CN104151593B - Surface treatment starch or surface-treated fiber element, cosmetics and surface treatment starch or the manufacturing method of surface-treated fiber element - Google Patents
Surface treatment starch or surface-treated fiber element, cosmetics and surface treatment starch or the manufacturing method of surface-treated fiber element Download PDFInfo
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- CN104151593B CN104151593B CN201410198040.1A CN201410198040A CN104151593B CN 104151593 B CN104151593 B CN 104151593B CN 201410198040 A CN201410198040 A CN 201410198040A CN 104151593 B CN104151593 B CN 104151593B
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Abstract
The present invention provides a kind of for the preferred various surface treatment starch of good performance of the cosmetics such as moist feeling, smear or surface-treated fiber element.The present invention provides a kind of surface treatment starch or surface-treated fiber is plain, shown in the surface such as following chemical formula (1) or (2) of starch or cellulose granules.
Description
Technical field
The present invention relates to surface treatment starch or surface-treated fiber element, cosmetics and surface treatment starch or surface treatments
The manufacturing method of cellulose.
Background technology
Up to now, for the powder used in cosmetics, to improve its characteristic (dispersibility, resistance to optical activity, surface-active
Inhibit the phenomenon that, water proofing property (Dial is aqueous), grease resistance, to adhesion of skin etc.) be surface-treated it is very much.It is being surface-treated
In, there are the processing carried out by physical absorption or the processing carried out using the chemical reaction with surface functional group.As passing through object
The processing that reason absorption carries out, there are the processing of following manner：Pending substance is dissolved in solvent, after mixed powder, distillation
Remove solvent；Or in ethanol dissolve pending substance, after mixed powder, water is added to reduce pending Solubility of Substances
It is precipitated, adsorbs on powder.As the example of chemical reaction, there are the processing of following manner etc.：It it is generation in silicone, fluorine processing etc.
In the inorganic agent of table, there will be Si-H or Si-OR (R：CH3、C2H5) etc. the inorganic agents of reaction sites be dissolved in solvent, mixed powder
Body is heated after solvent is distilled off, and makes processing agent molecule and powder surface knot by the-OH of powder surface or moisture etc.
It closes.
Above-mentioned processing method is disadvantageous in that, although it is contemplated that the powder characteristics of surface treatment selects most suitable side
Method, but the processing powder that can be satisfied with may not be able to be obtained by above-mentioned surface treatment.The powder modified by physical absorption
Body effect in the good solvent of the substance of surface treatment is poor；It, must in the case where being surface modified by chemical reaction
There must be reaction site, in addition in order to be reacted at high temperature (150 DEG C or so), it is also necessary to high temperature resistant.
In recent years, cosmetics gradually require the property of organic matter, and powder is also required as organic matter.Come as organic matter
The powder in source has various amylum grains, cellulose powder etc., patent document 1 (special table level 9-501942), patent document 2
The cosmetics that will contain ocentyl succinic cornstarch aluminium are reported in (special open 2005-170864) to improve as sense of touch
Agent uses.
Patent document
Patent document 1：Special table level 9-501942 bulletins
Patent document 2：Special open 2005-170864 bulletins
Invention content
The surface treatment of above-mentioned powder is had been carried out adequately studying however, can't say, due to moistening from shortcoming
Sense, the reasons such as smear (び) is insufficient, limit use.
Therefore, it is good for the preferred various characteristics of the cosmetics such as moist feeling, smear the subject of the invention is to provide one kind
Good surface treatment starch or surface-treated fiber element.
It is that surface treatment starch or surface-treated fiber are plain in the first aspect of the present invention to solve the above subject, starch
Or shown in the surface of cellulose granules such as following chemical formula (1) or (2).
(for chemical formula (1) or (2), the glucose backbone in repetitive unit shown in box W represents to form sediment in formula (1)
Powder skeleton represents cellulose skeleton in formula (2), and X is for hydrogen atom or as shown in following chemical formula (3), (4) or (5).)
(for chemical formula (3), (4) and (5), V following chemical formula (6) institutes as derived from having the binary acid there are two carboxyl
Show, a carboxylic acid of aforementioned binary acid and the hydroxyl of starch and/or cellulose form ester bond, another carboxylic acid be expressed as carboxylic acid from
Son, M represent one or more kinds of 2-4 valency polyvalent metal ions, and V and M form ionic bond, and Z is represented selected from carbon atom number 6-
22 aliphatic acid, amino acid, the amino acid combined with the aliphatic acid of carbon atom number 6-22, water-soluble acidic polysaccharose, water solubility
Acid synthesis macromolecule, one or more of water-soluble acid ultra-violet absorber compound ions, Z had
Some Carboxylic Acid Ions, sulfate ion and/or phosphate ion and M form ionic bond.)
- CORCOO- (6)
(for chemical formula (6), R represents alkyl, alkenyl or the alkynes optionally with substituent group that carbon atom number is more than 1
Base.)
The present invention surface treatment starch or surface-treated fiber element a kind of embodiment in, for chemical formula (3),
(4) and (5), polyvalent metal ion M be selected from calcium ion, magnesium ion, zinc ion, aluminium ion, copper ion, zirconium ion, iron ion,
One or more of barium ions, tin ion, titanium ion.
In the surface treatment starch of the present invention or the another embodiment of surface-treated fiber element, chemical formula (6) institute
Show, tool is selected from succinic acid, malonic acid, maleic acid, itaconic acid, O-phthalic there are two the derivative of the binary acid of carboxyl
Acid, adipic acid, hexenyl succinic acid, hexyl succinic acid, iso-octyl succinic acid, ocentyl succinic, octyl group succinic acid, decyl amber
Amber acid, decenyl succinic acid, dodecenyl-succinic acid, dodecyl succinate, myristyl succinic acid, tetradecene base amber
Acid, cetyl succinic acid, hexadecylene base succinic acid, octadecylsuccinic acid, octadecenyl succinic acid, iso-octadecyl succinic
One or more of group that acid, 2- (1- octyl group -2- decene base) succinic acid are formed.
In the surface treatment starch of the present invention or the another embodiment of surface-treated fiber element, for chemical formula
(3), (4) and (5), the aliphatic acid of the carbon atom number 6-22 of Z be selected from caproic acid, enanthic acid, new enanthic acid, octanoic acid, 2 ethyl hexanoic acid,
N-nonanoic acid, isononanoic acid, capric acid, decylenic acid, lauric acid, lauroleic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid,
Different palmitic acid, palmitoleic acid, Heptadecanoic acide, stearic acid, isostearic acid, oleic acid, linoleic acid, leukotrienes, hydroxy stearic acid, peanut
The one or more that acid, arachidonic acid, behenic acid, lignoceric acid and sinapic acid are selected.
In the surface treatment starch of the present invention or the another embodiment of surface-treated fiber element, for chemical formula
(3), (4) and (5), the amino acid of Z, the amino acid combined with the aliphatic acid of carbon atom number 6-22 be selected from alanine, arginine,
Asparagine, aspartic acid, cysteine, glutamine, glutamic acid, theanine, glycine, histidine, isoleucine, bright ammonia
Acid, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, γ-ammonia
Base-butyric acid, N- coco-nut oil fatty acids acyl group-Pidolidone, N- lauroyls-Pidolidone, N- myristoyl-L- paddy ammonia
Acid, N- acyl groups-Pidolidone, N- stearyls-Pidolidone, N- coco-nut oil fatty acids acylglycine, 2-pyrrolidone-5-carboxylic acid
One or more.
In the surface treatment starch of the present invention or the another embodiment of surface-treated fiber element, for chemical formula
(3), (4) and (5), the water-soluble acidic polysaccharose of Z is alginic acid, carragheen, pectin, xanthans, gellan gum；Aqueous acidic closes
It is to be selected from one or more of following (A) and (B) into macromolecule：
(A) gathered selected from one or more of acrylic acid, methacrylic acid, acryloyl dimethyl tauric acid
Close obtained high-molecular compound；Or
(B) selected from one or more of acrylic acid, methacrylic acid, acryloyl dimethyl tauric acid with selected from
What one or more of alkyl acrylate, alkyl methacrylate, vinyl pyrrolidone were polymerize
High-molecular compound.
In the surface treatment starch of the present invention or the another embodiment of surface-treated fiber element, for chemical formula
(3), (4) and (5), the water-soluble ultra-violet absorber of Z is one kind in benzimidazole sulfonic acid, p-methoxycinnamic acid
More than.
In the surface treatment starch of the present invention or the another embodiment of surface-treated fiber element, surface treatment starch
Or surface-treated fiber element is not gelatinized, and keeps shape of particle.
Another aspect of the present invention is contain the cosmetics of the surface treatment starch of the present invention or surface-treated fiber element.
