CN100435772C - Shampoo composition - Google Patents

Shampoo composition Download PDF

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CN100435772C
CN100435772C CNB200380103200XA CN200380103200A CN100435772C CN 100435772 C CN100435772 C CN 100435772C CN B200380103200X A CNB200380103200X A CN B200380103200XA CN 200380103200 A CN200380103200 A CN 200380103200A CN 100435772 C CN100435772 C CN 100435772C
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acid
shampoo composite
surfactant
shampoo
product
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CN1711070A (en
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大野真嗣
西村英司
大沼克典
太垣成实
下谷由纪
永原恭生
矶田由美
楠濑正浩
西田勇一
打越香悦
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Lion Corp
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/731—Cellulose; Quaternized cellulose derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0295—Liquid crystals
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair

Abstract

A shampoo composition comprising (A) a cationic surfactant, (B) a silicon-free oil component, and (C) one or more detergent surfactants selected from the group consisting of amphoteric surfactants, anionic surfactants, and nonionic surfactants, characterized in that the (B')/[(A)+(B')] mass ratio is 0.35 to 0.90 (wherein (B') is a part of the component (B) which forms by itself a liquid crystal structure together with the component (A), that the total content of the amphoteric surfactant and the anionic surfactant exceeds 2 % by mass with the proviso that the content of the anionic surfactant is less than 5% by mass, and that the liquid crystal structure formed from the components (A) and (B) is dispersed in the composition. The shampoo composition is reduced in the squeakiness in rinsing the shampoo out of hair, particularly dyed hair which is liable to become squeaky, and is excellent in foaming property and long-term dispersion stability.

Description

Shampoo composite
Technical field
The present invention relates to shampoo composite, when the rinsing hair, can give low hair friction sense, particularly be applied to when being easy to experience the colored hair of hair friction, its preparation method also is provided.
Background technology
In recent years, the hair dyeing of increasing consumer is so that their appearance seems more beautiful or make hair seem brighter.Yet, generally speaking, carry out chemical treatment owing to relate to alkali, hydrogen peroxide or analog, dyeing is tending towards bringing injury to hair.As the result of this injury, intensive hair friction sense when rinsing shampoo, the surface of hair is arranged to such an extent as to hydrophilic part is exposed to.This person of being to use does not wish to take place.
With the viewpoint that reduces hair friction sense, diverse ways is recommended, comprise and be used in combination acylamino-carboxylate type surfactant and/or dicarboximide type surfactant and other surfactant (Japan Patent postpones publication number 10-121090), in shampoo, add cationic polymeric compound (Japan Patent postpones publication number 11-236320), use amino-acid compound (Japan Patent postpones publication number 7-310100), use botanical extract (Japan Patent postpones publication number 2001-207191), or the like.Yet these methods are not enough, especially for colored hair.
On the other hand, as the compositions that can form liquid crystal structure, it is one liquid crystal structure dispersion composition of detergent wherein, comprise cationic surfactant, higher alcohol and polyglyceryl fatty acid ester (Japan Patent postpones publication number 2001-311099), a kind of hair cosmetic is included in preparation in the cationic surfactant of vehicle form (Japan Patent postpones publication number 9-87147) by UV absorbent and water-soluble substances, or the like.Yet it is effective inadequately for reducing the hair friction that these compositionss are considered to.
Disclosure of the Invention
An object of the present invention is to provide a kind of shampoo composite, can when it is rinsed, give low hair friction sense, especially when being applied to be easy to experience the colored hair of hair friction.
The inventor has been found that, in compositions, comprise (A) cationic surfactant, (B) not siliceous oil component and (C) one or more detergent surfactants, be selected from by amphoteric surfactant, the group that anion surfactant and non-ionic surface active agent are formed, comprise component (A) and oiliness composition (B '), described oiliness composition (B ') is contained in the component (B), and can form liquid crystal structure with component (A), specific weight ratio and in compositions component (C) the support liquid crystal structure of special ratios be scattered in and make the shampoo composite that can give low hair friction sense when obtaining rinsing become possibility in the compositions, especially when being applied to colored hair, also have excellent foaminess and fabulous dispersion stabilization.
Therefore, the invention provides following shampoo composite and its preparation method:
(1) a kind of shampoo composite comprises:
(A) cationic surfactant,
(B) not siliceous oil component and
(C) one or more detergent surfactants are selected from by amphoteric surfactant, the group that anion surfactant and non-ionic surface active agent are formed,
Wherein wt than (B ')/[(A)+(B ')] from 0.35 to 0.90, (B ') represents oil component, be contained in the component (B) and form liquid crystal structure with described component (A) independently, the total amount of wherein said amphoteric surfactant and anion surfactant surpasses 2%, in the total amount of compositions.And described anion surfactant mass content is lower than 5%, in the total amount of compositions.Described liquid crystal structure is formed by component (A) and component (B), is scattered in the compositions.
(2) shampoo composite of (1) description, wherein the mean particle size of liquid crystal structure is lower than 20 μ m.
(3) (1) or (2) shampoo composite of describing further comprises: (D) the water-soluble bloated clay mineral of 0.01wt% at least.
(4) shampoo composite of a description in (1)-(3) further comprises: (E) amine oxide.
(5) shampoo composite of each description in (1)-(4) further comprises: (F) have coefficient of refraction and be lower than 1.46 silicone derivative.
(6) shampoo composite of each description in (1)-(6) further comprises: (G) as the viscosity reinforcing agent, have the hydroxypropyl emthylcellulose of following formula construction unit:
Figure C20038010320000061
Wherein molecular end and Rs represent hydrogen atom or methyl or propoxyl group separately, the propoxyl group that comprises 25-35wt% methoxy group and 5-15%, condition is that hydroxyl, methoxy group and propoxyl group total quantity are 100wt%, and have from 2100 to 35000mpa.s viscosity, with the 2wt% aqueous solution 20 ℃ of mensuration.
(7) shampoo composite of each description in (1)-(6) is used for painted hair.
(7) method of production claim 1 shampoo composite, comprise step: the water that will contain detergent surfactant mixes under the mixing temperature of the crystallized temperature of the component that is not less than described formation liquid crystal structure with the component of the formation liquid crystal structure that comprises cationic surfactant (A) and not siliceous oil component (B), from described mixing temperature cooling mixture, thereby make this shampoo composite, wherein said liquid crystal structure is dispersed in the described aqueous phase that contains detergent surfactant.
(8) as (8) described method, wherein the mixture of gained connects partially by a part from described mixing temperature and continues drawing (drawing), and cancellation and return described gained mixture repeats described drawing, cancellation then and returns and be cooled.
(9) as (8) or (9) described method, further comprise the step of mixing clay mineral (D), clay mineral has been dispersed in the water or by water-soluble and has expanded, and described water comprises one or more detergent surfactants (C).
The accompanying drawing summary
Fig. 1 is piece figure, has explained the container that preferably is used for continuous part-part quenching process according to of the present invention.
Fig. 2 is the DSC chart, has write down the shampoo composite of the representative formula of measuring with differential scanning heat instrument.
Preferred forms of the present invention
Component of the present invention (A) is a cationic surfactant, has no particular limits in the scope that can be included in shampoo composite.For example, the alkyl quaternary ammonium salts of following formula (1) representative is fit to.
Figure C20038010320000071
R1 wherein, R2, R 3 and R4 represent alkyl independently of one another, hydroxyalkyl, alkenyl, polyalkylene oxides or benzyl group, R 1, R 2, R 3And R 4In one or two C that respectively does for oneself 10-24, preferred C 16-22Straight chained alkyl, hydroxyalkyl or kiki alkenyl group, all the other methyl of respectively doing for oneself, ethyl or benzyl group or polyalkylene oxides, by-(C 2H 4O) q-H or-(C 3H 6O) r-H represents, q and r represent the integer from 1-5 separately, can be identical or different, and Z represents anion.
Cationic surfactant generally is to sneak into the form of salt.Especially, can be used as for example hydrochloride of inorganic acid salt, hydrobromide, sulfate or phosphate; Or acylate gluconate for example, acetate, lactate, succinate, tartrate, citrate, amino acid salts, higher fatty acid salt, pyroglutamic acid salt or tosilate.
