acidifying with dilute acid, the solids were washed once and then several times.
Thaw with H7 and lyophilize the solution. This gives a beige powder of 31 ft. Yield about 74 inches. Example 4 Represented by formula (1), where Q is the alkyl group of the amino acid of keratin,
The aryl group represents an aralkyl group, T represents NH or 0, and MQ represents I (@ and the proportion of degree B is zero). Manufacturing of. The hydrolyzate obtained at the end of the second step of Example 1 was
) used as 1-ru. 0 t1 of hydrolyzed keratin obtained at the end of the second step of Example 1, the temperature of which was adjusted to +/-0.2° C., was charged into the reactor with 1.75 an of water. - Acetone 175 3, weight aqueous solution of sodium monohydroxide 5 c
m”, and 54 g (0.16 mol) of -3-benzylitine-camphor-10-sulbonyl chloride. After stirring for 2 hours, 3-benzylidene-camphor-1
A precipitate of sodium 0-sulfonate appears. This leaves ti++1. The p-liquid is treated as in the third step of Example 1. This gives a beige powder 36f. Yield approx. 34% 5 cases
5 Contains 1% of unit A 331Lil and 83.5% by weight of units represented by formula (1) and having the same formula as in Example 4, the group Z in unit B means all -8CH2COOIl, M
Production of hydrolyzate, where o represents 1■'. Preparation of the following mixture: Product 23f1 obtained at the end of Example 4 - Water 200(7), 95% strength by weight solution of monothioglycolic acid 2.95α
, and -30 parts h1. of sodium hydroxide in an amount sufficient to give a pH'i of 9 to 9.5. Concentrated aqueous solution. The mixture is stirred at room temperature under vacuum for 20 hours. Next, 11.34 f (0.12 mol) of monochloroacetic acid is added and the pH is adjusted to 9 to 9.5 using a 30 Tc*% aqueous solution of IJium hydroxide. After stirring for 4 hours, a small amount of insoluble matter was removed, and 1 solution was prepared with a pH of 2 to 2.
．． The solution is acidified to pH 5 and diluted with water, precipitated by filtration, washed with water until the pH of the washings becomes 6, dissolved in water at pH 7, and the solution is freeze-dried. This gives a beige powder 2Of. Yield: approximately 87 yen. Example 6 It is represented by the formula +11, and the formula (in this formula, Q is the alkyl group of the amino acid of keratin,
The hydrolyzate contains 14.5% of the units A corresponding to (represents an aralkyl group or an aralkyl group, and represents NH or 0), the proportion of units B is zero, and M represents H. Manufacture. The product obtained at the end of the second step of Example 1 is 531, - water 12.
5 cPn3, 125 tM of acetone, and enough sodium hydroxide to bring the pH to 9.
0% concentration aqueous solution, then p-methoxycinnamoylchlor')F29f(0,
147 mol) in 1 hour. For 2 hours, keep stirring on the one hand and maintain the temperature, and on the other hand keep the pH at 8.5-9.
Keep it. The mixture is then brought to room temperature over a period of 2 hours. Acidify to pH 6 with 6N hydrochloric acid solution, precipitate the formed p-methoxycinnamic acid, wash twice with 200 cm3 of 1 kr water, and
Acidic with a total pit of 5.5. Next, add P liquid to ether 300 cn? After extracting three times with concentrated hydrochloric acid, pH 2.5
Then, precipitate by diluting with water and 500 bacteria. The resulting gum is separated by decantation and dissolved in water. The obtained precipitate was filtered and the pH of the washing liquid was 6.
Rinse with water until clean. When ground, dissolved in pH 7 water and lyophilized, a beige powder 252 is obtained. Yield: 33 cm. Example 7 Formula (11), Formula (In this formula, Q is the alkyl group of the amino acid of keratin,
It is an aryl group or an aralkyl group, and T contains 30% of the unit A having 9 containing NHt or O, the proportion of the unit B is zero, and Mo represents H@.1] Water decomposition product Manufacture. A 2L reactor whose temperature was adjusted to 20±0.2°C was charged with the following: 〃■ Hydrolyzed keratin 0v obtained at the end of the second step of Example 1
A 30% strength by weight aqueous solution of elm sodium hydroxide sufficient to make 1 one water 250α, -acetone 2506n3, and -pi-1't 9. 2P-tertiary butylphenylbenzoxazole-6-sulfonyl chloride 4s? (0,128 mol)
The mixture was incubated at 20°C for 48 hours at p.
f (48.Stir at 5~9 and stir a little 111 insoluble matter'ν(y, Il, 1 person, d-1 solution is made σi with dilute hydrochloric acid solution, set to pJ (5,5, JC-7k 250
cm 't' Extracted three times, acidified with 0.5 N hydrochloric acid to a total pH of 2, diluted with 1 t of water, and separated the gum ttx- by decantation. comb, and the resulting precipitate is d″I
Filter and wash with water until the pJl of the washing solution reaches 6. Grind pJ
When dissolved in 17 liters of water and lyophilized, a beige powder 13 is obtained.