Another aspect of the present invention is the surface treatment starch of the present invention or the manufacturing methods of surface-treated fiber element, should
Method includes the following steps：
The first step, by starch and/or cellulose powder with as derived from having the binary acid there are two carboxyl dibasic acid anhydride into
Row coagulation, in powder surface formation-COO alkali metal salts；And
Second step as two stage treatment, makes the soluble polyvalent metal salt with 2-4 valence metal ions, alkali metal chemical combination
Object is reacted by polyvalent metal and the powder after coagulation, and the alkali metal compound is selected from carbon atom number 6-
22 aliphatic acid, amino acid, the amino acid combined with the aliphatic acid of carbon atom number 6-22, water-soluble acidic polysaccharose, water solubility
Acid synthesis macromolecule, one or more of water-soluble acid ultra-violet absorber alkali metal compound.
Pass through the present invention, it is possible to provide a kind of for the preferred various tables of good performance of the cosmetics such as moist feeling, smear
Surface treatment starch or surface-treated fiber element
Description of the drawings
Fig. 1：Reaction equation when in manufacturing process by two stage treatment generation octenyl succinic acid starch aluminium myristate.
Fig. 2：The transmitted spectrum of embodiment 7 and comparative example 1.
Specific embodiment
(surface treatment starch or the manufacturing method of surface-treated fiber element)
The manufacturing method of surface treatment starch in embodiment of the present invention or surface-treated fiber element is illustrated.
The manufacturing method of surface treatment starch or surface-treated fiber element in embodiments of the present invention includes：The first step, by starch
And/or cellulose powder carries out coagulation with the dibasic acid anhydride as derived from having the binary acid there are two carboxyl, in powder surface
Formation-COO alkali metal salts；And second step, as two stage treatment, make the water-soluble polyvalent metal with 2-4 valence metal ions
Salt, alkali metal compound are reacted by polyvalent metal and the powder after coagulation, and the alkali metal compound is
Aliphatic acid, amino acid selected from carbon atom number 6-22, the amino acid combined with the aliphatic acid of carbon atom number 6-22, water-soluble acid
Property polysaccharide, water-soluble acid synthesis macromolecule, one or more of water-soluble acid ultra-violet absorber alkali
Metallic compound.
As specific example, surface treatment starch or surface-treated fiber element in embodiment of the present invention can pass through progress
Each step of following (A)-(G) obtains.
(A) coagulation：The powder of starch or cellulose is dispersed in water and/or organic solvent, under alkaline condition,
Dibasic acid anhydride, which is added dropwise, makes its reaction, makes powder surface formation-COO alkali metal salts.
(B) it washs：The methods of powder after coagulation adds in cleaning solvent, passes through stirring is washed.
(C) cleaning solvent is removed：What the methods of by being filtered under diminished pressure, generated after being reacted by remaining dibasic acid anhydride and with water
Binary acid and alkali remove.
(D) two stage treatment：The powder after coagulation is made to disperse in water and/or organic solvent, adds in soluble polyvalent
Metal salt and water-soluble alkali compound make its reaction, make water-soluble chemical combination at the-COO of powder surface by polyvalent metal
Object reacts.
(E) it washs：The methods of powder after two stage treatment adds in cleaning solvent, passes through stirring is washed.
(F) cleaning solvent is removed：The methods of by being filtered under diminished pressure, is by remaining water soluble compound and/or soluble polyvalent
Metal salt removes.
(G) it is dry：By drying and removing cleaning solvent.
In above-mentioned (A), as amylum grain, corn, wheat, potato, mung bean, red bean, rice, acorn nut, cassava (タ can be enumerated
ピ オ カ), three-coloured amaranth, taro, the sources such as sweet potato (サ Star マ イ モ) amylum grain.As cellulose powder, conduct can be enumerated
The cellulose powder in the sources such as timber, cotton, bamboo, the fiber crops of plant fiber.
If starch, grain size is usually 2-80 μm or so；If cellulose, grain size is, for example, 5-200 μm or so,
Can be 40-500nm or so.If starch, shape of particle has the distinctive shape of native starch, can also be used in addition it is spherical,
Polygonal, flat etc..
In addition, if keep shape of particle and remain surface hydroxyl, it is possible to use producing starch.
By selecting grain size and shape of particle respectively, surface treatment starch, sense of touch of surface-treated fiber element etc. can be changed.
In order to show specific example, can enumerate solar eclipse cornstarch, solar eclipse waxy starch, solar eclipse high amylose starches (more than
Manufactured by Japan Food Chemical Co., Ltd), cornstarch Y (Sanwa Cornstarch Co., Ltd.'s manufacture), in potato starch
(な か ゃ り) (starch plants manufacture in oblique in raised path between farm fields agricultural synergistic combination in tiltedly), wheaten starch HS-325 (Chiba powder in tiltedly
Co., Ltd. manufactures), loose paddy campanulaceae (I I ょ う) (SongGu Chemical Industrial Co., Ltd's manufacture), sweet potato starch (National Agricultural association
Can be manufactured with combinatorial association), body な づ I (Nihon Starch Co., Ltd.'s manufacture), green starch (loose paddy chemical industry strain
Formula commercial firm manufactures), CELLULOBEADS serial (Daito Kasei Kogyo Co., Ltd's manufacture), cellulose fine particle (Asahi Chemical Industry せ
ん い Co. Ltd. systems), flaxen fiber element powder (manufacture of い ず body dyers Co., Ltd.), KC Off ロ ッ Network series (Japan Paper ケ ミ
カ Le Co., Ltd. manufactures) etc..
In above-mentioned (A), as dibasic acid anhydride, can enumerate succinic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride,
Adipic anhydride, hexenyl succinic acid acid anhydride, hexyl succinic anhydride, iso-octyl succinic anhydride, octenyl succinic acid anhydride, octyl group succinic acid
Acid anhydride, decyl succinic anhydride, decenyl succinic acid anhydride, dodecenylsuccinic anhydride, dodecyl succinic anhydride, myristyl amber
Acid anhydrides, tetradecene base succinic anhydride, cetyl succinic anhydride, hexadecylene base succinic anhydride, octadecylsuccinic acid acid anhydride, 18
The dibasic acid anhydrides such as alkenyl succinic anhydride, iso-octadecyl succinic acid anhydrides, 2- (1- octyl group -2- decene base) succinic anhydride.The present invention
Manufacturing step in the hydrolysis competitive reaction that occurs for powder surface and water of reaction, the few anhydride reaction of carbon atom number is violent,
The reactivity of acid anhydrides and powder surface more than carbon atom number reduces.In Cosmetic Market, it is used for using octenyl succinic
The powder that acid anhydrides is surface-treated.Ocentyl succinic cornstarch sodium commercially available product, it is possible to use the commercially available production
The surface-treated powder of the present invention is made in product.
In above-mentioned (A), as long as dibasic acid anhydride open loop can be made, alkaline condition is not particularly limited.It is advised as being used to form
Determine the basic catalyst of alkaline condition, can be used：The alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide；Carbonic acid
The alkali carbonates such as sodium, potassium carbonate, lithium carbonate；The phosphate such as tertiary sodium phosphate；The alkali metal such as sodium methoxide, sodium ethoxide, potassium methoxide
Alkoxide；Ammonia, methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, propylamine, di-n-propylamine, butylamine, isobutyl amine, sec-butylamine,
Tert-butylamine, amylamine, secondary amylamine, tertiary amylamine, hexylamine etc. have monoalkylamine, dialkylamine or the trialkylamine of alkyl；Three ethyl alcohol
Amine, triisopropanolamine, diethanol amine etc. have single methanol amine, glycol amine or three hydramine of alcohol radical etc..
Process for primary treatment in above-mentioned (A) can be carried out according to usual method.That is, the powder of starch or cellulose is disperseed
In 1-5 times of water or aqueous organic solvent, then, dropwise addition dibasic acid anhydride while pH is kept to make its reaction with alkali.By every 1
The dehydrated glucose (No water グ ル コ ー ス of a monosaccharide unit for forming starch or cellulose) as 1mol, calculate starch or fibre
Tie up the usage amount of element.Relative to every 1mol starch or cellulose, the amount of dibasic acid anhydride is preferably 0.01-1.0mol, further excellent
It is selected as 0.02-0.8mol.If the amount of dibasic acid anhydride is in 0.01mol hereinafter, the effect showed is very weak；Even if addition
More than 1.0mol will not react, and can remain instead.Rise with the concentration of dibasic acid anhydride, degree of substitution increases in logarithmic fashion
It is high.For dibasic acid anhydride is made to react, the pH in reaction is necessary for alkalinity；In addition, the pH in reaction has to be lower than amylum grain
Or the pH of gelatinization and/or dissolving occurs for cellulose granules.In the case of starch is used, pH is preferably remained as 7-9；For using
The situation of cellulose preferably remains pH as 7-11.Reaction temperature is necessary for from room temperature to amylum grain or cellulose granules occur
The temperature of gelatinization and/or dissolving is hereinafter, the higher reaction efficiency of temperature is higher.In the case of amylum grain, with raw materials used
Source and it is different, such as in the case of cornstarch be preferably less than 60 DEG C.