Object lesson by the component (A) of formula (1) expression comprises stearyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, INCROQUAT TMC-80 ECONOL TM22,16 octadecyl trimethyl ammonium chloride,, VARISOFT TA100 and two (docosyl) alkyl dimethyl ammonium chloride.
Wherein, preferably those contain the straight chained alkyl group, particularly hexadecyltrimethylammonium chloride of 16-22 carbon, stearyl trimethyl ammonium chloride, INCROQUAT TMC-80 ECONOL TM22, and VARISOFT TA100.More preferably, they are forms of hydrochloride or hydrobromide.
Further, guanidine derivatives or its salt of formula (2) representative also can be used as suitable cationic surfactant,
Figure C20038010320000072
R wherein 5Represent straight or branched, C 1-21Alkyl or kiki alkenyl group, A are represented straight or branched C 1-10Alkylidene or alkenylene, t representative be from the integer of 1-5, when t is 2 or when bigger, and may be different as individual unit.
R in the formula (2) 5Be straight or branched C 1-21Preferred C 11-19Alkyl or kiki alkenyl group, suitable example comprises for example C 11H 23-, C 12H 25-, C 13H 27-, C 14H 29-, C 15H 31-, C 16H 33-, C 17H 35-, (C 8H 17) 2CH-, and 4-C 2H 5C 15H 30-.
Substituent A is a straight or branched, C 1-10, preferred C 2-6Alkylidene or alkylene group group, example comprises methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, isopropylidene, 2-amylene and 2-ethyl butylidene group.
The guanidine derivatives of formula (2) representative generally is to sneak into the form of salt.Especially, can be used as for example hydrochloride of inorganic acid salt, hydrobromide, sulfate or phosphate; Or acylate gluconate for example, acetate, lactate, succinate, tartrate, citrate, amino acid salts, higher fatty acid salt, pyroglutamic acid salt or tosilate.Wherein, preferred form is a hydrochloride, hydrobromide, acetate, lactate, citrate, amino acid salts.
The amino acid pattern cationic surfactant also can be used as suitable cationic surfactant.The example of amino acid pattern cationic surfactant is the lower alkyl esters of single (long acyl) basic amino acid of N-.The example that forms the basic amino acid of these chemical compounds comprises natural amino acid for example bird amino acid, lysine and spermine acid.Further, synthesizing amino acid is α for example, and β-DAB also can be used.They can be optical active substance or racemic modification.
Its carboxyl groups can be saturated or unsaturated, C 8-22The higher fatty acids residue.It can be derived or synthetic the acquisition from natural materials.The example that is fit to comprises for example lauroyl of single higher fatty acids residue, myristoyl, palmityl and stearyl; Natural, mix higher fatty acids residue group for example fatty acid distribution of coconut oil residue group and tallow fatty acid residue group.
The example of preferred lower alkyl esters composition comprises methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, own ester, heptyl ester and monooctyl ester.These lower alkyl esters compositions generally are to sneak into the form of salt.Especially, they can be used as for example hydrochloride of inorganic acid salt, hydrobromide, sulfate or phosphate; Or as acylate gluconate for example, acetate, lactate, succinate, tartrate, citrate, amino acid salts, higher fatty acid salt, L-or DL-pyrrolidone carboxylic acid salt, pyroglutamic acid hydrochlorate or tosilate.Wherein, preferred form is a hydrochloride, L-or DL-pyrrolidone carboxylic acid salt, and amino acid salts.
Further, acyl ammonia amine surfactant also can be used as suitable cationic surfactants.As for acyl ammonia amine surfactant, can use the chemical compound of formula (3) expression,
Figure C20038010320000091
R wherein 6Be C 7-23, preferred C 9-22, more preferably C 13-22Fatty acid residue, R 7Be C 1-4Alkyl group, preferable methyl or ethyl group, the m representative is from the integer of 2-4.
The example of the acyl ammonia amine surfactant of formula (3) representative comprises
Stearic acid lignocaine acetamide,
Stearic acid dimethylamino acetamide,
Palmic acid lignocaine acetamide,
Fatty acid distribution of coconut oil lignocaine propionic acid amide.,
Palmic acid dimethylamino acetamide,
Myristic acid lignocaine acetamide,
Myristic acid dimethylamino acetamide,
Behenic acid lignocaine acetamide,
Behenic acid dimethylamino acetamide,
Stearic acid lignocaine propionic acid amide.,
Stearic acid dimethylamino propionic acid amide.,
Palmic acid lignocaine propionic acid amide.,
Palmic acid dimethylamino propionic acid amide.,
Myristic acid lignocaine propionic acid amide.,
Myristic acid dimethylamino propionic acid amide.,
Behenic acid lignocaine propionic acid amide.,
Behenic acid dimethylamino propionic acid amide..They are generally sneaked into the form of salt.Concrete, they can be used as for example hydrochloride of inorganic acid salt, hydrobromide, sulfate or phosphate; Or as acylate gluconate for example, acetate, lactate, succinate, tartrate, citrate, amino acid salts, higher fatty acid salt, pyroglutamic acid hydrochlorate or tosilate.Wherein, preferred form is amino acid salts, citrate and hydrochloride.Incidental, one or more salt can be used to neutralization.Wherein, dimethylstearylamide base propionic acid amide., stearic acid diethylin acetamide and fatty acid distribution of coconut oil diethylin propionic acid amide. are to be fit to use.In the present invention, one or more acylamino-amine surfactant can be used.
Particularly from the liquid crystal structure viewpoint of stability in time, be used for cationic surfactant of the present invention (A) and distribute at the carbon number (chain length) of cationic surfactant aliphatic hydrocarbyl and preferably contain 50% or more, preferred 80% or more C 22Aliphatic hydrocarbyl.
Cationic surfactant ratio in the present invention as component (A) is had no particular limits, but in shampoo composite according to the present invention, the preferred 0.05wt% of lower limit or more, more preferably 0.5wt% or more, preferred especially 1wt% or more, and the upper limit can be preferably 7wt% or still less, more preferably 5wt% or still less, preferred especially 4wt% or still less.Unsuitable small scale can not give enough slickness of hair and flexibility sometimes when rinsing, can give the hair oiliness and cross a large amount of ratios.As component (A), the cationic surfactant of above example can use separately also and can be used in combination.
Especially, when the guanidine derivatives of the alkyl quaternary amine salt of formula (1) representative or formula (2) representative or its salt are combined, its ratio lower limit is preferably 0.05wt% or more in shampoo composite, more preferably 0.5wt% or more, preferred especially 1wt% or more, and the upper limit can be preferably 6wt% or still less, more preferably 4wt% or still less, preferred especially 3wt% or still less.
When amino acid pattern cationic surfactant when for example single (chain alkyl) basic amino acid Arrcostab of N-is combined, its ratio lower limit is preferably 0.1wt% or more in shampoo composite, more preferably 0.3wt% or more, and the upper limit is preferably 5wt% or still less, more preferably 3wt% or still less.
When the acylamino-amine surfactant was combined, its ratio lower limit was preferably 0.1wt% or more in shampoo composite, and more preferably 0.5wt% or more, and the upper limit is preferably 7wt% or still less, more preferably 5wt% or still less.
Component (B) is not siliceous oil component, it should be noted that oil component (B ') is included in the component (B), and in shampoo composite according to the present invention, can form liquid crystal structure by self and component (A), can significantly reduce the hair friction that rinses after the shampoo effectively, be necessary to shampoo composite.The example of component (B) comprises following monomer or condensation product (1)-(5).As the component among the present invention (B), they can use separately or be used in combination.
(1) by formula R 12Pure I shown in the-OH
(2) by formula R 13Fatty acid II shown in the-COOH
(3) the condensation substance IV of pure I and polyhydric alcohol III
(4) the condensation substance V of fatty acid II and polyhydric alcohol III
(5) pure I or condensation substance IV and fatty acid II, the condensation substance of condensation substance V or polyprotic acid VI.