2 is obtained. Yield about 15 inches. Example 8 Expressed by the formula (11, in the formula, the proportion of single (i'lJ3 is zero, the proportion V of the Qi position A is about 20% by weight, and the unit A is expressed by the formula (In the formula, Q represents an alkyl group, an aryl group, or an aralkyl group of an amino acid of gelatin, and T represents N f (t or all O). Reaction temperature controlled at 35 ° C. Charge the following into the container.
T) Ceratin (1.75 mm containing 7 min-/f) 100f, and -acetone 25
Add 0cm3° of a 30% concentration aqueous solution of sodium hydroxide to prepare pit'i-9. Next, 3-benzylidene-camphor-4'-sulfonyl chloride 599 (0,174 mol) was added to the male blade for 3 hours.
The pH is maintained at 8.9 to 9.2 by adding a 30% by weight aqueous solution of sodium hydroxide. After reacting at 50°C for 5 hours, 16 cm of concentrated hydrochloric acid was added to the solution to adjust the pH to -2.5. The formed precipitate is collected and washed with water until the PL of the washing solution becomes 4, and then redissolved in a 5% sodium hydroxide water bath solution of 75%. After freeze-drying, a beige powder 1069 is obtained. Yield about 70%. Example 9 It is represented by the formula fTl, in which the proportion of unit B is zero, the proportion to the unit is about 25rR, Gt%, (
+) (-1-) M represents H, and the unit A is represented by the formula (in the formula, Q represents an alkyl group, aryl group, or aralkyl group of the amino acid of casein, and P represents NH or 0) Preparation of protein derivatives. 1st step: Enzymatic hydrolysis of casein 100 g of edible casein was poured into 11 ml of water and warmed to temperature. -1 by adding 65% hydrochloric acid to 1.8-2. [1 to 1
Do one verse. After the temperature stabilized at 38±1°C, 1:60.
Add 0.1 V of pepsin (JOO Sigma (311GMA, registered trade name). After stirring for 81 minutes at this temperature, Pl (8-8,5 at 10:1...The enzyme is inactivated and the solution is heated to an ultraviolet temperature. Excludes both salt-free and molecular R1000 or less. After freeze-drying, amine-containing 12.54 ml/〃
85p of hydrolyzate was obtained. 2nd step: Gelaft formation of molecules with light-shielding effect The hydrolysis obtained by 5K as shown in the first step! using baby casein as the starting material. Hydrolyzed casein (amino nitrogen containing ffi 2.54 mEq'Wr, /
The procedure is the same as @8 except that the ultraviolet absorbing derivative is 4'-methoxy-3-penzylidene-10-sulfonyl chloride. Yield is 52 cm. Example 10 Expressed by formula (1), the proportion of unit B in the formula is 79
0, the proportion of unit A is about 25% by weight, and (+'
) ('4) M represents H-, and the unit A is a formula (in this formula, Q is an alkyl group of an amino acid of casein,
(representing an aryl group or an aralkyl group, and T represents NH or O). The product obtained at the end of the first step of Example 9 is used as starting material. Hydrolyzed casein (containing 112.54 mmol/7g of amino nitrogen) is used instead of gelatin to create a derivative that absorbs ultraviolet rays.
-Proceed as in the previous day except for using sulfonyl chloride. Yield is 43%. Example 11 Expressed by formula (1), in the formula, the proportion of unit B is zero, the proportion of unit A is about 20 times, and the proportion is d. The unit □ represents yo P. 1 (In this formula, Q is the alkyl group of the amino acid of casein,
Production of a protein derivative represented by an aryl group or an aralkyl group (r represents NH or 0). The product obtained at the end of the first step of Example 9 is used as starting material. Next, instead of gelatin, hydrolyzed casein (Amino Chishi Hiromiya Yu If 2.54 milliliter/g) was used, and a derivative that absorbs ultraviolet rays or 3-penzolidene-camphor 4'-sulfonyl chloride was used. The operation is the same as in Example 8 except that. Yield is 50%. Shio 1j12 formula (represented by 11, in the formula, the proportion of unit B is zero, the proportion to the unit is about 60tKFk%, C)
(G) M represents H\, unit A represents the formula (in this formula, represents an alkyl crystal, aryl group, or aralkyl group of Qf-terminated fructalbumin amino acid, and T represents N[(or represents 0) of a protein visiting conductor). Manufacture. Example 8 except that hydrolyzed lactalbumin (amino nitrogen containing t5.6 meq/I) was used instead of gelatin.
Operate in the same way. Yield is 58 cm. The properties of the protein derivative obtained in Example 1-12 are shown in Table m1.