In the case where dibasic acid anhydride is liquid, preferably directly it is added dropwise.In the case where dibasic acid anhydride is solid, can heat
As being added dropwise after liquid or be added dropwise after being dissolved in acetone and other organic solvent.
In addition, also can coagulation be carried out by the method for No. 9-110902 record of Unexamined Patent.That is, by starch or fiber
The powder of element is scattered in 1-5 times of water or water-containing organic solvent, and it is less than 7, preferably 2-3 to adjust pH by acid, adds in binary acid
Acid anhydride is fully stirred.Later, pH can be also maintained at and more than 7 is reacted (preferably for using the situation of starch can will
PH is maintained at 7-9, can pH be maintained at 7-11 in the case of cellulose is used).This method is for chain alkyl, alkenyl
Dibasic acid anhydride as low with water affinity substance it is especially effective.
- COO alkali metal salts in above-mentioned (A) calculate the degree of substitution of starch in the following way.That is, by sample
5g is scattered in 50ml water, adds in few drops of phenolphthalein indicators, adds in 0.1N sodium hydroxides until dispersion liquid is in pale red.Addition
The sodium hydroxide 25ml of 0.5N, room temperature are shaken 30 minutes.After concussion, with 0.2N titration with hydrochloric acid to colourless.For untreated
Starch or cellulose are also similarly operated, and blank value is obtained, is calculated by following formula.
Degree of substitution (%)=(B-M) × 0.2/1000 × (V+M)/sample size (g) × 100
Note, B are the 0.2N hydrochloric acid titrations (ml) of blank, and M is the 0.2N hydrochloric acid titrations (ml) of sample, and V, M are expressed as
The quality of V, M shown in chemical formula (3), (4) and (5).Degree of substitution (DS)=162 × degree of substitution (%)/((V+M) × 100- (V
+ M-1) × degree of substitution (%))
Starch or cellulose can be carried out really with reacting for dibasic acid anhydride by the ester peak of infrared spectroscopy spectrum in above-mentioned (A)
Recognize.
In above-mentioned (B) and (E), as cleaning solvent, the mixed liquor of one or more of following solvents can be used：
Water；The alcohols such as methanol, ethyl alcohol, isopropanol, propyl alcohol；Acetone, methyl ethyl ketone, diethyl ketone ketone.
The usage amount of cleaning solvent is not particularly limited, preferably the powder after coagulation or two stage treatment etc. weight
To 5 times of amount ranges.
In above-mentioned (B) and (E), washing refer to from the powder dispersion after coagulation by remaining dibasic acid anhydride, with
Binary acid and/or binary acid alkali metal salt, alkali for being generated after water reaction etc. are transferred in cleaning solvent and after two stage treatment
Powder dispersion in remaining water soluble compound, soluble polyvalent metal salt etc. are transferred to step in cleaning solvent；
Cleaning solvent is added in into the powder after coagulation or two stage treatment, propeller, blender, mixer etc., which can be used, usually to be made
Stirring operation.
Wash temperature is preferably below room temperature to starch gelatinization temperature.If more than the gelatinization point of starch, starch meeting
It is gelatinized, it is impossible to show the effect of the present invention；If in room temperature hereinafter, from the point of view of extraction efficiency not preferably.
In above-mentioned (C) and (F), remove cleaning solvent can be used decantation, be filtered under diminished pressure, pressure filtration, centrifugal process etc. it is logical
Normal solid-liquid separation means.In being filtered under diminished pressure, it is filtered under diminished pressure, is removed by using funnel, filter paper, filter flask, decompressor
Remove cleaning solvent.It in pressure filtration, can be pressurizeed, removed by using funnel, filter paper, pressue device, non-active gas
Remove cleaning solvent.In decantation, the dispersion liquid of the powder after two stage treatment and cleaning solvent can be stood such as 3-5 hours
After left and right, only supernatant (cleaning solvent) is removed.It, can be by the powder after two stage treatment and cleaning solvent in centrifugal process
Dispersion liquid centrifugation only removes supernatant (cleaning solvent) for example after 5000rpm is centrifuged 10 minutes.In filtering is squeezed,
The powder and the dispersion liquid of cleaning solvent that can be packed into filter cloth etc. after two stage treatment by squeezing, only remove cleaning solvent.
In above-mentioned (D), workable soluble polyvalent metal salt is calcium, magnesium, zinc, aluminium, copper, zirconium, iron, barium, tin, titanium etc.
Chloride, sulfate.For example, calcium chloride, magnesium chloride, zinc chloride, aluminium chloride, calcium sulfate etc. can be enumerated.
In above-mentioned (D), as water-soluble alkali compound, as long as water-soluble be then not particularly limited, example can be enumerated
The alkali metal salt of substance as shown in following (1)-(6)；
(1) aliphatic acid of carbon atom number 6-22：Caproic acid, enanthic acid, new enanthic acid, octanoic acid, 2 ethyl hexanoic acid, n-nonanoic acid, isononanoic acid,
Capric acid, decylenic acid, lauric acid, lauroleic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, different palmitic acid, palm
Oleic acid, Heptadecanoic acide, stearic acid, isostearic acid, oleic acid, linoleic acid, leukotrienes, hydroxy stearic acid, arachidic acid, arachidonic
Acid, behenic acid, lignoceric acid, sinapic acid etc.；
(2) amino acid：Alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, tea
Propylhomoserin, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, Soviet Union
Propylhomoserin, tryptophan, tyrosine, valine, gamma-amino-butyric acid, 2-pyrrolidone-5-carboxylic acid etc.；
(3) amino acid combined with the aliphatic acid of carbon atom number 6-22：Glutamic acid, glycine, alanine, arginine etc. with
The amino acid that the aliphatic acid of carbon atom number 6-22 combines, such as N- coco-nut oil fatty acids acyl group-Pidolidone, N- lauroyls-L-
Glutamic acid, N- myristoyls-Pidolidone, N- acyl groups-Pidolidone, N- stearyls-Pidolidone, N- coconut oil fats
Sour acylglycine etc.；
(4) water-soluble acidic polysaccharose：In molecule have carboxyl or sulfonic water-soluble polysaccharide, as alginic acid, carragheen,
Pectin, xanthans, gellan gum etc.；
(5) water-soluble acid macromolecule：
(a) gathered selected from one or more of acrylic acid, methacrylic acid, acryloyl dimethyl tauric acid
Close obtained high-molecular compound；
(b) selected from one or more of acrylic acid, methacrylic acid, acryloyl dimethyl tauric acid with selected from
What one or more of alkyl acrylate, alkyl methacrylate, vinyl pyrrolidone were polymerize
High-molecular compound；
(6) Water-soluble UV-absorbents：Benzimidazole sulfonate sodium, p-methoxycinnamic acid etc..
Two stage treatment method in above-mentioned (D) is reacted by following step：Powder after coagulation is scattered in
Water or water-containing organic solvent add in water-soluble alkali compound or are dissolved in the water-soluble alkali compound of water etc. in advance,
Soluble polyvalent metal salt is added in, the powder after coagulation and water-soluble alkali compound is made to pass through water-soluble polyvalent metal
The polyvalent metal of salt forms ionic bond.
In above-mentioned (D), relative to the molal quantity of water-soluble alkali compound, the additive amount of soluble polyvalent metal salt is excellent
It is selected as 0.4-10 times mole, further preferably 0.5-8 times mole.Relative to starch or cellulose, water-soluble alkali chemical combination
The additive amount of object is preferably 0.1 mass %-10 mass %, further preferably 1.0 mass %-3.0 mass %.Processing time does not have
There is the range of special limitation, preferably -1 hour 30 minutes.Treatment temperature is necessary for from room temperature to amylum grain or cellulose grain
The temperature of gelatinization and/or dissolving occurs for son hereinafter, the higher reaction efficiency of temperature is higher.In the case of amylum grain, processing temperature
Degree is different according to raw materials used source, such as the situation of cornstarch is preferably less than 60 DEG C.
The common sides such as spray drying, fluidized bed drying, the dry, freeze-drying of the canopy formula universe can be used in drying in above-mentioned (G)
Method.Can drying temperature be determined by the heat resistance of the type of cleaning solvent used, starch used and/or cellulose.
(surface treatment starch or surface-treated fiber element)
The surface treatment starch or surface-treated fiber element of the present invention is to meet the surface treatment starch or table of following conditions
Surface treatment cellulose：Shown in the surface of starch or cellulose granules such as following chemical formula (1) or (2).
Specifically, surface treatment starch of the invention or surface-treated fiber element keep amylum grain and cellulose granules
Shape of particle, X shown in chemical formula (1) or (2) leads on a part of hydroxyl on amylum grain and cellulose granules surface
Ester bond is crossed to be chemically modified.The inside of amylum grain and cellulose granules is not chemically modified completely by X.