By formula R 12Pure I shown in the-OH is saturated, undersaturated or branched-chain alcoho or hydroxyl alcohol, each R 12Has from 1 to 40 carbon atom.Special example comprises methylol, isopropyl alcohol, n-butyl alcohol, isobutanol, n-octyl alcohol, 2-Ethylhexyl Alcohol, isononyl alcohol, Decanol, isodecanol, undecyl alcohol, lauryl alcohol, lauryl alcohol,, different tridecanol, tetradecyl alchohol, hexadecanol, 2-hexyl decyl alcohol, 16 octadecanol, octadecanol, i-octadecanol, octyl group dodecyl alcohol, aralkyl alcohol, docosanol, oleyl alcohol, anti-(formula) oleic alcohol, inferior oleyl alcohol, tetracosanol, hexacosyl alcohol, cholesterol and plant sterol.Wherein, from the preferred straight chain alcohol of angle (hexadecanol, octadecanol, docosanol or the like of in time stability.) and branched-chain alcoho (2-hexyl decyl alcohol, 2-Ethylhexyl Alcohol, i-octadecanol or the like.), straight chain alcohol is particularly preferred.As for branched-chain alcoho, more preferably the side chain position more approaching corresponding terminated those.From the angle of chain length, C 8-22Alcohol is preferred, more preferably straight chain C 16-22Alcohol (hexadecanol, octadecanol, docosanol or the like.)。Wherein, docosanol is most preferred.These alcohol can use separately or be used in combination.Yet.From stable angle in time, what contain 22 carbon atoms preferably accounts for 40% or more, and more preferably 70% or more.
By formula R 13Fatty acid II shown in the-COOH is saturated, undersaturated or branched chain fatty acid or hydroxy fatty acid, each R 13Have 4-40 carbon atom.Concrete example comprises butanoic acid, and is sad, different n-nonanoic acid, tetramethyl n-nonanoic acid, capric acid, lauric acid, tetradecylic acid, 2-hexyldecanoic acid, Palmic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, 2-heptyl undecanoic acid, tetracosanoic acid, hydroxyhexacosanoic acid, nonacosanoic acid, triacontanoic acid, laruolanic acid, oleic acid, elaidic acid, erucic acid, 20 acid, 3,5,5-tri-methyl hexanoic acid, linoleic acid, eleostearic acid, linolenic acid, castor oil acid, arachidonic acid, eicosapentaenoic acid, docosahexenoic acid, hydrogenated castor oil fatty, fatty acid distribution of coconut oil, lanolin fatty acid, methacrylic acid, sad (2 ethyl hexanoic acid), neodecanoic acid (2, the 2-dimethyl is sad), citronellic acid, abietic acid, dehydroabietic acid, neoabietic acid, Parastrinicacid, dextropimaric acid, isodextropimaric acid, lactic acid and 12-hydroxy stearic acid.When oil component is a monomer, preferred example comprises C 8-24Fatty acid.Wherein, from the angle of in time stability, C 16-22Fatty acid (Palmic acid, stearic acid, behenic acid or the like) is more preferred.
The example of polyhydroxy-alcohol III comprises the represented polyhydroxy-alcohol of following formula (4):
HO((CaH 2a)O) b((CcH 2c)O) dH (4)
Wherein a, b, c and d are had no particular limits, a and c can be identical, but on behalf of the integer of 2-10 and b and d, preferred a and c represent the integer of 1-150 separately separately.
The example of the polyhydroxy-alcohol of formula (4) representative is an ethylene glycol, diethylene glycol, hexylidene glycol, Polyethylene Glycol, propylene glycol, dipropylene glycol, polypropylene glycol, isoprenediol, glycerol, two glycerol, triglycerin, four glycerol, six glycerol, ten glycerol, 1,3-butylidene glycol, trimethylolpropane, erithritol, tetramethylolmethane, two (gathering) tetramethylolmethane, glucose, mannose, galactose, sucrose, fructose, maltose, multitol, xylitol, inositol, dehydration Pyrusussuriensis (sugar) alcohol, the EO adduct of Pyrusussuriensis (sugar) alcohol and these polyhydroxy-alcohols.
The example of polyprotic acid VI comprises for example succinic acid of carboxylic acid, 1,3-propanedicarboxylic acid, adipic acid, maleic acid, tartaric acid, malic acid, citric acid, phthalic acid, partially originally three acid, decanedioic acid; With mineral acid for example phosphoric acid and sulphuric acid.
(3) the condensation substance IV of pure I and polyhydric alcohol III, (4) the condensation substance V of fatty acid II and polyhydric alcohol III and (5) pure I or condensation substance IV and fatty acid II, the example of the condensation substance of condensation substance V or polyprotic acid VI is by higher alcohol EO or PO adduct, and fatty acid EO or PO adduct obtain, and comprise for example glyceryl monostearate of polyglyceryl fatty acid ester, two glyceryl monostearates, six glyceryl monostearates, SY-Glyster MSW 750, two glycerol distearates, six glycerol distearates, ten glycerol distearates, five glycerol tristearates, six glycerol tristearates, ten glycerol tristearates, six glycerol tetrastearates, ten glycerol tetrastearates, four glycerol the five kinds of stiffness in infant fat acid esters, six glycerol the five kinds of stiffness in infant fat acid esters, ten glycerol the five kinds of stiffness in infant fat acid esters, five glycerol, six stearates, six glycerol, six stearates, six glycerol, eight stearates, ten glycerol, ten stearates, glycerol list isostearate, two glycerol list isostearates, six glycerol list isostearates, ten glycerol list isostearates, two glycerol diisopstearates, six glycerol diisopstearates, ten glycerol diisopstearates, five glycerol, three isostearates, six glycerol, three isostearates, ten glycerol, three isostearates, six glycerol tetraoctyl stearates, ten glycerol tetraoctyl stearates, four glycerol, five isostearates, six glycerol, five isostearates, ten glycerol, five isostearates, five glycerol, six isostearates, six glycerol, six isostearates, six glycerol, eight isostearates, ten glycerol, ten isostearates, two glycerin mono-fatty acid esters, diolein, glycerol monohydroxystearate, monomyristin, ten glycerol Qi behenic acid esters, SUNSOFT A-173E, five glycerol San behenic acid esters, five glycerol Si behenic acid esters, five glycerol Wu behenic acid esters, triglycerin Er behenic acid ester, triglycerin San behenic acid ester, triglycerin Si behenic acid ester, glycerol three (2-ethylhexanoate) and glycerol three (caprylate or capric acid); With ester trimethylolpropane tris caprylate for example, trimethyl propane three (2-ethylhexanoate), the trimethylolpropane tris stearate, the trimethylolpropane tris isostearate, five erithritols, four caprylates, five erithritols four (2-ethylhexanoate), two five erithritol hexahydroxystearic acid esters, two five red moss ester fatty acid esters, the propylene glycol dicaprylate, Capryol 90, the propylene glycol dicaprylate, Arlacel-83, octyl group dodecyl lactate, the hexyl laurate, the myristyl caprylate, the palmityl caprylate, the stearyl caprylate, the cetyl tricaprylate, isonoyl isononanote, tridecyl isononanoate, isopropyl myristic acid ester, the butyl myristinate, the myristyl myristinate, the 2-Wickenol 142,2-hexyl decyl myristinate, 2-hexyl decyl stearate, isopropyl cetylate, the iso stearyl cetylate, the octyl group cetylate, 2-hexyl decyl cetylate, the cetyl cetylate, the methyl stearate, the butyl stearate, the hexyl stearate, the octyl group stearate, stearyl stearate, 2-hexyl decyl isostearate, Witconol 2310, the octyl group hydroxy stearic acid ester, the ethyl oleate, the oil base oleate, octyl group dodecyl oleate, the octyl group Arachidate, the isobutylated lanolin fatty acid, octyl group dodecyl lanolin fatty acid, the ethyl linoleate, the isopropyl linoleate, the dioctyl succinate, diethoxy ethyl succinate, the diisopropyl adipate ester, diisopropyl dimerization dilinoleic acid ester, the diethyl sebacate, the diisopropyl sebacate, two isostearic acid base malates, three (2-ethylhexyl) citrate, 2-heptyl undecyl adipate ester, diethoxy ethyl succinate, glycerine fatty acid-adipic acid condensation substance, the different cetylate of two glyceryls-decanedioic acid condensation substance, single steroid thiazolinyl stearate, single steroid thiazolinyl isostearate, single steroid thiazolinyl hydroxy stearic acid ester, plant steroid base hydroxy stearic acid ester, with plant steroid base isostearate.