-1-2g-stearic acid -1-3g-self-emulsifying glycerol stearer) ---3g-cetyl alcohol
-112g-Vaseline oil
---io, v-grape seed oil
---6y-Sunflower oil -112
g-Triethanolamine -1-1g-methyl hydroxybenzoate -0,29-fragrance
- 0,3 g - Antioxidant - 100 g Demineralized water (sufficient amount) - 100 g Repeated use of this composition protects the skin well against the weather and at the same time makes it supple and supple. It turned out to keep. Example 14 Compound of Example 6 for IR preparation of a protective moisturizing cream with the following formulation - m-3I-zinc lanolate --- 2,7 g - lanolin alcohol - 11 3 g - vaseline oil
-1-22,! i+-Vaseline
---isg-methyl rose hydroxybenzoate --
-0,3,9-Fragrance -m
- Sufficient amount - Salt water (sufficient IIl:)
---100 Jl It has been found that repeated use of this cream gives suppleness and softness to the skin and at the same time prevents it from drying out. Example 15 A protective hand cream having the following formulation is prepared: -11 2g of the compound of Example 5 -Polyethylene glycol stearate (ethylene oxide 20g)
molar content), (Sold under the name of ATLAS MYRJ 49″)
---3g-Self-emulsifying glycerol stearer) ---3#-Cetyl alcohol-1-1g-Vaseline oil
-15g- High molecular weight carboxyvinyl yt derived from acrylic acid? IJ-r- (GOODRZCHCHFI; MI (1'C from AL company)
! Sold under the name ARBOPOL 940'')---0,
3,V-triethanolamine-(1,3g-
Preservatives - m - Adequate amount - Flavoring
-m-sufficient amount-salt water (sufficient, 1
1)---100gThis hand cream was found to protect the hands from everyday external influences and to give them flexibility with repeated use. Example 16 Example 2 of manufacturing a sunscreen cream with the following formulation:
Compound -5 g of cetyl-stearyl alcohol and all-cetyl alcohol, both ethyleneated with 25 moles of ethylene in m-7 g/'
Ricerol Monostearer) ---2&-Vaseline Oil -15,9-Dimethylpolysiloxane -1,5g-Cetyl Alcohol
-1,5,9-glycerol -20#
- Anti-deception agent, fragrance - M - Shibu Ling - Sterile demineralized water (sufficient amount) - 1 ~ ioo y Repeated use of this cream will keep the skin supple and supple, and at the same time have a good sunburn prevention effect. found. Example 17 Compound of Example 7 for producing a tanning emulsion with the following formulation: 4i - Cetyl-steryl alcohol and oleyl cetyl alcohol, both oxyethylenated with 25 moles of ethyleneoxyl - 5 g - Vaseline oil -1-61-isopropyl myristate ---3g-Silicone oil
---1g-cetyl alcohol -1-
1g - Preservatives, fragrances - m - Sufficient amount - Sterile demineralized water (enough - Jl) --- 100g Repeated use of this emulsion keeps the skin soft and supple, and good tanning has a commercial effect. There was found. Example 18 Compound of Example 1 to produce a shampoo with the following formulation -i, 2g-triethanolamine alkyl (Cx2-C□,)-sulfa-) ---8,
Cycloimidacillin derivative of 0,9-coconut oil (MTl (sold by ANOL under the name 2yInANob c2u))
---Adjusted to 7.5 with 4,0,5F-pilin HCI--Water (sufficient quantity) ---100 g When applied to natural hair, this shampoo gives softness and shine to the hair. When applied to dyed hair, it also protects against 41 harmful substances in the outside air. Example 19 Need to manufacture a shampoo with the following formulation h゛1f11
Compound 3 ---i, sg complete set R-C
'H011-CH2-0-(CH2-CHOH-CH2
-0) tl-H (in the formula, R represents a mixture of an-c and alkylno, and n represents an average ai number of 1 and 3.5)
Nonionic surfactant represented by---89-laurinzoethanolate ξto---1,5#-N^ct
---5,5/7- rJI 7.
3 to 6 one water (sufficient) ---100,? When applied to dyed hair, this shampoo provides flexibility, makes it easy to apply, and protects it from harmful substances in the outside air. Example 20 A mixture of cetyl-stearyl alcohol and cetyl-stearyl alcohol oxyethylated with 1.5 mol of ethylene (I (TeNKEL)) , Social 81NN
OWAX AO” (1) Sold under the name)
---Mixture of 3,9-fatty alcohol and oxyethylated product ("POLAWAX GP200" from CRODA)
---1,5,9-Hydroxyethyl cellulose (sold under the name "JLLO8TZE QP 4400" from UNION CARBID) ---0.5g ---(double-desalinated water (enough tons) adjusted to 7 ---Apply 100g of this composition to clean damp hair for 5-10 minutes, then wash and dry the hair.The hair will be shiny.Example 21 Make a setting lotion with the following formulation. Compound of Knee Example 4---o, a, p-6
0/40 gynylpyrrorylene/vinyl acetate copolymer --,0,5,? −
Trimethylcetylammonium bromide --0.2. ! 7-