The degree of substitution of X is 0.005 to 0.1.Degree of substitution is every 1 glucose (as the monosaccharide for forming starch or cellulose
Unit) substituted hydroxy number average value.For example, degree of substitution 0.01 is expressed as having 1 hydroxyl to be replaced by X in 100 glucose.
If instead of degree not up to 0.05, substitution effect can not be shown；It is more than 0.1 if instead of degree, effect can not be observed with taking
Increase for degree.
(for chemical formula (1) or (2), the glucose in repetitive unit shown in box W represents starch bone in formula (1)
Frame represents cellulose skeleton in formula (2), and X is for hydrogen atom or as shown in following chemical formula (3), (4) or (5).)
(for chemical formula (3), (4) and (5), V is the following chemical formula (6) as derived from having the binary acid there are two carboxyl
Shown, a carboxylic acid and the hydroxyl of starch and/or cellulose of aforementioned binary acid form ester bond, another carboxylic acid is expressed as carboxylic acid
Ion, M represent one or more kinds of 2-4 valency polyvalent metal ions, and V and M form ionic bond, and Z is represented selected from carbon atom number
It is the aliphatic acid of 6-22, amino acid, the amino acid combined with the aliphatic acid of carbon atom number 6-22, water-soluble acidic polysaccharose, water-soluble
Property acid synthesis macromolecule, one or more of water-soluble acid ultra-violet absorber compound ions, Z tools
Some Carboxylic Acid Ions, sulfate ion and/or phosphate ion and M form ionic bond.)
- CORCOO- (6)
(for chemical formula (6), R represent carbon atom number be more than 1, alkyl, alkenyl or alkynes that optionally there is substituent group
Base.)
In addition, in chemical formula (3), the valence state of M is divalent, any one in trivalent, 4 valencys；In chemical formula (4), M's
Valence state is any one in trivalent, 4 valencys.
In chemical formula (3), (4) and (5), polyvalent metal ion M be selected from calcium ion, magnesium ion, zinc ion, aluminium from
One or more of son, copper ion, zirconium ion, iron ion, barium ions, tin ion, titanium ion.
Tool shown in chemical formula (6) is selected from by succinic acid, malonic acid, maleic acid, clothing there are two the binary acid of carboxyl
Health acid, phthalic acid, adipic acid, hexenyl succinic acid, hexyl succinic acid, iso-octyl succinic acid, ocentyl succinic, octyl group
Succinic acid, decyl succinic acid, decenyl succinic acid, dodecenyl-succinic acid, dodecyl succinate, myristyl succinic acid,
Tetradecene base succinic acid, cetyl succinic acid, hexadecylene base succinic acid, octadecylsuccinic acid, octadecenyl succinic are sour, different
One or more of group that octadecylsuccinic acid, 2- (1- octyl group -2- decene base) succinic acid are formed.
In chemical formula (3), (4) and (5), if Z is the aliphatic acid of carbon atom number 6-22, surface of the present invention is used
The usability of cosmetics of processing starch or surface-treated fiber element, moist feeling, smear, prevent obscure, persistence of making up, when
Between stable type become more good.Furthermore, it by the hydrophobicity of the aliphatic acid of carbon atom number 6-22, improves and uses this
Invent the water proofing property and water resistance of the cosmetics of the surface treatment starch or surface-treated fiber element.In chemical formula (3), (4)
And in (5), the aliphatic acid of the carbon atom number 6-22 of Z be selected from caproic acid, enanthic acid, new enanthic acid, octanoic acid, 2 ethyl hexanoic acid, n-nonanoic acid,
Isononanoic acid, capric acid, decylenic acid, lauric acid, lauroleic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, different palm
Acid, palmitoleic acid, Heptadecanoic acide, stearic acid, isostearic acid, oleic acid, linoleic acid, leukotrienes, hydroxy stearic acid, arachidic acid, flower
One or more of raw tetraenoic acid, behenic acid, lignoceric acid and sinapic acid.
In chemical formula (3), (4) and (5), if Z is amino acid, surface treatment starch of the present invention or surface are used
It handles the usability of the cosmetics of cellulose, moist feeling, smear, prevent obscure, makeup persistence, time stable type from becoming more
It is good.Furthermore, it by the water solubility of amino acid, improves using at surface treatment starch of the present invention or surface
Manage oil absorption, emollient and the adhesion to skin of the cosmetics of cellulose.In chemical formula (3), (4) and (5), the ammonia of Z
Base acid is selected from alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, theanine, sweet
Propylhomoserin, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, color
One or more of propylhomoserin, tyrosine, valine, gamma-amino-butyric acid, 2-pyrrolidone-5-carboxylic acid.
In chemical formula (3), (4) and (5), if Z is the amino acid combined with the aliphatic acid of carbon atom number 6-22, use
The usability of the cosmetics of surface treatment starch of the present invention or surface-treated fiber element, smear, prevents secretly moist feeling
Heavy, makeup persistence, time stable type become more good.Furthermore, pass through the aliphatic acid knot with carbon atom number 6-22
The hydrophobicity of the amino acid of conjunction is improved using the cosmetics of surface treatment starch of the present invention or surface-treated fiber element
Water proofing property and water resistance.In chemical formula (3), (4) and (5), the amino acid combined with the aliphatic acid of carbon atom number 6-22 of Z is
The amino acid combined with the aliphatic acid of the carbon atom number 6-22 of the combinations such as glutamic acid, glycine, alanine, arginine, Ke Yishi
Selected from N- coco-nut oil fatty acids acyl group-Pidolidone, N- lauroyls-Pidolidone, N- myristoyls-Pidolidone, N-
One or more of acyl group-Pidolidone, N- stearyls-Pidolidone, N- coco-nut oil fatty acid acylglycines.
In chemical formula (3), (4) and (5), if Z is acidic polysaccharose, using surface treatment starch of the present invention or
The usability of the cosmetics of surface-treated fiber element, smear, prevents obscure, makeup persistence, time stability from becoming at moist feeling
It obtains more good.Furthermore, by the water solubility of acidic polysaccharose, improve using surface treatment starch of the present invention or
Oil absorption, emollient and the adhesion to skin of the cosmetics of surface-treated fiber element.In chemical formula (3), (4) and (5),
The aqueous acidic polysaccharide of Z is alginic acid, carragheen, pectin, xanthans, gellan gum.
In chemical formula (3), (4) and (5), if Z is water-soluble acid macromolecule, surface of the present invention is used
The usability of cosmetics of processing starch or surface-treated fiber element, moist feeling, smear, prevent obscure, persistence of making up, when
Between stability become more good.Furthermore, it by the water-soluble high molecular water solubility of acidity, improves and uses this hair
Oil absorption, emollient and the adhesion to skin of the cosmetics of the bright surface treatment starch or surface-treated fiber element.
In chemical formula (3), (4) and (5), the aqueous acidic macromolecule of Z can be selected from one or both of following (A) and (B) with
On：(A) selected from one or more of acrylic acid, methacrylic acid, acryloyl dimethyl tauric acid polymerize
The high-molecular compound arrived；Or the one kind or two of (B) in acrylic acid, methacrylic acid, acryloyl dimethyl tauric acid
Kind or more with selected from alkyl acrylate, alkyl methacrylate, one or more of vinyl pyrrolidone into
The high-molecular compound that row polymerization obtains.
In chemical formula (3), (4) and (5), if Z is water-soluble acid ultra-violet absorber, institute of the present invention is used
It states the usability of the cosmetics of surface treatment starch or surface-treated fiber element, moist feeling, smear, prevent obscure, makeup from holding
Long property, time stability become more good.Furthermore, it by acid ultra-violet absorber, improves using the present invention
Water proofing property, water resistance and the adhesion to skin of the cosmetics of the surface treatment starch or surface-treated fiber element.Into one
For step, preventing ultraviolet effect is improved by acid ultra-violet absorber.In chemical formula (3), (4) and (5), Z's is water-soluble
Property acid ultra-violet absorber can be selected from one or more of benzimidazole sulfonic acid, p-methoxycinnamic acid.
As the surface treatment starch of the present invention or the typical example of surface-treated fiber element, following surface treatments can be enumerated and formed sediment
Powder or surface-treated fiber element, wherein, the octenyl succinic acid starch myristic acid of surface such as Fig. 1 of starch or cellulose granules
Shown in the glucose backbone of aluminium.In fig. 1 it is shown that ocentyl succinic is generated by the two stage treatment in above-mentioned manufacturing step
Reaction equation during starch aluminium myristate.
The surface treatment starch or surface-treated fiber element of the invention surface treatment outstanding available for function and/or sense of touch
The various uses of powder is suitable as skin care, cosmetic product, hair product, antiperspirant products, antiultraviolet product etc.
Raw material, can be by matching especially as the raw material suitable for whole cosmetics of external application on skin and/or hair with cosmetics
The mode of conjunction provides function and/or the outstanding cosmetics of sense of touch.Although different according to the type of cosmetics and dosage form, with change
In the case that cosmetic coordinates, 0.1-99 weight % can be integrally coordinated relative to cosmetics.