Other oil component, what can be mentioned is alkyl ether phosphoric acid and salt and alkyl ether phosphoric acid POE (polyoxyethylene groups) derivant, alkylamine and POE derivant thereof; Fatty acid amide and POE derivant thereof; Oleum Ricini; Castor oil hydrogenated and POE derivant thereof, grass tree wax is Brazil wax, candelilla wax and Japan wax for example; Animal wax is Cera Flava, spermaceti and lanocerin for example; Pertroleum wax is paraffin and microwax for example; With mineral wax montan wax for example, (pure) ceresine and ceresine.
Wherein, from storage stability angle in time, senior (carbon number: 16-22) pure fusing point is that 45 ℃ or higher (cetearyl alcohol, stearyl alcohol, arachidic alcohol, behenyl alcohol, or the like) are preferred.
In the present invention, it is necessary allocating oil component into, and it can form liquid crystal structure by self and component (A), as component (B '), from the convenient angle that forms liquid crystal, exists in compositions with ratio component (A) with cited below.Illustrative component (B ') is alcohol above-mentioned (1) and fatty acid (2), and has condensation substance (3) and (4) greater than 4 HLB value.As component (B '), they can use separately or be used in combination.In conjunction with being possible, as component (B), can not be by self other not siliceous oil component with any liquid crystal of component (A) formation, for example, pearling agent is ethylene glycol bisthioglycolate (fatty acid) ester or glycol distearate for example, or viscosity increasing agent, minimizing agent or stabilizing agent for example POE castor oil hydrogenated, POE methyl glucoside dioleate or alkyl fatty acid amide.Component in shampoo composite (A) and component (B ') ratio is (B ')/((A)+(B ')) from 0.35 to 0.90, the preferred lower limit and the upper limit respectively do for oneself 0.50 and 0.80.If ratio (B ')/((A)+(B ')) is less than 0.35 or greater than 0.90, the hair friction can not reduce a lot during rinsing.
Be most preferred component (A) and combination (B) below:
(i) (A) C 16-22Monoalkyl cationic surfactant and (B) C 16-22Alcohol, and the combination of (B ')/((A)+(B '))=0.6 to 0.8; With
(ii) (A) C 16-22Dialkyl cationic surfactant and and (B) C 16-22Alcohol, and the combination of (B ')/((A)+(B '))=0.5 to 0.7.
Be different from component (B '), have no particular limits for the toatl proportion of component (B ') and not siliceous oil component.Yet generally speaking, its lower limit is preferably 0.5wt% or more in shampoo composite, the preferred 10wt% of more preferably 2wt% or more, and the upper limit or littler, more preferably 8wt% or littler.Ratio may cause the usability deficiency less than 0.5wt%, and ratio may cause the time stability of difference greater than 10wt% simultaneously.
Component (C) is made up of one or more detergent surfactant, is selected from the group that is made up of amphoteric surfactant, anion surfactant non-ionic surface active agent.
The example of zwitterionic surfactant comprises the alkyl betaine-type surfactant, amido betaine type surfactant, sulfobetaines type surfactant, hydroxyl sulfo betaine type surfactant, amidosulfobetaines type surfactant, phosphoric acid betaine type surfactant, imidazolinium betaine type surfactant, alanine type surfactant, and amino acid type surfactant.
Wherein, CAB lauramide preferably, betanin lauryl dimethyl aminoacetate, the fatty acid distribution of coconut oil amido propyl betaine, fatty acid distribution of coconut oil dimethylamino acetas betanin, lauryl hydroxyl sulfo betaine, 2-alkyl-N carboxymethyl-N-hydroxyethyl imidazole quinoline betanin, lauryl imino-diacetic propyl ester, N-(3-alkyl (12,14) oxygen-2-hydroxypropyl)-L-arginine hydrochloride.
Examples of anionic surfactants comprises alkylsulfonate; alkyl sulfate; acylated amino salt; polyoxyethylene alkyl ether sulfate salt; alkylbenzenesulfonate, N-acyl group-N methyl taurine salt, alpha-alefinically sulfonate; the higher fatty acids sulfonated ester; the alkyl ether acetate, polyoxyethylene alkyl ether acetate, fatty acid soaps; alkyl phosphate salt; the N-lauroyl glutamate, N-palmityl glutamate, Glu, N-lauroyl-Ethylglycocoll salt; N-Hamposyl L salt and N-myristoyl-Beta-alanine salt.
The example of non-ionic surface active agent comprises polyoxyethylene fatty acid ester, polyoxyethylene hydrogenated Oleum Ricini, polyoxyethylene dehydration Pyrusussuriensis (sugar) alcohol fatty acid ester, polyoxy fatty acid glyceride, polyoxyethylene alkyl ether, the polyoxyethylene polyoxypropylene glycol, the fatty acid distribution of coconut oil alkanolamide, sucrose fatty acid ester, alkylglycoside, alkyl glycerol base glucoside and methyl glucoside fatty acid ester.Wherein, polyethylene glycol mono stearate preferably, decyl glyceryl monolaurate, single Gan You behenic acid ester, polyoxyethylene lauryl ether, polyoxyethylene 8 stearate ether, Ju oxygen ethylene behenic acid ether, polyoxyethylene (160) polyoxypropylene (30) glycol, alkylglycoside, or the like.
The lower limit of component in shampoo composite (C) ratio is preferably 2wt% or more, more preferably 10wt% or more, and the upper limit is preferably 60wt% or still less simultaneously, more preferably 50wt% or still less.In the present invention, the ratio of ionic surface active agent (amphoteric surfactant and/or anion surfactant) need be greater than 2wt%, preferred 5wt% or more, especially, 10wt% or more, from the foaminess angle based on total composition.The upper limit ratio of the surfactant of performance ion characteristic generally is 30wt%, is suggested although have no particular limits at this.From the angle of dispersion stabilization, the surfactant ratio of performance anion characteristic (anion surfactant) needs low 5wt%, preferred 2wt% or still less, especially 1wt% or still less.Showing the ratio lower limit of the surfactant of anion characteristic, generally is 0.1wt%, is suggested although have no particular limits at this.By way of parenthesis, keep the angle of prevention friction effect during from rinsing, it is preferred using amphoteric surfactant separately.
It is preferred allocating (D) water swelling clay mineral in shampoo composite according to the present invention into.By allocate water swelling clay mineral (D) in shampoo composite according to the present invention, its dispersion stabilization is significantly improved.The example of water swelling clay mineral comprises natural or synthetic smectic clays and the organic substance modified clay by using quaternary ammonium salt cation surfactant, non-ionic surface active agent and/or analog processing to obtain.As illustration is bentonite, montorillonite clay, beidellite, nontronite, Pulvis Talci, hectorite, sauconite and STEVENSITE.Swelling Muscovitum or the like also can be used.Wherein, beidellite, montorillonite clay and Pulvis Talci are particularly preferred.As component (D), these water swelling clay minerals also can be by separately or be used in combination.
Water swelling clay mineral, especially those effects that may not show them fully that obtain from natural resources are if they comprise more non-swelling impurity for example calcite, tridymite, cloud diamond stone, quartz, various inorganic substances or the like.Therefore clay mineral can preferably have 90wt% or higher, especially 95wt% or higher purity.
From the angle of dispersion stabilization, the ratio of component (D) in shampoo composite is preferably 0.01wt% or more.The ratio lower limit is preferably 0.05wt% or more, and simultaneously upper limit thing is preferably 5wt% or still less, more preferably 2wt% or still less.