Water (100 AJ) Apply this lotion to clean hair. Dry hair is easily combed and protected from the elements. Example 22 Compound of Example B for the preparation of a water-resistant cream with the following formulation: 217-T)-2-ethylhexyl dimethylaminobenzoate -1-49-ethylene oxide 2()molwoxim, laurate ester of sorbitol -- -4
,5g-,lr IJ phenylmethylsiloxane (5i
Sold under the name licone DC55 (S”)
-115g-glyceryl monostearer) ---4,5y-sorbitan monostearer)
---4μm stearic acid -115g
-Glycerol ---3,5,? -Magnesium aluminum ξnilam silicate -1-2I-Fragrance-Preservative = 5-chloro 2-methyl-4-inchazolin-3-one, 2-methyl-4-inchazolin-5-one and magnesium chloride and layer A 1.5% concentration aqueous solution of a mixture of calcium chloride (sold by ROHM and HAAS under the name "KATHON CG")
) ---1uog This sunscreen cream protects the skin from UV-B- and keeps it supple in its natural state. Example 23 To prepare a sunscreen cream with the following formulation: Compound of Example 11 - m-4y-stearic acid -1-5y-sorbitol
---3g-Lanolin-1-2g-Isozorovir myristate --2.9-
Cetyl alcohol -0,15g-pa-2-hydroxyamne, probyl monozoate ---0,1,9-
Acrylic polymer with a molecular weight of 2-6 million (sold by GOODRICH CHFMICAL under the name C'ARBOPOL 934'')
---0,19-Fragrance - Triethanolamine - Enough amount of water to make 17 (enough: l) ---100,
Results similar to those in Example 9 and 22 are observed. 1124 Example 1 of manufacturing a sunscreen cream with the following formulation:
0 compound -115g=mineral oil
-21# -Self-emulsifying glyceryl monostearate--7g
- Kujiro 5 ---1.5. V
- Stearic acid --- 21-Glycerol - 2,5 g - Lanolin alcohol containing 5 moles of ethylene oxide --- 1 g - Methyl parahydroxybenzoate -- o, i g - Progyl parahydroxybenzoate - 0.19 -Perfume water (ten books) ---100
,! Results similar to those in Example 9 and 22 are observed. Example 25 Compound of Example 8 -1-2g-4-(
2-oxo-lunylidene-6-methyl)-phenyltrimethylammoniummethylsulfur-) (UV-Bfi light agent stimulant ---4,
9-Isozolovir myristate ---4,
3,! $-Triethanolamine lauryl sulfate ---o,sg-diethylene glycol monostearate -1-2g-cetyl alcohol ---0,5#-stearic acid -3,5g-fragrance-1-methyl parahydroxybenzoate- 0.15g-triethanolamine-111g-water (100g) ---100g Similar results to Example 22 are observed. Example 26 Example 11 of manufacturing a tanning pill with the following formulation:
Compound -m-8g-2-phenylbenzimidazole-5-sulfonic acid sodium salt -116g -Molecular weight 2-6 million acrylic acid polymer (GOODRICHC"HE") from JICAL under the name "CARBOPOL 954" Sales) ---
0,1# monohexane-1.2.6-)liol --14.9-
Sodium hydroxide --- 0.4 g - Perfume and water (sufficient amount) --- 100 g Repeated use of this pill has been shown to keep the skin supple and supple while at the same time providing good sun protection. Il
l Shita. Example 27 Compound of Example 12 for producing a sunscreen lotion with the following formulation -1-roy-mineral oil
---25, SF-ren rubitan monostearate ---1,57 = engineered tyrene oxide 2
Sorbitan monostearard containing 0 mol - 9 g - Zolobylla hydroxybenzoate - 0.1 g - Water (sufficient amount) - 100 g prevent. Example 2 B Use the following combination of sunscreen aerosols! ! ! Compound of Nisho 1110 ---1y-ethyl alcohol -5511-glycerol
-m-6g-castor oil
-11.9-Stearyl alcohol containing 2 moles of ethylene oxide 5 g - Water
---29g-Propellant: Zochlorozofluoromethane (Freon 12)/dichlorotitrafluoroethane (Freon 14) (ratio 40/60) ---8#
I will not accept the same result as the previous example. Example 29 Example 1 of producing a day-care cream with the following formulation:
Compound 1 -112g-Self-emulsifying glycerol stearer) ---5,!
il-cetyl alcohol ---1g-stearic acid-115g-Vaseline oil
---10g-glycerol
---sg-methyl parahydroxybenzoate-1-0,3g-polymer carboxyvinylpoly-r-(C from GOODRICH CHEMICAL
(Sold under the name “ARBOPOL 940”)
---0,4g-triethanolamine ---0,11-water (sufficient amount)
---100g Repeated use of this composition protects the skin from the weather and at the same time keeps it soft and supple. Compound No. 9 -112g-Polyethylene glycol stearer-) (Sold by ATLAS under the name MYRJ 49'') ---0.8g-Self-emulsifying glycerol stearer) ---2g-Cetyl alcohol-0, 5g - sesame oil
---iog-stearic acid
-112g-glycerol---3
g-methyl hydroxybenzoate --0.3.9-
Molecular landscape 2-3 million 0 acrylic acid 1 R - (GOODRICHCHf1JJICA
L. Sold under the name "C" ARBOPOL 934" by the company --0.2g-Triethanolamine 0.29-Fragrance
---0.8g - water (enough amount)
---100# Repeated use of this emulsion keeps the skin soft and supple. Example 31 Example 8 of manufacturing a protective TL cream with the following formulation:
Compound -116g=Magnesium2
Norato --5,2511-Lanolin alcohol --7,50#-Vaseline oil
-22g-Verhydrosqualene-
15,? -Vaseline -1-12