It can be enumerated as cosmetics：Toner, lotion, frost, detergent (Network レ Application ジ Application グ), facial mask (パ ッ Network), oiliness
The skin protection cosmetics such as liquid (オ イ Le リ キ ッ De), massage material, detergent (clean drug), deodorant, hand lotion, lip gloss；Change
The cosmetics such as adornment matrix, powder (white powder), foundation emulsion, oleaginous base, blush, eye shadow, mascara, informer, eyebrow pencil, lipstick are made up
Product；The hair cosmetic compositions such as shampoo, rinse conditioner (リ Application ス), treatment wax (ト リ ー ト メ Application ト), setting agent (セ ッ ト drug)；
Antiultraviolets cosmetics such as antiperspirant, ultra light sun block lotion and suncream etc..In addition, the shape as above-mentioned cosmetics, may be selected liquid
Body shape, emulsion form, white shape, solid-like, paste, gel, powdered, pie (プ レ ス shapes), multilayer shape, mousse, spraying
The various forms such as shape, rodlike, lip pencil.
Embodiment
Next the embodiment of the present invention is provided, the embodiment is for a better understanding of the present invention and its mesh of advantage
And provide, but the present invention is not intended to be limited to these embodiments.In addition, unless limited otherwise, it is otherwise hereinafter recorded
" % " expression " weight % ".
Embodiment 1
The preparation of ocentyl succinic cornstarch aluminium myristate
By the cornstarch of the 100g cornstarch Y of the manufacture of starch Co., Ltd. (three and) (being converted into no water number) (by nothing
Water monosaccharide unit converts into 0.62 mole) add in 200g water in, with blender (ス リ ー ワ ン モ ー タ ー) and propeller stirred
Mixing makes it be uniformly dispersed, while the sodium hydrate aqueous solution for adding in appropriate 1N keeps pH7.9-8.2, and by the octenyl amber of 5.0g
Amber acid anhydrides (the リ カ シ ッ De OSA of New Japan Chem Co., Ltd's manufacture) (being 0.04 times mole relative to starch) was held with 1 hour
Continuous a small amount of addition makes its reaction.Reaction carries out 5 hours (starting to be added dropwise to reaction completion) at 35 DEG C.A part of reactant is taken out,
It is dry after being washed with a small amount, it carries out degree of substitution (DS) and measures.Degree of substitution (DS) measure the result is that degree of substitution (DS) is
0.030.In addition, confirm the ester peak (1740cm in IR analyses-1) after, be transferred to after the step of.Then, it is added in 200g water
Reactant makes it be washed at room temperature with water 10 minutes after disperseing by stirring.The slurry containing reactant is filtered with No.2 again
Paper is filtered under diminished pressure, and obtains reactant.Water washing is further repeated and is filtered under diminished pressure 2 times.It is added in again into 200g water
Reactant after washing is stirred, while is added in dissolved with 1.5g potassium myristates (being 1.5 mass % relative to starch)
Aqueous solution 5g.Potassium myristate dissolves in 40 DEG C or so of warm water in advance.Then, it adds in dissolved with six water of 2.27g aluminium chloride
The aqueous solution 10g of object (being 1.84 times moles relative to potassium myristate) is closed, persistently stirring 30 minutes makes its reaction.Contain reaction
The slurry of object is filtered under diminished pressure with No.2 filter paper, carries out 2 washings with method similar to the above later.After washing, reaction
Object aeration-drying 12 hours at 40 DEG C obtain the ocentyl succinic cornstarch aluminium myristate of 98.5g.
Embodiment 2
The preparation of ocentyl succinic green starch lauroyl glutamate aluminium
Except the cornstarch in embodiment 1 being replaced with green starch, and potassium myristate is replaced with lauroyl paddy
Except propylhomoserin sodium 2.32g (being 2.3 mass % relative to starch), similarly operated, obtain the ocentyl succinic of 92.3g
Green starch lauroyl glutamate aluminium.
Embodiment 3
The preparation of ocentyl succinic flaxen fiber element zinc palmitate
Except the cornstarch in embodiment 1 is replaced with flaxen fiber element powder, with reacting 50 for octenyl succinic acid anhydride
It is carried out 5 hours at DEG C, potassium myristate is replaced with into sodium palmitate 4.00g (being 4.0 mass % relative to cellulose), and by chlorine
Change aluminium to replace with except zinc chloride 4.0g (being 2.04 times moles relative to sodium palmitate), similarly operated, obtain 90.4g
Ocentyl succinic flaxen fiber element zinc palmitate.
Embodiment 4
The preparation of dodecenyl-succinic acid wheaten starch myristoyl glutamic acid aluminium
By 100g wheaten starches (wheaten starch of Chiba Flour Milling Co., Ltd.'s manufacture) (being converted into no water number) (by anhydrous list
Sugar unit converts into 0.62 mole) add in 200g water, with blender (ス リ ー ワ ン モ ー タ ー) and propeller be stirred and make
After it is uniformly dispersed, pH2.0 is adjusted to hydrochloric acid.Add in the dodecenylsuccinic anhydride (New Japan Chem Co., Ltd of 8.0g
The リ カ シ ッ De DDSA of manufacture) and (relative to starch be 0.05 times mole) it is made to be uniformly dispersed.Add in appropriate 1N sodium hydroxides water
While solution maintains pH7.9-8.2, reacted 5 hours at 35 DEG C.Later, except the potassium myristate in embodiment 1 is replaced with
Except myristoyl sodium glutamate 2.36g (being 2.4 mass % relative to starch), similarly operated, obtain 90.2g's
Dodecenyl-succinic acid wheaten starch myristoyl glutamic acid aluminium.
Embodiment 5
The preparation of ocentyl succinic amylomaize aluminum stearate
Except the cornstarch in embodiment 1 being replaced with amylomaize, and potassium myristate is replaced with tristearin
Except sour potassium 1.93g (being 1.9 mass % relative to starch), similarly operated, the ocentyl succinic for obtaining 91.5g is high
Straight chain corn starch aluminum stearate.
Embodiment 6
The preparation of ocentyl succinic cornstarch palmitic acid titanium
Except the octenyl succinic acid anhydride 5g in embodiment 1 is replaced with 100g, 1N sodium hydroxides are replaced with into 1N sodium carbonate,
50 DEG C are replaced with reacting for octenyl succinic acid anhydride, aluminium chloride is replaced with titanium chloride 2.27g (is relative to sodium palmitate
0.41 times mole), and potassium myristate is replaced with except sodium palmitate 10g (being 10 mass % relative to starch), it carries out same
The operation of sample obtains the ocentyl succinic cornstarch palmitic acid titanium of 91.9g.
Embodiment 7
The preparation of ocentyl succinic cornstarch p-methoxycinnamic acid aluminium
Cornstarch into embodiment 1 is in octenyl succinic acid anhydride reactant obtained by the reaction, adding in and being dissolved in hydrogen
P-methoxycinnamic acid 2.0g (being 2.0% relative to starch) in aqueous solution of sodium oxide, then, adds in dissolved with 2.91g chlorine
Changing the aqueous solution of aluminium hexahydrate (being 1.1 times moles relative to p-methoxycinnamic acid) makes its reaction.Reactant water is multiple
It is dry after washing, obtain the ocentyl succinic cornstarch p-methoxycinnamic acid aluminium of 86.4g.
Embodiment 8
The preparation of succinic acid rice starch alginic acid aluminium
Except the cornstarch in embodiment 1 is replaced with rice starch, it is (opposite that ocentyl succinic is replaced with into succinic acid 5g
In starch be 0.08 times mole), and by potassium myristate replace with mosanom 1.84g (relative to starch be 1.8 mass %) it
Outside, it is similarly operated, obtains the succinic acid rice starch alginic acid aluminium of 92.1g.
Comparative example 1
The preparation of ocentyl succinic cornstarch aluminium
The cornstarch of 100g, which is added to the water, makes it be uniformly dispersed, and the sodium hydrate aqueous solution for adding in appropriate 1N is kept
While pH8.0-8.5, continuing to add 20.0g octenyl succinic acid anhydrides on a small quantity makes its reaction.Leaching reactant after the completion of reaction,
It is repeatedly washed with water.Into the reactant, aqueous solution of the addition dissolved with 9.0g aluminum chloride hexahydrates is reacted.It will with water
Reactant is dry after repeatedly washing, and obtains the ocentyl succinic cornstarch aluminium of 98.80g.
Comparative example 2
The preparation of ocentyl succinic green starch aluminium
It in addition to the cornstarch in comparative example 1 is replaced with green starch, is similarly operated, obtains 94.55g's
Ocentyl succinic green starch aluminium.
Comparative example 3
The preparation of ocentyl succinic flaxen fiber element aluminium
It in addition to the cornstarch in comparative example 1 is replaced with flaxen fiber element, is similarly operated, obtains 97.61g's
Ocentyl succinic flaxen fiber element aluminium.