Also preferably allocate amine oxide component (E) into according to shampoo composite of the present invention.Allocate amine oxide component (E) into and make the emulsus foam.As the amine oxide of component (E), the amine oxide shown in the following formula (5) can be mentioned,
Wherein, R 8Represent C 8-24, preferred C 8-18The univalence hydrocarbyl group, C 8-18The straight chained alkyl group is particularly preferred.R 9And R 10Each represents C 1-3Alkyl or hydroxyalkyl group or by unit price substituted radical and preferable methyl or the hydroxyethyl groups shown in the formula (6), n represent the 0 or from the integer of 1-5, the 0th, and be preferred,
Figure C20038010320000162
R wherein 11Represent hydrogen atom or methyl group, p represents 1-5.
As being used for amine oxide of the present invention, lauryl dimethyl amine oxide, stearyl dimethyl amine oxide, lauryl dihydroxy ethyl amine oxide, polyoxyethylene lauryl dimethyl amine oxide (3 moles of average addition ethylene oxides), or analog is fit to.
Preferably, the amine oxide shown in one or more said structure formulas respectively, can be added into according in the shampoo composite of the present invention.By these amine oxides of trade name example, " SOFTAMINEL " (Toho chemical industry Co., Ltd product), " Oxamin-ALS " (KYOEI company limited product), " Aromox C/12 ", " Aromox C/12W ", " Aromox DMC-W ", " Aromox CM12D-W (C) " (all are Lion Akzo company limited products), or the like.
From producing the foamy angle of emulsus, be preferably 0.1wt% or more as the ratio lower limit of the amine oxide of component (E), more preferably 0.3wt% or more, the upper limit is preferably 5wt% or still less simultaneously, more preferably 2wt% or still less.
In the scope of not damaging the object of the invention, if desired, the various additives that are generally used in the shampoo composite can be added into, and except above-mentioned necessary component, optional ingredient and water are for example purified waste water.These additives can be used singly or in combination.
The illustration of various additives has silicone derivative, anionic polymer, cationic polymer, non-ionic polymers, polyol, inorganic salt is sodium chloride and sodium sulfate for example, organic salt, wetting agent is propylene glycol for example, nourishing agent, solubilizing agent, antioxidant is BHT and alpha-tocopherol for example, antibacterial is triclosan and Amolden MCM 400 (trichlorocarban) for example, viscosity-control additive is macromolecular compound for example, fatty monoethanol amide and fatty diglycollic amide, UV absorbent, protein derivatives, the animal or plant extract, anti-dandruff dose of for example pirooctone olamine and pyrithione zinc, antiinflammatory is Radix Glycyrrhizae dipotassium hydrochlorate for example, antiseptic is benzoic acid and salt thereof for example, metagin and " triumphant loose CG ", the PH regulator is citric acid and triethanolamine for example, pearling agent is ethylene glycol bisthioglycolate (fatty acid) ester for example, emulsifying agent, hydrotropic agent, lower alkyl alcohol, vitamin, the ethereal oil composition, hydrophobic solvent, diluent, pigment, and spice.These additives can be mixed alone or in combination and be mixed.They can be added in the scope of not damaging according to the excellent results of shampoo composite of the present invention.
Have no particular limits for the silicone derivative kind and to be suggested.Available silicon additive is that those generally are used in the shampoo composite.Example comprises dimethyl polysiloxane (comprising highly polymeric dimethyl polysiloxane and silicone rubber), methyl phenyl silicone, polyether modified siloxane, poly-ammonia modified siloxane, betanin modified siloxane, pure modified siloxane, fluorine modified siloxane, epoxide modified siloxanes, sulfhydryl modified siloxanes, carboxy-modified siloxanes, fatty acid modified siloxanes, silicone grafted polymers, cyclosiloxane, alkyl-modified siloxanes, trimethyl first siloxanes-terminal dimethyl polysiloxane and silanol-terminal dimethyl polysiloxane.They can be used alone or in combination as required.Wherein, dimethyl polysiloxane, polyether modified siloxane and poly-ammonia modified siloxane are to be fit to use.
In these silicone derivatives, those indexs of refraction are less than 1.46, especially less than 1.42 be preferred, from the angle of improving of final slickness.The lower limit of index of refraction is preferably 1.39 or higher, is suggested although have no particular limits at this.
Index of refraction comprises " LEOFLOW DMS-55 " (lion princes and dukes department product) less than the object lesson of 1.46 silicone derivative (component (F)), " SM8704C " (DOW CORNING Toure siloxanes company limited product) and " SH3775M " (DOW CORNING Toure siloxanes company limited product).
In the present invention, each index of refraction is the value that obtains according to JSCI conventional determining method (Abbe refractometer) mensuration by at 25 ℃.
Have no particular limits for viscosity of these silicone derivatives or the like.Yet generally speaking, have 25 ℃ from 1-20,000, the viscosity of 000cst, preferably from 30-1,000,000cst viscosity is fit to be used.
Silicone derivative also can be used with the emulsive form of emulsifying agent.Have no particular limits for emulsifying agent and emulsification method.Therefore, various emulsifying agents and emulsification method can selectedly use.When such silicone derivative is allocated into, according to shampoo composite product viscosity of the present invention preferably from 500 to 15,000mpa.s, especially preferably from 1,000 to 10,000mpa.s is from the angle of dispersion stabilization.Viscosity is lower than the dispersion stabilization that 500mpa.s may cause the siloxanes difference, and viscosity is higher than 15, and 000mpa.s may cause the distributivity of difference in container and therefore cause the ease of use of difference.
The object lesson of anionic polymer and non-ionic polymers comprises pectin, antler glue, guar gum, locust bean gum, gelatin, xanthan gum, carboxy vinyl polymer, carboxymethyl hydroxyethyl cellulose, hydroxyethyl-cellulose, hydroxypropyl emthylcellulose, arginine salt, starch, polyvinyl alcohol, polyacrylate, poly-methyl acrylate, polymethyl acrylate salt, Polyethylene Glycol, polyoxyethylene and tragacanth gum.
In the present invention, preferably allocate (G) hydroxypropyl emthylcellulose into the construction unit shown in the following formula as thickening agent, contain 25 to 35wt% methoxy group and 5 to 15wt% propoxyl groups (prerequisite is that total oh group, methoxy group and propoxyl group is 100wt%), and have 2,100-35,000mpa.s viscosity, with the 2wt% aqueous solution 20 ℃ of mensuration.Allocating the shampoo composite that such hydroxypropyl emthylcellulose make to obtain to have good solubility into especially becomes possibility, does not have hair friction sense when rinse, and forms careful foam during foaming,
Figure C20038010320000191
Wherein molecular end and Rs each represent hydrogen atom or methyl or propoxyl group.
In hydroxypropyl emthylcellulose, the oh group of some fibre element is replaced by methoxy group or propoxyl group.If oh group, methoxy group and propoxyl group sum reach 100wt%, methoxy group content can be from 25-35wt%, preferably can be from 5-15wt%, preferably from 7-12wt% from 28-30wt% and propoxyl group.Unless these content fall into corresponding scope, it can be difficult to show the emulsus foam effect of improvement in some cases.
The viscosity of hydroxypropyl emthylcellulose is recorded with 30rpm at 20 ℃ by BM type viscometer by its 2wt% aqueous solution.Viscosity is lower than 2, and 100mpa.s may cause showing in some cases that foam improves effect failure, and viscosity is higher than 35, and 000mpa.s may cause that dissolubility is not enough in some cases.
Hydroxypropyl emthylcellulose can be synthetic by known method.It also can be commercially available.
When allocating hydroxypropyl emthylcellulose into, can be 0.01wt% or more according to its ratio lower limit in the shampoo composite of the present invention, 0.1wt% or more more preferably, especially the preferred 0.2wt% or the more and upper limit be 2wt% or still less preferably, more preferably 0.5wt% or still less, especially preferred 0.3wt% or still less is all from good spumescence.