,25,fil? -Methyl rose hydroxybenzoate-
--0.3g-Demineralized water (enough it) --
-100g Similar results to Example 29 are observed. Example 32 Compound of Example 8 for preparing a shampoo with the following formulation --- Sodium salt of sulfated alkanol (01a-Cxa) oxyethylenated with 0,3,9-2,2 moles of ethylene oxide --- -8,0#-Laurinciethanolamide---1,5g-NaCJ
+++! 1.511
- Adjust Jl to 7.6 with Hct 1 water (enough amount) ---100g Apply this shampoo to natural hair to maintain its flexibility and shine. When used on dyed hair, it protects it from harmful substances in the outside air. Example 36 Compound of Example 11 -1,0g-R-CHOH-CH20
-(OH2-CHOH-CO20). -H (in the formula, R represents the r17+ linkage of a Co-C12 alkyl group, n represents an average statistical number of about 6.5 ---1i), Og-hydroxyethyl cellulose CHERCULES From the company” NATF (0801゜2
Sold under the name 50 HHR'') 0.6
g-1・) Adjust 1 to 7 with NεOH (enough ii!: ) ---
Similar results were observed when the 100g sample was dodged. Example 34 Compound 11B manufactured by Linske with the following formulation---0.8J
/-Cetyl-stearyl alcohol, a mixture of cetyl-stearyl alcohol oxyethylated with 1.5 mol of ethylene oxide (HENKlj: 8INNOWAXAO from Company L)
sold under the name) ---3,0#-)I
Mixture of W fatty alcohol and oxyethylated product (sold by C!RODA under the name "POLAWAX GP 200") ---1,5#-Hydroxyethylcellulose (UNION CARBII) l"C'ELL from Company E
Sold under the name O8IZE QP 4400'')
---0,511--1 adjusted to 5 with HCI 1 water (enough) - m-1 river y Apply this composition to clean, damp hair for about 10 minutes and then wash the hair. The hair is soft and the repeated use of this composition protects the hair well from harmful substances in the atmosphere. example! +5 Produce a flow-through type after-shampoo in aerosol form having the following formulation as the active substance; Compound of Example 11 -2,0 #Lauryl alcohol polyoxyethylated with 12 moles of ethylene oxide -0, 5, p-water (
(sufficiently dispersed) ---100&-pif
to 7.2 with HCl. Koten as a Taibushi aerosol was prepared by dichlorodifluoromethane (Freon 12) and dichlorotetrafluoroethane (
A propellant consisting of a 50150 i compound with Freon 114) was used in a proportion of 90% by weight of active substance and 10% by weight rIk of propellant. Similar results are observed when the previous example is busy. -685-

Claims (1)

[Claims] (IJ molecule i11 is about 500 to 50,000
%, and the following general formula %) [In this formula, Y must be the pattern of the molecule that absorbs 21% outside the system, Pl and P2&, which are not acylated and desired. 4>tl:
IJ' IJil 'E 7L! 'J- is a bracket of the protein γJ'5 that has not been chemically denatured by the editor, M+ is H+, alkali metal kama fc is the cation extracted from magnesium, or N+ ( R2)
, (wherein hliR2 may be the same or different and represents a hydroxyalkyl or alkyl mother-in-law that does not contain a xylem atom or 4 or more atom(s)), and Q represents a protein. 〈jIj〉 represents an alkyl, an aralkyl, or an aralkyl amino acid, or represents 0 or NH, or represents S when the protein contains cysteine, and 2 represents a group 8o3. A+ (in the formula - the ionic needle is the same young as in 1j11, south of the embryo), and Kema 5R3 (in the formula, R3 is an integer from O to 5'1, R4j; L
Hydrogen atoms also ◆'', 4(lI′11 or less carbon 1Il(
6R6 6 (in the formula, Df + all f'rl) is a straight or branched alkylene group with 2 to 10 carbon atoms, and a cation bend As above, the group R6 is a hydroxyalkyl or alkyl group which may be the same, different or different, and which contains a hydrogen atom or up to 4 atoms; It represents a smell and is a halogen ion, but RGOO-1Rso3-114 is an RS
O4, where R represents 1-1c carbon atoms or a hydrogen dihydride group), or represents a salt of protein value (h) Derived from amino I'f'/, iJ
The same droplet as in the above, the flavor R3 represents the amine group that is missing from mono 14 and e, and q IrJ, 11≦number from 1 to 5, but t/
When representing Koshi 2 or Tsumugi s oae M or ij, SR3, q must be equal to 1, and the kumbaku substance uses cystine, and ) 1゛ i position AiL protein * 4 m body no 1 -7021
< fik percent;
7tj percent] corresponds to 'fc Ili < h. (2) Manufactured M1j, (Protein 11) whose raw protein is protein 1J derived from an animal-derived substance selected from the group consisting of keratin, gelatin, ovalbumin, blood albumin, casein and lactalbumin. 1) The protein group described in 5. (3) The protein as a manufacturing raw material is selected from the phase consisting of soybean, peanut and Aju fruit.