Water Resistance Test
For the water resistance for the powder that above-described embodiment and comparative example obtain, evaluated by the following method.Its result
As shown in table 1.
Evaluation method：Ethyl alcohol is made:Water=2:0.1g powders are lightly floated on the mixing by 8 mixed solution 5ml
On solution.After 1 minute, confirm whether powder infiltrates sedimentation, the degree as water resistance.
Evaluation criterion：Non-settling substance is denoted as "○" after 1 minute, and the substance of sedimentation is denoted as "×".
Confirmed by table 1, either case can be determined in embodiment 1-7 enables water resistance by carrying out two stage treatment
It improves.
【Table 1】
| Powder | Water resistance |
| Embodiment 1 | ○ |
| Embodiment 2 | ○ |
| Embodiment 3 | ○ |
| Embodiment 4 | ○ |
| Embodiment 5 | ○ |
| Embodiment 6 | ○ |
| Embodiment 7 | ○ |
| Comparative example 1 | × |
| Comparative example 2 | × |
| Comparative example 3 | × |
Ultraviolet absorption ability is tested
20wt% is respectively adopted in the powder obtained in embodiment 7 and comparative example 1, three isostearic acids two are added in each sample
The mixture that glyceride 80wt% is mixed at room temperature is clipped in quartz plate, is measured with spectrophotometer, obtains Fig. 2
Transmitted spectrum.Show that ocentyl succinic cornstarch is to first compared with ocentyl succinic cornstarch aluminium by Fig. 2
Transmitted spectrum (%) of the oxygroup cinnamic acid aluminium near 290-350nm is relatively low, thus with ultraviolet absorption ability.Muffin (パ
ウ ダ ー Off ァ ン デ ー シ ョ Application) evaluation
It is manufactured (respectively according to the formula and following manufacturing methods of table 2 using the muffin of gained powder in embodiment 1,2
For embodiment 9,10).In addition, used the muffin of commercially available powder used for cosmetic according to the formula of table 2 and following manufacturing methods into
Row manufacture (being respectively comparative example 4,5).
【Table 2】
Muffin is made by following A-D：
A：Ingredient 4-15 is uniformly mixed；
B：Ingredient 1-3 Hybrid Heatings is uniform；
C：B is added in into A to be uniformly mixed；
D：Muffin is made in C compression moldings.
It for obtained muffin, is carried out by the panel of expert of 50 women using test, for usability good degree, wet
Moisture feeling, smear ease, makeup persistence good degree and obscure elimination situation are (with the shape after coating after 2 hours
State is evaluated), the standard according to table 3 is evaluated.
【Table 3】
The average mark obtained by above-mentioned evaluation, according to following standards with zero × judged.
More than average mark 4.5 divides：◎
More than average mark 3.5 divides, not up to 4.5 points：○
More than average mark 2.5 divides, not up to 3.5 points：△
More than average mark 1.5 divides, not up to 2.5 points：×
Average mark is not up to 1.5 points：××
The results are shown in Table 4 for judgement.
【Table 4】
| Embodiment 9 | Embodiment 10 | Comparative example 4 | Comparative example 5 | |
| Usability good degree | ◎ | ◎ | ○ | △ |
| Moist feeling | ◎ | ◎ | △ | △ |
| Smear ease | ◎ | ◎ | ○ | × |
| Makeup persistence good degree | ◎ | ◎ | ○ | ○ |
| Obscure elimination situation | ◎ | ◎ | ○ | ○ |
By table 4 as it can be seen that compared with comparative example 4,5, the muffin of embodiment 9,10 is that usability is good, easily smears, very
Moistening, sense of touch is outstanding, elimination is obscure, the makeup good muffin of persistence.
The evaluation of oil-in-water type face cream
Using the powder obtained in embodiment 3 and embodiment 8, water packet is manufactured by the formula of table 5 and following manufacturing methods
Oil type frost.
【Table 5】
| Ingredient | It forms (weight %) | |
| 1 | Saualane | 7.0 |
| 2 | SIMMONDSIA CHINENSIS SEED OIL | 3.0 |
| 3 | 3 obtained powder of embodiment | 3.0 |
| 4 | 8 obtained powder of embodiment | 2.0 |
| 5 | Palmitic acid 2- ethylhexyls | 5.0 |
| 6 | Stearic acid | 0.5 |
| 7 | Docosyl alcohol (ベ ヘ ニ Le ア ル コ ー Le) | 2.2 |
| 8 | Tristerin (SE) | 1.1 |
| 9 | The smooth sesquialter isostearate of sorb | 0.5 |
| 10 | Polyglycerol stearate -10 | 1.2 |
| 11 | Dimethicone | 0.1 |
| 12 | Tocopherol | 0.1 |
| 13 | 1,3 butylene glycol | 8.0 |
| 14 | Glycerine | 8.0 |
| 15 | Carbomer (1% aqueous solution) | 16.0 |
| 16 | Xanthans (2% aqueous solution) | 2.0 |
| 17 | Sodium hydroxide (1% aqueous solution) | 9.0 |
| 18 | Preservative | In right amount |
| 19 | Fragrance | In right amount |
| 20 | Purified Water | 31.3 |
Oil-in-water type frost is made by following A-D.
A：Ingredient 1-12 is mixed, is dissolved by heating；
B：Ingredient 13-16,18,20 are mixed, heating；
C：A is added in into stirring and emulsifying in B；
D：Ingredient 17 is added in into C to neutralize, and adds in ingredient 19.
Obtained oil-in-water type frost realizes quality exquisiteness, smears and sprawl light and dry and comfortable (without viscosity and oiliness), this
Outside, makeup persistence is very good while moistening water tender and frank use feeling is given, show not vary with temperature and
Time and change, stability is outstanding.
The evaluation of oil-in-water type UV frosts
Using 7 obtained powder of embodiment, oil-in-water type UV frosts are made by the formula and following manufacturing methods of table 6.
【Table 6】
Oil-in-water type UV frosts are made by following A-F.
A：Ingredient 1-8 is mixed, is dissolved by heating；
B：Ingredient 9 is dispersed in a part for ingredient 18；
C：Ingredient 10-12,18 remainder are mixed, heating；
D：Ingredient 13-17 is mixed；
E：A is added in into stirring and emulsifying in C, cooling；
F：B and D is added in into E.
Obtained oil-in-water type UV face creams realize smearing and sprawl light and dry and comfortable (without viscosity and oiliness), give frankness
Use feeling while, it is strong for the water resistance of sweat and water, makeup persistence it is very good, show not vary with temperature and when
Between and change, stability is outstanding.
Embodiment 11
The preparation of ocentyl succinic cornstarch myristic acid iron
It is (opposite except the aluminum chloride hexahydrate 2.27g in embodiment 1 is replaced with iron chloride (III) hexahydrate 2.54g
In potassium myristate be 1.8 times moles) except, similarly operated, obtain the ocentyl succinic cornstarch meat of 92.5g
Myristic acid iron.
Embodiment 12
The preparation of ocentyl succinic cornstarch magnesium myristate
Except the potassium myristate 1.5g in embodiment 1 is replaced with 4.5g, aluminum chloride hexahydrate 2.27g is replaced with into chlorine
Change except magnesium hexahydrate 6.24g (being 2.0 times moles relative to potassium myristate), similarly operated, obtain 92.4g's
Ocentyl succinic cornstarch magnesium myristate
Embodiment 13
The preparation of ocentyl succinic cornstarch calcium myristate
Except the potassium myristate 1.5g in embodiment 1 is replaced with 3.0g, aluminum chloride hexahydrate 2.27g is replaced with into chlorine
Change except calcium 2.27g (being 2.0 times moles relative to potassium myristate), similarly operated, obtain the octenyl amber of 93.6g
Amber acid cornstarch calcium myristate.
Embodiment 14
The preparation of succinic acid potato starch aluminium myristate
Except the cornstarch in embodiment 1 is replaced with potato starch, octenyl succinic acid anhydride 5.0g is replaced with into amber
Except amber acid anhydrides 2.47g (being 0.04 times mole relative to starch), similarly operated, obtain the succinic acid Ma Ling of 87.5g
Sweet potato starch aluminium myristate.
Embodiment 15
The preparation of ocentyl succinic cornstarch (myristic acid/glutamic acid) aluminium
Except by the octenyl succinic acid anhydride 5.0g in embodiment 1 replace with 25.9g (relative to starch be 0.19 times mole),
Potassium myristate 1.5g is replaced with into potassium myristate 3.5g and sodium glutamate 2.0g (being 5.5 mass % relative to starch), and
Aluminum chloride hexahydrate 2.27g is replaced with except 5.28g (potassium myristate and sodium glutamate amount to 0.75 times mole), into
The same operation of row, obtains ocentyl succinic cornstarch (myristic acid/glutamic acid) aluminium of 105g.