The illustration of cationic polymer is dimethyl diallyl ammonium chloride homopolymer and dimethyl diallyl ammonium chloride-acrylamide copolymer, each all contains dimethyl diallyl ammonium chloride as functional group, Poise C-80M, JR-125, the cationization dextrin, the cationization amylopectin, quaternized vinyl pyrrolidone-amino-ethyl methacrylate copolymer, polyethylene-imines, the dipropylenetriamine condensation substance, dimethyl adipic acid-amino hydroxypropyl diethyl triamine copolymer and contain quaternary nitrogen starch; In addition, hydrolysis of keratin, hydrolyzed silk protein, hydrolytic collagen, hydrolyzed wheat protein, cation group obtains by introducing in hydrolyzed protein with those, for example cation hydrolysis keratin, cation hydrolysis fibroin, cation hydrolytic collagen, cation hydrolysis wheat protein, siloxanes-modified hydrolyzed collagen protein and siloxanes-modified-fibroin.These polymer can be used alone or in combination.
The object lesson of spice comprises that synthetic perfume comprises hydrocarbon for example aliphatic hydrocarbon, terpene hydrocarbon and aromatic hydrocarbons; Alcohol is aliphatic alcohol for example, terpenol and aromatic alcohol; Ether is aliphatic ether and aromatic ether for example; Oxide is fat oxidation thing and terpenes oxide for example; Aldehyde is fatty aldehyde, terpene aldehyde, alicyclic aldehyde, thioaldehydes and aromatic aldehyde for example; Ketone is aliphatic ketone, terpenone, alicyclic ketone, nonbenzenoid aromatic ketone and aromatic ketone for example; Acetal; Ketal; Phenols; The 2, 2-Oxydiphenol class; Acid is fatty acid for example, terpenes carboxylic acid, alicyclic carboxylic acid and aromatic carboxylic acids; Amide; Lactone is aliphatic lactone, macrolide, terpenes lactone, alicyclic lactone and aromatic series lactone for example; Ester is aliphatic ester, furancarboxylic acid ester, alicyclic carboxylic ether, cyclohexane carboxylic acid ester, terpenes carboxylate and aromatic carboxylates for example; Nitrogen-containing compound is nitro musk, nitrile, amine, pyridine, quinoline, pyrroles and indole for example; Acquisition is from the natural perfume material of animal and plant; And the spice mixt that contains natural perfume material and/or synthetic perfume.They can be used alone or in combination.
As synthetic perfume, for example at INDO, Motokazu, " Gosei Koryo Kagaku toShohin Chishiki (synthetic perfume and flavor chemistry knowledge and commodity) " The ChemicalDaily Co., Ltd. (1996) publishes, ARCTANDER, Steffen, " perfume and flavor chemistry " Montclair, N, J. (1969), or the like what describe is available.As natural perfume material, compile by Japanese perfume and essence association at " Kaorino Hyakka (spice encyclopedia) ".
The object lesson of first kind of spice comprises C 6-12Aldehyde; anisaldehyde; acetal; 1-Phenylethanone.; Acetyl-.alpha.-cedrene; adoxal; pi-allyl amyl group oxyacetate; pi-allyl cyclohexylamine propionic ester; α-damascone; β-damascone; δ-damascone; ambroxan; the amylbenzene hexenal; amylbenzene hexenal dimethyl-acetal; the amyl group valerate; the amyl group salicylate; the isoamyl acetic acid ester; the isopentyl salicylate; aurantiol; the adetyl eugenol; bacdanol; the benzylacetic acid ester; benzylalcohol; the benzyl salicylate; bergamyl acetate; borneol acetate; the butyl butyrate; patchone; right-the tert-butylcyclohexyl acetas; verdol; o-tert-butyl cyclohexyl-acetic acid ester; benzaldehyde; benzyl formate; caryophyllene; cashmerane; carbone; cedroamber; Cedryl acetate.; cedrol; celestolide; cinnamyl alcohol; cinnamic aldehyde; cis-jasmone; citral; Fructus Citri Limoniae dimethyl two acetals; citrasal; citronellal; citronellol; geraniol acetate; geraniol formate; 3,7-Dimethyl-6-octenenitrile; cyclaset; cyclamen aldehyde; cyclaprop; caron, coumarin; the cinnamyl acetas; δ-C 6-C 13Lactone, dimethyl benzyl carbinol, dihydro jasmone, dihydro linalool, dihydromyrcenol, dimetol, myricanol, diphenyl oxidation thing, ethyl vanillin, acetaminol, fruit acid esters, fenchol, phenethyl phenylacetic acid ester, galaxolide, γ-C 6-C 13Lactone, australene, nopinene, limonene, myrcene, β-caryophyllone, geraniol, the geranyl acetas, the geranyl formic acid esters, geranonitrile, hedion, hellional, heliotropine, cis-3-hexanol, suitable-3-hexenyl acetas, suitable-3-hexenyl salicylate, jasminolene, the hexyl salicylate, the hyacinth dimethyl-acetal, water-soluble alcohol, hydroxycitronellal, indole, ionoionone, isobornyl acetate, isocyclocitral, Iso E Super, isoeugenol, different nonyl acetas, Isobutylquinoline., jasmal, ja smolacetone, jasmophyllan, corvone, ligustoral, lilial, the limette oxide, linalool, Linalool oxide, linalyl acetate, lyral, manzanate, myol, menthanyl acetate, menthonate, methyl ammonia Fructus Foeniculi ester, methyleugenol, menthol, the Alpha-Methyl ionoionone, the Beta-methyl ionoionone, cetone gamma, the methyl isoeugenol, methyl lavandula angustifolia ketone, the cresotinic acid acid esters, muguet aldehyde, mugol, astrotone M-II, Moschus 781, Moschus C 14Muscone, cibetone, cyclopentadecanone, Cyclohexadecanone, cyclopentadecanolide, ambrettolide, cyclohexadecanolide, 10-oxahexadecanolide, 11-oxahexadecanolide, 12-oxahexadecanolide, vinyl Brazil acid esters, ethylenedodecanedioate, oxahexadecen-2-one, 14-methyl-hexadecenolide, 14-methyl-hexadecanolide, muscone, musk Tibetene, nopol, acetas is foretold in promise, neryl acetate, nerol, the aminomethyl phenyl acetas, myrac aldehyde, neobergamate, oak moss tree No. 1, orvne, oxybenzene ketone, p-cresyl methyl ether, pentalide, phenethyl alcohol, the phenethyl acetas, rubafuran, damascenone, raspberry ketone, dimethyl benzyl dimethylbenzyl ethyl methyl acetic acid ester, jasmacyclene, the methyl naphthyl ketone, rosephenone, the Flos Rosae Rugosae oxide, " sandalore ", " sandela "; " santalex "; styterlacetate; styrallyl propionic ester; terpinol; tirpinyl acetate; tetrahydrolialool, the tetrahydrolialool acetas, tetrahydrogeraniol, tetrahydrochysene geranyl acetas, tonalide, traseolide, tripral, thymol, vanillin, verdox, jara jara, anis oil, laurel, bois derose oil, Cananga odorata oil, cardamon oil, cassia oil, Cedrus deoclar (Roxb.) G. Don oil, oleum Citri sinensis, mandarin oil, tangerine oil, basil oil, Semen Myristicae oil, citronella oil, cloves oil, Fructus Coriandri oil, elemi oil, eucaryptus oil, fennel oil, galbanum oil geranium wilfordii oil, hiba oil, hinoki oil, Jasmin oil, lavandin oil, Oleum lavandula angustifolia, Fructus Citri Limoniae oil, lemonglass oil, lime oil, naroli oil, oak moss oil, ocotea oil, patchouli oil, Oleum menthae, perilla oil, petitgrain oil, Oleum Pini, Oleum Rosae Rugosae, oil of rosemary, Oleum Camphora, ho leaf oil, sage oil, orange Oleum sesami, spearmint oil, the spike Oleum lavandula angustifolia, star anis oil, thyme oil, the tonkabean tincture, Oleum Terebinthinae, the vanilla bean tincture, vetiver oil, cananga oil, grape-fruit seed oil, yuzu (Citrus Junos Tanaka) oil, Benzoinum, face cream, tolu balsam, tuberose oil, absolute oakmoss, the fur face cream, musk tincture, castrium tincture, civet tincture and ambergris tincture.