,! l (1iiJ, which is a kumbaku substance derived from 〃l)
m (1) 11 Kageki's protein jkl ii+'r
J: J9 bodies. (4) To hydrolysis 1/1 bale is further chemically denatured/Baku Et hydrolysis 1! / Before weaving from one item ηノ(υ−(3
The protein T'iL) which is described in the 9 bodies. (5) The group Y is not substituted with the following: 1; i.e. 11 or 11. lower alkoxy group of 1 or more, (cinnamoyl) 1 (, baradialkylaminobenzoyl), zarythyloyl group, Mj: an alkyl group, a lower alkoxy group, or a sulfo group, or an alkenyl group containing one or more alkoxycarbonyl groups, and (or) Acyl A derived from [1] to carbon 6 or sulfonic acid from benzyritine-camphor, which is replaced by 11 by sulfo group in carbon + K IQ.
I4 i Tattyosulfonyl group, unsubstituted or ICt twisted sulfonyl derived from isonthalidene-camphor M or terephthalipone camphor group) 1(,2-arylbenzoxazole, 2- Arylbenzofuran, 2-arylbenzoxazole,
2-arylbenzotriazole and 2-arylindole are combined into I.j4; carbonyl or sulfonyl groups derived from a set of absorption 111; S-'J absorption in hydroxybenzophenones? tl
The acyl bracket derived from the carbonyl group or sulfone 1t, which tends to be more likely to be an acyl group or a sulfonyl group, is unsubstituted or 111.・t&f(Q, d et al. 11; 3
The acyl Tsumugi that is asked, monophenyl cyano acrylic or diphenyl dino acrylic (1), which is not converted to t + 7 or is 4 converted in the aromatic nucleus, is an acyl that can be converted to bIJ. groups, and Ii'j, depending on whether they are free or one or more hydroxyl, lower alkoxy or alkyl groups,
The famous dibenzoylmethane hlt n's W-n.
1mataha; From j, l nou! ) 77111 people or sulfonyl group, which is 2, from 1! Pruning to Rurui 11/15 +1) -(4
) +ljQ protein t'l-'&,j
H body. (6) The group Y- is the following group, i.e., (R= H, OH3,01'!t'', 0OH3)OH
3 to 41]. (7) The molecular weight is 5. Lloo or 30.0
00. The protein-targeted Wb protein according to any one of (1) to (6) above. (8) 1ift Kyu & Z “R3 Tetsui Was L-*t
-L Rs t-L Corresponds to either formula (01 or GV) and is R4 company water purple atom and is equal to ship p&yuO 11
1j Sot (t) - (7) The protein trader 5 exclusive substance according to any one of (7). (9) First, if necessary, add the raw protein so that the molecules of the raw protein are about 500 to 5 (1,000). The following formula (this formula is "7'X'tJ)\represents the logon atom, Y
is the group of molecules that absorb
4! One or more compounds are either unhydrolyzed or stopped, hydrolyzed proteins (!'s amine J
By making ar, a remainder or part of an alcohol group or a Bumer group anti-unilateral, a group that absorbs ultraviolet light can be created on a protein molecule that has not been hydrolyzed or has been hydrolyzed. , Thirdly, if necessary, ultraviolet absorption
After the chemical crafting of l;
When the amine J1ζ is represented by t, the following formula [where xl represents a halogen atom, pr, t
: An integer from o to 5, R4 is a hydrogen atom or an alkyl group containing 4111'11 or less carbon atoms, and R is R 6 R6 (wherein D is 2 to i o lRx in total). Direct or branched j (alkylene group, gift ion P is H +, alkali metal 1
↓The positive ion derived from magnesium is also N (R2), (in the formula n2tri may be the same or y1 may be the same, hydrogen atom or Fl
Hydroxyalkyl or alkyl having up to 4 carbon atoms. represents a hydrogen atom or a tri,
4111'i or less carbon atoms are hydroxyalkyl or alkyl, l, Ii, p&-L, or R (100-1R8O3- or R
8O,-, where 1 (←1.1-10 fllA
n71J represents a water atom or an alkyl plant that has seven carbon atoms of 4111n or less, and 1
11 and li+i, by an alkylating agent corresponding to 411 in one of the (1, 41 pots), the N-alkylated anti-1 center is TIl, and in 2154, if necessary, When used as a protein containing cystine, all or part of the disulfide of the cystine group of the protein treated with NilJ is mononucleated to become a saturated -803H group, After this oxidation;) 11th rilz
If the -8o3H group is used as its salt, tdaPi &) +
The disulfide of the cystine group of protein 1J was completely processed! I sent all of L to V and part of it so that it would become Chimeru 1i-814, and what about this part? &
'li! Formula I (Ilaλ(lla), (lVa)
and S-alkylation' by an algylating agent with one to one center of (lV'a)! % [Based on this formula, Y is 1''1), Pl and P2&Y are unacylated and nuclear t
l 1-j fall ibukoha lr:j hello 1
q target g f', 4: Unknown kumbak 111
541. At the base of the body, Q is protein! (111)
When α-amino alkyl, aryl, l, or aralkyl (A) or e (NH) or the protein contains cysteine, it represents S, and 2 represents S. 171 (803M (formula c1 month field ion M+ has the same meaning as above), and t, I 5R3 (in the formula RI 4 or -(OHg) pO to 0 to R5 (Iv) (in the formula, T'%R4fu・yohiR5 is oiJ's 7 is 11
1 Kuzu ni Komyo・Suru) represents the basic amino acids of proteins, and is the same as IN-ki.
1, the amino group which has been mono-11° I-screwed or di-IR replaced by 114m, which removes the younger sister, and q is from 1 to 5.