Embodiment 16
The preparation of ocentyl succinic cornstarch (myristic acid/lauroyl glutamate) aluminium
Except the potassium myristate 1.5g in embodiment 1 is replaced with potassium myristate 0.75g and sodium lauroyl glutamate
Except 0.88g (being 1.63 mass % relative to starch), similarly operated, obtain the ocentyl succinic corn of 94.4g
Starch (myristic acid/lauroyl glutamate) aluminium.
Embodiment 17
The preparation of ocentyl succinic sweet potato starch (myristic acid/oleic acid) aluminium
Except the cornstarch in embodiment 1 is replaced with sweet potato starch, octenyl succinic acid anhydride 5.0g is replaced with into 13.0g
(being 0.10 times mole relative to starch), and potassium myristate 1.5g is replaced with into potassium myristate 5g and enuatrol 2g (relatively
In starch be 7.0 mass %) except, similarly operated, obtain the ocentyl succinic sweet potato starch (nutmeg of 92.0g
Acid/oleic acid) aluminium.
Embodiment 18
The preparation of ocentyl succinic wheaten starch (oleic acid/stearyl glutamic acid) aluminium
Except the cornstarch in embodiment 1 being replaced with wheaten starch, and potassium myristate 1.5g is replaced with enuatrol
Except 0.75g and stearyl sodium glutamate 0.75g (being 1.5 mass % relative to starch), similarly operated, obtained
Ocentyl succinic wheaten starch (oleic acid/stearyl glutamic acid) aluminium of 93.1g.
Embodiment 19
The preparation of ocentyl succinic wheaten starch (palmitic acid/palmityl proline) aluminium
Except the cornstarch in embodiment 1 is replaced with wheaten starch, octenyl succinic acid anhydride 5.0g is replaced with into 10.0g
(being 0.08 times mole relative to starch), and potassium myristate 1.5g is replaced with into sodium palmitate 1.5g and palmityl proline
Except sodium 1.5g (being 3.0 mass % relative to starch), similarly operated, obtain the ocentyl succinic wheat of 95.2g
Starch (palmitic acid/palmityl proline) aluminium.
Embodiment 20
The preparation of ocentyl succinic cornstarch (coco-nut oil fatty acid/isostearic acid) aluminium
Except by the octenyl succinic acid anhydride 5.0g in embodiment 1 replace with 2.6g (relative to starch be 0.02 times mole),
And it (is 1.2 matter relative to starch that potassium myristate 1.5g is replaced with coco-nut oil fatty acid potassium 1.0g and isostearic acid potassium 0.2g
Measure %) except, it is similarly operated, obtains the ocentyl succinic cornstarch (coco-nut oil fatty acid/different tristearin of 92.9g
Acid) aluminium.
Embodiment 21
The preparation of succinic acid green starch (glycine/pectin) aluminium
Except the cornstarch in embodiment 1 is replaced with green starch, octenyl succinic acid anhydride 5.0g is replaced with into amber
Acid anhydrides 2.47g (being 0.04 times mole relative to starch), Sodium Glycinate 1.0g and pectin are replaced with by potassium myristate 1.5g
It except 0.5g (relative to 1.5 mass % of starch), is similarly operated, obtains succinic acid green starch (the sweet ammonia of 89.0g
Acid/pectin) aluminium.
Embodiment 22
Ocentyl succinic green starch (myristic acid/(acrylic acid/acryloyl dimethyl tauric acid) copolymer) aluminium
Preparation
Except the cornstarch in embodiment 1 being replaced with green starch, and potassium myristate 1.5g is replaced with nutmeg
Except sour potassium 1.5g and (sodium acrylate/acryloyl dimethyl tauric acid) copolymer 0.5g (relative to 2.0 mass % of starch),
It is similarly operated, obtains the ocentyl succinic green starch (myristic acid/(acrylic acid/acryloyl group diformazan of 96.3g
Base taurine) copolymer) aluminium.
Embodiment 23
The preparation of ocentyl succinic tapioca (isostearic acid/theanine) magnesium
Except the cornstarch in embodiment 1 is replaced with tapioca, octenyl succinic acid anhydride 5.0g is replaced with into 17.0g
(being 0.13 times mole relative to starch), potassium myristate 1.5g replaces with isostearic acid potassium 6.0g and containing theanine 2.0g
The sodium hydrate aqueous solution of (being 8.0 mass % relative to starch), and aluminum chloride hexahydrate 2.27g is replaced with into magnesium chloride six
Except hydrate 10g (1.6 times moles of the total of isostearic acid and theanine), similarly operated, obtain the pungent of 104g
Alkenyl succinic acid tapioca (isostearic acid/theanine) magnesium.
Embodiment 24
The preparation of ocentyl succinic tapioca (myristic acid/p-methoxycinnamic acid) aluminium
Except the cornstarch in embodiment 1 is replaced with tapioca, octenyl succinic acid anhydride 5.0g is replaced with into 17.0g
(being 0.13 times mole relative to starch), and potassium myristate 1.5g is replaced with into potassium myristate 1.0g and containing to methoxyl group
Except the sodium hydrate aqueous solution of cinnamic acid 2.0g (being 3.0 mass % relative to starch), similarly operated, obtained
Ocentyl succinic tapioca (myristic acid/p-methoxycinnamic acid) aluminium of 99.5g.
Water Resistance Test
For the water resistance of powder obtained in above-described embodiment 11-16, evaluated by the following method.Its result is such as
Shown in table 7.
Evaluation method：Ethyl alcohol is made:Water=2:0.1g powders are lightly floated on the mixing by 8 mixed solution 5ml
On solution.After 1 minute, confirm whether powder infiltrates sedimentation, the degree as water resistance.
Evaluation criterion：Non-settling substance is denoted as "○" after 1 minute, and the substance of sedimentation is denoted as "×".
Confirmed by table 7, can be determined in embodiment 11-16 is improved water resistance by carrying out two stage treatment.
【Table 7】
| Powder | Water resistance |
| Embodiment 11 | ○ |
| Embodiment 12 | ○ |
| Embodiment 13 | ○ |
| Embodiment 14 | ○ |
| Embodiment 15 | ○ |
| Embodiment 16 | ○ |
The evaluation of substrate of making up (メ イ Network ア ッ プ ベ ー ス)
Using the powder obtained in embodiment 5,11,15,20,21,22, formula and following manufacturer's legal systems by table 8
The makeup substrate coordinated into embodiment 25,26,27.
【Table 8】
Makeup substrate is manufactured by following A-D：
A：Ingredient 1-5 is mixed, is dissolved by heating；
B：Ingredient 12-16 is mixed, heating；
C：B is added in into stirring and emulsifying in A；
D：Ingredient 6-11 is added in into C.
The makeup substrate obtained in embodiment 25 realizes smearing and sprawls easily, without viscosity and oiliness and with wet
Frank sense after moisture feeling and coating, makeup persistence is very good, do not vary with temperature with the time and change, stability
It is outstanding.
The makeup base obtained in embodiment 26 shows with moist feeling and attaches sense (adhesion sense), and smear is good
Good, without viscosity and oiliness, makeup persistence is very good, do not vary with temperature with the time and change, stability is excellent
It is elegant.
The makeup base obtained in embodiment 27 realizes smearing and sprawls easily, without viscosity and oiliness and with wet
Frank sense after moisture feeling and adhering sense, coating, makeup persistence is very good, do not vary with temperature with the time and become
Change, stability is outstanding.
The evaluation of eye shadow (ア イ カ ラ ー)
Using the powder obtained in embodiment 12, according to the formula of table 9 and following manufacturing methods be made embodiment 28,29,
The eye shadow of 30 cooperations.
【Table 9】
Eye shadow is manufactured by following A-D.
A：Ingredient 1-14 is mixed and is disperseed；
B：Ingredient 15-19 is mixed, is dissolved by heating；
C：After B mixing is added in into A, crush；
D：Filling is pressed in canister.
While the eye shadow obtained in embodiment 28 has the use feeling easily smeared, moist feeling attaches and feels outstanding, makeup
Persistence is good.
While the eye shadow obtained in embodiment 29 has the use feeling of smooth smearing, moist feeling attaches and feels outstanding, makeup
Persistence is good.
While the eye shadow obtained in embodiment 30 has the soft use feeling of smooth smearing, moist feeling attaches and feels outstanding,
Persistence of making up is good.
The evaluation of water-in-oil base
Using the powder in embodiment 5,6,13, water-in-oil type base is made by the formula and following manufacturing methods of table 10
Matter.
【Table 10】
Water-in-oil base is manufactured by following A-D：
A：Ingredient 1-3 is mixed, is dissolved by heating；
B：4-11 stirrings are added in into A；
C：Ingredient 12-16 is mixed, is dissolved by heating；
D：C stirring and emulsifyings, cooling are added in into B.
Obtained water-in-oil base realizes smearing and sprawls easily, without viscosity and oiliness and with moist feeling, painting
Frank sense after cloth, makeup persistence is very good, do not vary with temperature with the time and change, stability is outstanding.
The evaluation of massage gel
With the powder obtained in embodiment 18, embodiment 31,32,33 is manufactured by the formula of table 11 and following manufacturing methods
The massage gel of cooperation.