What can be used as solvent or volatilization prevention agent in these spice is diethyl phthalate, dipropylidene diol, benzyl benzoate, isopropyl myristic acid ester, " Hercolyn ", isopentane, orange terpenes or the like.
In shampoo composite according to the present invention, the liquid crystal structure that forms from cationic surfactant (A) and not siliceous oil component (B) is scattered in the compositions.This dispersive liquid crystal structure has brought benefit, makes when rinse, and the serious color hair hair friction when rinse of the sense that especially rubs reduces and shampoo composite has fabulous spumescence and fabulous dispersion stability with time.Liquid crystal structure is formed by component (A) and component (B).Except these two components, other component also can exist by trace.
By way of parenthesis, liquid crystal structure can be confirmed by X-ray diffraction meter, optical microscope, ultramicroscope or the like.It is dispersive and not dissolving that term " dispersion " means liquid crystal structure at this.
Be dispersed in the liquid crystal structure upper limit in the shampoo composite and can be preferably and be lower than 20 μ m, more preferably 10 μ m or still less, especially preferred 5 μ m or still less, and lower limit can preferred 0.05 μ m or more, more preferably 0.1 μ m or more.20 μ m or bigger mean diameter cause when rinsing producing reduces friction that the slickness of effect reduction and arrangement, oils and fats arrangement reduces and dispersion stabilization reduces.On the other hand, 0.05 μ m or less mean diameter may cause spumescence reduction, the reduction of oils and fats arrangement property owing to the influence of emulsifying agent, and also cause the inferior position of cost aspect.In the present invention, the mean diameter of each liquid crystal structure can be seen particle image by optical microscope by input, 100 in hope enter computer, regulate their expansion multiplying power at par, standing image processing then (for example decides, by using " winROOF ", computer software).
Can be according to shampoo composite of the present invention by disclosed method preparation among conventional method or the JP2001-311099A.Preferred preparation preparation method is to mix the water that contains detergent surfactant (C), and cationic surfactant (A) and not siliceous oil component (B), temperature is not less than the crystallization temperature of component (A) and mixture (B), then from being not less than the temperature cooling mixture of crystallization temperature.The water that more preferably contains detergent surfactant (C) by mixing, with cationic surfactant (A) and not siliceous oil component (B), continuous drawing of piecemeal and cancellation mixture, and return cancellation part in mixture, repeat drawing, cancellation and return from being not less than the temperature cooling mixture of crystallization temperature.According to this method, can be shortened cool time.When the swollen clay mineral of water (D) when allocating into, on the other hand, water swelling clay mineral, its dispersion or swell in the water, it is preferred mixing with the water that contains detergent surfactant.When continuing to produce many batches, this method can be exempted clean container inside between per two batches, and therefore can significantly improve production efficiency.
During blending ingredients, having no particular limits aspect their the interpolation order.The composition of liquid crystal structure can be added in the aqueous phase that contains detergent surfactant, and vice versa.If temperature is low, liquid crystal structure tends to solidify, and from finishing dispersive angle just, agitator treating agent surfactant under heating is preferred in heating and dissolved state annex solution crystal structure while.
Mixing temperature is equal to or higher than the crystallization temperature of the constituents mixt that forms liquid crystal structure.By the married operation under such temperature, liquid crystal structure can mix and be dispersed in the detergent surfactant equably.
The crystallization temperature (after this being abbreviated as " T ℃ ") that forms the component mixture of liquid crystal structure is not that the mixture that shows them simply mixes, heating and dissolved crystallization temperature, and has shown the crystalline mixture temperature at the aqueous phase that contains detergent surfactant.T ℃ can be by providing shampoo composite as sample and use differential scanning calorimetry (DSC) to measure simply.T ℃ can be by operational measure under following condition by mensuration-sample number: 5-50mg the most accurately, temperature scanning rate: 0.5-2.0 ℃/min.
The dsc measurement figure of the typical shampoo composite of following prescription is shown in Fig. 2.Shampoo composite (33mg) is measured under 1 ℃/min of temperature scanning rate.In Fig. 2, the transition peak that leftmost big endothermic peak is a liquid crystal structure, and, can observe little endothermic peak on the higher temperature one side at transition peak.T ℃ of correspondence is at the endothermic temperature of endothermic peak end.T ℃ is 73 ℃ under the situation of this sample.
Figure C20038010320000241
In order to produce its T ℃ with measured shampoo composite, the constituents mixt that forms liquid crystal structure in compositions is at first prepared.Heating blends is measured its solution temperature.At least be higher than at detergent surfactant and liquid crystal structure thoroughly mix under the temperature of 10 ℃ of solution temperatures after, consequent mixture is cooled to 30 ℃ or lower (for cooling means, common chuck cooling is available; Cooldown rate: 0.5-2.0 ℃/min).After preparation, consequent mixture is placed 3 days or longer, measures its T ℃ by DSC as sample then.
Next preparation in accordance with the present invention, consequent mixture are cooled off from the temperature that is not less than crystallization temperature.Have no particular limits for cooling means.Mixture can be cooled, and crosses the chuck that mixes on the container outer wall or constantly piecemeal drawing and cancellation mixture and returned the cancellation part to mixture and repeat drawing, cancellation and return (after this owing to write a Chinese character in simplified form be called " the constantly cancellation method of a part part ") by cooling water flow.Especially from shortening the angle of cool time, constantly the cancellation method of a part part is preferred.Herein the term of Shi Yonging " cancellation " mean mixture in moment by its hot state by cancellation to 10-35 ℃.
Cancellation method about a continuous part part will be described.
In the method for preparation shampoo composite of the present invention, compositions exists with the form of composition of detergent and liquid crystal structure mixture, and temperature is T ℃ or higher soon before beginning to cool down.Constantly the cancellation method feature of a part part is constantly a part of drawing and cancellation mixture, returns the part of cancellation and repeats drawing, cancellation and return, and the temperature of whole like this mixture is lowered.The object lesson that is suitable for constantly the container of the cancellation method of a part part is shown in the chart among Fig. 1.
In mixer 1 preparation T ℃ or higher shampoo composite be recycled by circulation route 2.Circulation route 2 is equipped with heat exchanger 4 at the middle part.Cold water, gushes by cooling water circuit 3 by cooling water circuit 3 inflow heat exchangers 4 then from water chiller 5.The shampoo composite that recycle circuit 2 is passed in circulation is continued cooling and is returned mixer 1 by heat exchanger 4.
More solito is characterised in that the cooling water by the external container chuck of flowing through progressively flows into, and said method make to shorten cool time to 1/2 and becomes possibility to 1/5.In this case, the temperature of cooling water can from 1 to 25 ℃, preferably from 1 to 15 ℃.Be lower than 1 ℃ temperature and cause cooling water to freeze hindering cooling, and temperature is higher than 25 ℃ and causes low cooling effectiveness.If the handling capacity height of heat exchanger 4 increases the circulation volume of shampoo composite in each constant time, cooling effectiveness can be further improved.From the angle of convenient control cooling terminal temperature, preferably set the temperature of shampoo composite and cooling water, they a part connect part cooling back when heat exchanger 4 comes out at 5-20 ℃, be lower than the whole composition cools terminal temperature of setting.
In order to realize this a part of constantly cancellation method that connects a part, it is essential that the viscosity of shampoo composite can not significantly improve around the temperature of cooling water.High viscosity may cause the cooling segment of shampoo composite in heat exchanger to solidify, thereby can not further cool off.For fear of this problem, the temperature of cooling water can be established highlyer.Yet such high temperature is set may cause the slower rate of cooling of shampoo composite, and therefore, may make economic interests shrink.If the viscosity of shampoo composite is 2.0pa.s or lower at 5 ℃, for example, can obtain high cooling effectiveness.
By way of parenthesis, this viscosity shows shampoo composite viscosity in the preparation, and therefore, be different from substantially when compositions and be cooled to 5 ℃, its form final composition as cooling the viscosity as a result the time, because after forming final composition, along with the time forms in the liquid crystal structure process, cause viscosity to increase in system.