is an integer up to, but 2 is ih 5o3e cape t
it: rz When expressing SR3, t, i, q t must not be equal to 1, and protein T', cystine 1 is included, j4I, position A [protein ¥11. dis 1-7
(Represents HkJ 1%, represents 1 unit BL protein value - 5 yuzu body 0-15Ji - mouse percent) Method for producing chemically injected protein protein body expressed as: (10) For stool use S-Alkylating agent Also, 4N-alkylation has 1j quadratic formula (in this formula, 1x and plane are 0+J 3J+ (9 beds are set and 1 is 1 Bo +114, ?1.-7'3i) for 1 core. JLI (method described in 9J). (11) 1% conversion to +t; tk
9). (12) The group Y is the next hL"j-, i.e., t(ff), where tfc is a cinnamoylno, which is replaced by i+C5j↓ by a lower alkoxy group of 111 or more directions, and a baradialkylaminobenzoyl group, Trityroyl group, 11"j (by one or more alkyl group, lower alkoxy group or sulfo group in the middle or lower position)! fc rJ, one or more alkoxycarbonyl group I
An acyl group derived from the calphone tik or sulfone 1 family, which is replaced by a sulfo group on the I+' child,
it, sulfonyl group, 1α unspecified or modified sulfonyl derived from isophthalyritene-camphor or terephthalylidene-camphor, su, 2-arylbenzimidazole, 2-arylbenzofuran, 2-aryl Acid group derived from carboxylic acid or sulfonic acid derived from a complex absorbent belonging to 1#IX consisting of penzokituzole, 2-rubenzotrianol and 2-7 arylindole In addition, a sulfonyl extract, an absorbent belonging to hydroxybenzophenone 4i1, etc.
Carfone or rosulpon is used as an acyl group or sulfonyl group, which is unsubstituted or substituted with one or more lower alkyl or alkoxy groups, calphothysylmarine hlf The acyl group that is extracted from the absorbent of the structure, ir, i is not converted or 'y/l in the nucleus.
monophenyldi7noacrylic or diphenylcyanoacrylic + 111D, which is surrounded by t', has an acyl group that is luxo, and 1i', c , ((JV A)< lj twisted by either an alkoxy group or an alkyl group, the acyldyl 19 that is extracted from the 117 ilJ of dibenzoylmethane Kl 'IM is sulfonylno, 11, jj to J8+ consisting of sulfonylno, 11, ', E++I term (9) - (1
The method described in any one of 1). (13) The previous clause (9) -(12
). (14) In the presence of a phase that cosmetically obtains N'l->iL, the general formula of effective h(% formula % [in this formula fL, Y is the molecular stripe that makes Shiyu 1 fence tl'z + and P and P26 are groups of the protein 'l'/tvs Nj that have not been chemically modified by acylated nucleophilic addition or 1ejl!/!,
M+t, tH+, alkali gold kJ'h or magnesium to J, "■ metal ion or N" (R2)
4 (in the formula, J+l; R2 may be positive or negative and represents a hydrogen atom or a hydroxyalkyl or alkyl group having a carbon dot of 41bi+ or less)
41 of Q4i protein 44 (i)
+u, O-E or NH is not expressed, and when a protein converter refers to cysteine, it represents S, and 2 represents the group So-M+ (in the formula, the anion M+ represents the same frazzle as above), or 8R3 (13ii4 (in the formula, 1p is M&/ from 0 to 5'1 υ, R
4 is a hydrogen atom or an alkyl group having up to 4 carbon atoms, R5li 6 6 (wherein D is 2 to 10 in total (1/d carbon atoms) , it is a branched alkylene group, and the falling ionic plane is similar to that in the book 1-1. Hydrogen atom or cane 4 (II + A or less carbon h (represents hydroxyalkyl or alkyl side with eno child, sum is halokene ion or 1000-1
1111 (represents a group of a hydrocarbon wheel with a child -J')) or the protein value of Same as Fu!, monoIfj is replaced by the group R3 that gives a taste, and t
Yoji b't 111! represents the amine ^(,
q is an integer from 1 to 5, provided that 2 is 5t
When expressing 13e or SR3, q becomes 1] and the protein value includes cystine, and the unit A is the protein value A2R1 body 1-701411+i
%, and J1L position B is the protein lIi "3 cryogenic body 0-1513
The treatment of the skin and its transformation into the body surface using ultraviolet light (representing the percentage of tE), which is characterized by the presence of 15 proteins expressed in 44 brown bodies. Group h'i, thing. In addition, P and P2 are 1-acylated, and chemically denatured by nucleophilic addition or 1U conversion, the protein value is exclusive to hD, M0 is H+, and alkali metal. kJ5
or cations derived from magnesium or N
+(R2)4 (wherein the groups R8 may be the same or different and represent a hydrogen atom or a hydroxyalkyl or alkyl box containing up to 4 nitrogen atoms), Q is based on whether the alkyl in kin amino r1 of the protein value is 7 reel or aralkyl, T! ;l O
Or it represents kJH, or if the protein let contains cysteine, it represents rock + J, S, and Zr, L no.l; SO2-M (14-4 (off M''
tj, +jiJ Same as W, ta, taste IJ)
, or 5R3 (in the formula, R3 is 4 (in the formula, p is an integer from 0 to 5, p1R4 is a hydrogen atom or 4 (if is an alkyl group having a child), R5 is 6R6 and ij N B B02o'5) yfkJ6 (In the formula, D is a total of 2 to 10 (14 carbon groups (direct 81 or branched alkylene groups with no children), and the same village as JBBnrs. Fu!, for a taste, even if the group R6 is the same) tN!, it represents a hydroxyalkyl or alkyl group that cures the carbon N child of hydrogen K (child or L4 or more) , ρ is a halogen ion or ROOO-1R803t or Rso4
-, where Rr, J, represents a hydrocarbon containing 1-10 carbon atoms) or t- represents a salt of protein phthalate, J, a heavy amino acid Originated from the above and 1
It represents an amino crystal which is di-substituted by R3 to the mole L4 gap and e, which does not satisfy the meaning 11k, and has a ring number from 1 to 5, and 2 is a group 5oe.