【Table 11】
Massage gel is made by following A-B：
A：Ingredient 1,2,8 is mixed, is dissolved by heating；
B：3-7,9 stirrings are added in into A.
The massage oil obtained in embodiment 31 shows soft and easily smear, without oiliness, and with attaching
Sense, moist feeling.
The massage oil obtained in embodiment 32 shows soft and easily smear, no sticky and oiliness, and have
There is moist feeling.
The massage oil obtained in embodiment 33 shows very smooth smear, without viscosity and oiliness, and has
Moist feeling.
Claims (10)
1. a kind of surface such as following chemical formula (1) of surface treatment starch or surface-treated fiber element, starch or cellulose granules
Or shown in (2)：
For chemical formula (1) or (2), the glucose backbone in repetitive unit shown in box W represents starch bone in formula (1)
Frame represents cellulose skeleton in formula (2), and X is for hydrogen atom or as shown in following chemical formula (3), (4) or (5)；The degree of substitution of X
The average value of the substituted hydroxy number of every 1 glucose as the monosaccharide unit for forming starch or cellulose, be 0.005 to
0.1：
-V-M-Z (3)
For chemical formula (3), (4) and (5), V is as derived from having the binary acid there are two carboxyl shown in following chemical formula (6), institute
The carboxylic acid and the hydroxyl of starch and/or cellulose for stating binary acid form ester bond, another carboxylic acid is expressed as Carboxylic Acid Ions, M
Represent one or more kinds of 2-4 valency polyvalent metal ions, V and M form ionic bond, and Z is represented selected from carbon atom number 6-22
Aliphatic acid, amino acid, the amino acid combined with the aliphatic acid of carbon atom number 6-22, water-soluble acidic polysaccharose, water-soluble acid
Property synthesis macromolecule, one or more of water-soluble acid ultra-violet absorber compound ions, possessed by Z
Carboxylic Acid Ions, sulfate ion and/or phosphate ion and M form ionic bond；
- CORCOO- (6)
For chemical formula (6), R represent carbon atom number be more than 1, alkyl, alkenyl or alkynyl that optionally there is substituent group.
2. surface treatment starch as described in claim 1 or surface-treated fiber element, wherein, for chemical formula (3), (4) and
(5), polyvalent metal ion M be selected from calcium ion, magnesium ion, zinc ion, aluminium ion, copper ion, zirconium ion, iron ion, barium from
One or more of son, tin ion, titanium ion.
3. surface treatment starch as described in claim 1 or surface-treated fiber element, wherein, shown in formation chemical formula (6),
Tool there are two carboxyl binary acid derivative binary acid be selected from by succinic acid, malonic acid, maleic acid, itaconic acid, oneself
Diacid, hexenyl succinic acid, hexyl succinic acid, iso-octyl succinic acid, ocentyl succinic, octyl group succinic acid, decyl succinic acid,
Decenyl succinic acid, dodecenyl-succinic acid, dodecyl succinate, myristyl succinic acid, tetradecene base succinic acid, 16
Alkyl succinic acid, hexadecylene base succinic acid, octadecylsuccinic acid, octadecenyl succinic acid, iso-octadecyl succinic acid, 2-
One or more of group that (1- octyl group -2- decene base) succinic acid is formed.
4. surface treatment starch as described in claim 1 or surface-treated fiber element, wherein, for chemical formula (3), (4) and
(5), the aliphatic acid of the carbon atom number 6-22 of Z is selected from caproic acid, enanthic acid, new enanthic acid, octanoic acid, 2 ethyl hexanoic acid, n-nonanoic acid, different nonyl
Acid, capric acid, decylenic acid, lauric acid, lauroleic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, different palmitic acid,
Palmitoleic acid, Heptadecanoic acide, stearic acid, isostearic acid, oleic acid, linoleic acid, leukotrienes, hydroxy stearic acid, arachidic acid, peanut four
One or more of olefin(e) acid, behenic acid and sinapic acid.
5. surface treatment starch as described in claim 1 or surface-treated fiber element, wherein, for chemical formula (3), (4) and
(5), the amino acid of Z, the amino acid that is combined with the aliphatic acid of carbon atom number 6-22 be selected from alanine, arginine, asparagine,
Aspartic acid, glutamine, glutamic acid, theanine, glycine, histidine, isoleucine, leucine, relies ammonia at cysteine
Acid, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, γ-aminobutyric acid, N-
Coco-nut oil fatty acid acyl group-Pidolidone, N- lauroyls-Pidolidone, N- myristoyls-Pidolidone, N- acyl groups-L-
Glutamic acid, N- stearyls-Pidolidone, N- coco-nut oil fatty acids acylglycine, one kind in 2-pyrrolidone-5-carboxylic acid or two
Kind or more.
6. surface treatment starch as described in claim 1 or surface-treated fiber element, wherein, for chemical formula (3), (4) and
(5), the water-soluble acidic polysaccharose of Z is alginic acid, carragheen, pectin, xanthans, gellan gum；Water-soluble acid synthesis high score
Son is selected from one or more of following (A) and (B)：
(A) selected from one or more of acrylic acid, methacrylic acid, acryloyl dimethyl tauric acid polymerize
The high-molecular compound arrived；Or
(B) selected from one or more of acrylic acid, methacrylic acid, acryloyl dimethyl tauric acid with selected from propylene
The high score that one or more of acid alkyl ester, alkyl methacrylate, vinyl pyrrolidone are polymerize
Sub- compound.
7. surface treatment starch as described in claim 1 or surface-treated fiber element, wherein, for chemical formula (3), (4) and
(5), the water-soluble acid ultra-violet absorber of Z is selected from one or more of benzimidazole sulfonic acid, p-methoxycinnamic acid.
8. surface treatment starch as described in claim 1 or surface-treated fiber element, wherein, the surface treatment starch or table
Surface treatment cellulose is not gelatinized, and keeps shape of particle.
9. a kind of cosmetics, which is characterized in that the surface treatment that the cosmetics contain described in any one of claim 1-8 is formed sediment
Powder or surface-treated fiber element.
10. the manufacturing method of the surface treatment starch or surface-treated fiber element described in any one of claim 1-8, wherein,
It the described method comprises the following steps：
Starch and/or cellulose powder are carried out one by the first step with the dibasic acid anhydride as derived from having the binary acid there are two carboxyl
Grade processing, in powder surface formation-COO alkali metal salts；And
Second step as two stage treatment, makes that there is the soluble polyvalent metal salt of 2-4 valence metal ions, alkali metal compound to lead to
It crosses polyvalent metal to react with the powder after coagulation, the alkali metal compound is selected from carbon atom number 6-22's
Aliphatic acid, amino acid, the amino acid combined with the aliphatic acid of carbon atom number 6-22, water-soluble acidic polysaccharose, water-soluble acid
Property synthesis macromolecule, one or more of water-soluble acid ultra-violet absorber alkali metal compound.
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| JP2014069755A JP6212424B2 (en) | 2013-05-13 | 2014-03-28 | Surface-treated starch or surface-treated cellulose, cosmetics, and method for producing surface-treated starch or surface-treated cellulose |
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| TWI653985B (en) * | 2013-11-15 | 2019-03-21 | 高絲股份有限公司 | Surface treatment powder using the acid of aminic acid and cosmetics containing the same |
| US20170079893A1 (en) * | 2015-09-18 | 2017-03-23 | Johnson & Johnson Consumer Inc. | Phase-stable sunscreen compositions comprising an ultraviolet radiation-absorbing compound and superhydrophilic amphiphilic copolymers |
| CN107325192A (en) * | 2017-06-30 | 2017-11-07 | 武汉理工大学 | A kind of sulfhydrylation Cellulose nanocrystal and preparation method thereof |
| CN107822947A (en) * | 2017-11-10 | 2018-03-23 | 丁玉琴 | A kind of preparation method of conditioner |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103584C (en) * | 1993-09-01 | 2003-03-26 | 尤尼利弗公司 | Petroleum jelly cream |
| CN102070722A (en) * | 2010-02-03 | 2011-05-25 | 内蒙古奈伦农业科技股份有限公司 | Octenyl succinate distarch phosphate and preparation method and applications thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4082749B2 (en) * | 1995-12-28 | 2008-04-30 | 日澱化學株式会社 | Colored starch composition |
| US20030219391A1 (en) * | 2002-02-28 | 2003-11-27 | L'oreal | Dispersed powders providing ultraviolet light protection, suitable for use in cosmetic compositions |
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2014
- 2014-05-12 CN CN201410198040.1A patent/CN104151593B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103584C (en) * | 1993-09-01 | 2003-03-26 | 尤尼利弗公司 | Petroleum jelly cream |
| CN102070722A (en) * | 2010-02-03 | 2011-05-25 | 内蒙古奈伦农业科技股份有限公司 | Octenyl succinate distarch phosphate and preparation method and applications thereof |
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