When expressing =, + total or SR3, ctlt should be equal to 1, and iJ should be equal to 1, and Kumbak ¥ I should represent cystine. Night display λ η 1st place B1-1 Kumbak first small '52b body 0-15 car i
t) ku-cent fully displayed] De! A composition for treating natural or sensitized hair to protect it from photochemical deterioration, characterized by the presence of at least one hair follicle. (16) The protein 7+ i^ of formula (11) is 0.5 to 15'51 (f
jc percentage if, exists+i+j Ji
+The composition according to any one of (14) and (15). (17) The protein 'M lfs body of formula (13) is termed as a combination of water, lower monoalcohols or e', polyols and alcohols that emit heat from the water bath. 16)
Composition of 12 sails. (1B) sV viscosity A'i, softening rjlJ, humectant, excess bh adhesion agent, softening agent, 6. "HAL", surfactant, anti-1&i+ri, anti-foam/i11, oil, wax, x1
1 containing a coloring agent and/or at least one auxiliary agent selected from 1 Composition of lees; Karasai II!
The shape of the number of holes is 1. Milk rfla liquid in jelly form 1
JPN club or fill up on aerosol women's thoughts 1) ij
The silk material according to any one of items (14) and (16) to (18). (20) Nonionic, anionic, cationic or amphoteric world 1
f+i activity Ha11, animal origin, mineral*r tl-1JiIt
Materials 1-1: 1 oil or wax, 1 silicone, 1 ltf alcohol, anionic, cationic 1. 4. A toymenic or amphoteric fat, an emulsifier, a solar irradiation compatible with the compound of formula (1), an organic bath medium,
jV/viscosity ff+], milky white side, defense 11+! + cut, gold#,
li ion sealant (agent, oxidation 1 () J inhibitor, chargeable, Shinju Jousawaya) agent, 7 fat 1 coloring agent, TIHh:41'IIi j
? 'l, ii 4-element agent, 14L Kaiga, oxidizing agent, natural product 'i'l, 1ltl anti-grease agent, anti-grease agent (an
(ti-grease) agent, anti-fogging agent and c)restruaturing aF!, 5nt) i
rh et u4 LrJ. +itJ term (15
)-(17) A composition for treating hair, protecting it from ultraviolet rays, and treating the hair as described in item 4< above. (21) Before or after shampooing,
Also &, 1 Mosen's dull color and 1c, ff1l white before and after perm, DiI or lotion that is washed off after, celery or tri emulsion, Squillin lotion or Tyu treatment lotion. , broad line lotion or setting lotion, hair lacquer or hair perming, dyeing or camphor 1 composition or t+j+ノ枳(15)-(
17) and (20) i1t'ii x
Jt composition. (22) Shampoo is aI17W, and the compound represented by the formula (!) is anion, cation, or both of the compound represented by the formula (!). i sex i1j 2 50Jliiχ
The composition according to item lliJ (21), which does not contain percent. (23) Zan'B,l jl"2 (lsave-on)
o −shoy 'l ``rj'1t h and formula (1
) of the compound represented by 0.1-1 anionic, nonionic, ionic or amphoteric polymer.
0 nails jJ (perceyt, &11 tyo 0.1--3
M< J+t before containing percent JJ'K 21
) is written in set 1 of l1tQ. (24) Make a GIrl wash-type lotion and use an aqueous solution or alcohol'f? Addition of alcoholic bath containing at least one compound of formula (1) and, if necessary, 0.1 to 10 percent nonionic or cationic surfactant. Previous section to J (21
) The group listed in )! Boruto. (25) Washing-type nonionic emulsion (-°·i) and oil and (1) fatty alcohol-containing, borimexyethylated 11tT alcohol and water? (Currently,
The composition according to item 011 (21), which contains at least one compound represented by the formula. (26) Sentoshifuri's anionic Kudaku reason is 7) J'y
+, , and the set 1 according to item J (21) containing at least one of the compounds represented by the formula and phosphorous
戊11Δ0(27) jelly bI71 and at least one compound represented by formula (13 and 0.5-3
Item 131 containing 0 AILk percent thickener (
21) The construction site and item 〇