Further, preferably comprise the mixed clay mineral according to the preparation method of shampoo composite of the present invention, it can and contain the step of the water of detergent surfactant by aqueous dispersion or swelling.This additional step makes the crystalline precipitation that fully suppresses the liquid crystal structure component become possibility, even connect cancellation process partially in a part that continues, when wherein crystal took place especially easily, liquid crystal structure can disperse with being stabilized.Be accompanied by a problem in the method that water swelling clay mineral directly adds, continue to produce multiple batches of at identical mixer if desired, after producing any front batch, the shampoo composite that still is retained in the inwall etc. of container in ensuing production process is sneaked into, and influences the effect that water swelling clay mineral suppresses crystal settling.For fear of this problem, the production of next batch needs to carry out after clean container inside.Yet, this between two batches clean container inside can eliminate by being dispersed in the water or mixing with the water that contains detergent surfactant with the swollen clay mineral of water, so production efficiency can be significantly increased.In addition, the liquid mixture that contains the water-soluble bloated clay of 1-5wt% that exists with the dispersion or the form in the water that swells in, can change into liquid mixture, it has high security and low viscosity and transfer easily, by heating previously mentioned liquid mixture as required to 50-80 ℃.
Can use with the usual amounts of shampoo according to conventional methods according to shampoo composite of the present invention.It can bring such beneficial effect, gives low hair friction sense and fabulous spumescence and fabulous dispersion stability with time.Therefore, preferably use shampoo composite of the present invention, especially for because the hair that dyeing has damaged.
Can be loaded into according to shampoo composite of the present invention in the pipe of aluminium flake pipe for example, EVAL pipe and aluminum pipe, also can place the container dispersion cup for example that uses mechanical pressure or different pressure, squeeze receptacle, membrane container, spray containers, lipstick container and bottle container.Thin film generally is equipped with multilamellar, be two-layer or more multi-layered, each layer by synthetic resin for example polyethylene, poly-terephthalic acids second diester, polyester, two spindle guides to polypropylene, non-guiding polypropylene, polyacrylonitrile or vinyl-vinyl acetate copolymer, paper, plastic-aluminum or the like make.From the angle of intensity, elasticity, weathering resistance or the like, 2 to 5 layer films generally are used.As for the material of bottle, polyethylene, polypropylene, poly-terephthalic acids second diester, polystyrene, polrvinyl chloride, ethylene-vinyl alcohol resin, acrylonitrile-styrene resin, ABS resin, polyamide, glass or the like can be used to form the two-layer or multiwalled combination of monolayer.
According to the present invention, it is possible obtaining such shampoo composite, and it gives low hair friction sense after rinsing, when making the user feel the colored hair of hair friction, and fabulous spumescence and fabulous dispersion stability with time.
Embodiment
Based on the following examples and comparative examples, the present invention is carried out clear and definite description., what need remember is that the present invention is not limited in the following examples.In the following embodiments, " % " of expression and the compositions relation that is useful on is meant " wt% ".
Embodiment 1-12 and comparative examples 1-8
According to following table 1 and 2 described prescriptions, described production routine prepares shampoo composite below adopting.They rub residual by spumescence, nothing and dispersion stabilization marking.The result also is listed in table 1 and 2.It should be noted that in form each " (B ') " expression comprises the oil-phase component in correspondingly (B) composition, and can form liquid crystal structure with corresponding composition (A).
[production routine]
I. oil-soluble composition, just composition (A), composition (B) and other oil-soluble compositions are heated between 45 ℃ to 80 ℃ dissolving and make oil phase.
Ii. surfactant and other water soluble ingredients are dissolved between room temperature to 80 ℃ and make water in the purified water.
Iii. the oil phase that the i step is obtained joins the aqueous phase that the ii step obtains, and stirs in a homogeneous phase agitator then, forms the O/W emulsion.
Iv. emulsion is cooled to room temperature gradually under the oar formula stirs, and the selectable pH value that carries out is regulated under the situation of needs, and obtains shampoo composite.
[shampoo spumescence grade]
＜method 〉
Each shampoo composite is had 10 women panels of expert that are short to middle length and dyed the hair of brown to be used 10 days.In use, the spumescence of shampoo composite is arranged based on the rating fraction that describes below.In form, the total points that 10 panels of expert provide is to draw according to the hierarchical arrangement standard that describes below.
As product for example rinsing or the conditioner of can taking a shower, and non-shower product for example Hairstyling composition or hair care product, these all use after using shampoo, and each specialist crew who is tried uses those that she uses usual every day.
＜rating fraction 〉
+ 2: fine
+ 1: have a few
-1: somewhat bad
-2: very bad
＜standard 〉
◎: gross score 〉=15
◎-zero: 14 〉=gross score 〉=10
Zero: 9 〉=gross score 〉=5
△: 4 〉=gross score 〉=0
△-* :-1 〉=gross score 〉=-4
* :-5 〉=gross score
[hair after using the rinsing shampoo rub tactile grade]
＜method 〉
Each shampoo composite is had 10 women panels of expert that are short to middle length and dyed the hair of brown to be used 10 days.In use, the friction of the hair after rinsing sense of touch is arranged based on the rating fraction that describes below.In form, the total points that 10 panels of expert provide is to draw according to the hierarchical arrangement standard that describes below.
As product for example rinsing or the conditioner of can taking a shower, and non-shower product for example Hairstyling composition or hair care product, these all use after using shampoo, and each specialist crew who is tried uses those that she uses usual every day.
＜rating fraction 〉
+ 2: fine
+ 1: have a few
-1: somewhat bad
-2: very bad
＜standard 〉
◎: gross score 〉=15
◎-zero: 14 〉=gross score 〉=10
Zero: 9 〉=gross score 〉=5
△: 4 〉=gross score 〉=0
△-* :-1 〉=gross score 〉=-4
* :-5 〉=gross score
[with respect to the grade of the dispersion stabilization of time]
＜method 〉
The shampoo composite for preparing is placed on 50 ℃ of next months.By observing its outward appearance and in the observation of polarizing microscope, they are arranged on dispersing uniformity based on following classification standard.
＜standard 〉
◎: fine
Zero: good
△: general
*: bad
By shampoo composite being filled in the storage of carrying out certain hour in the following described container (1) to (9) respectively.In the following description, following abbreviation is useful-PE: polyethylene, PP: polypropylene, PET: polyethylene terephthalate, PA: polyamide, HDPE: high density polyethylene (HDPE).
＜bottle container 〉
(1) body part: PP, bottle cap: PP
(2) body part: HDPE, bottle cap: PP
(3) body part: PET, bottle cap: PP
(4) body part: PP/HDPE, bottle cap: PP
＜pump equipment container 〉
(5) body part: PP, dispenser portion: PP, PE, SUS304
(6) body part: HDPE, dispenser portion: PP, PE, SUS304
(7) body part: PET, dispenser portion: PP, PE, SUS304
(8) body part: PP/HDPE, dispenser portion: PP, PE, SUS304
＜packed container 〉
(9) calorize Polythene Bag
Figure C20038010320000301
Figure C20038010320000311
Figure C20038010320000321
Figure C20038010320000331
Figure C20038010320000341
Figure C20038010320000351
Embodiment 13-22 and comparative examples 9-14
According to following table 3 and 4 described prescriptions, described production routine prepares shampoo composite below adopting.Based on following described rank method, they are arranged according to spumescence, nothing friction rinsing, arrangement compliance, the no greasy of arrangement and dispersion stabilization.The result also is listed in table 3 and 4.
[production routine]
I. oil-soluble composition, just composition (A), composition (B) and other oil-soluble compositions are heated between 60 ℃ to 80 ℃ dissolving and make oil phase.
Ii. surfactant and other water soluble ingredients are dissolved between 60 ℃ to 80 ℃ and make water in the purified water.
Iii. the oil phase that the i step is obtained joins the aqueous phase that the ii step obtains, and stirs in a homogeneous phase agitator then, forms the O/W emulsion.
Iv. emulsion is cooled to room temperature gradually under the oar formula stirs, and the selectable pH value that carries out is regulated under the situation of needs, obtains shampoo composite.
By the way, composition (F) may be combined in the i oil phase in step according to their character separately or is blended in the ii aqueous phase in step, or is blended in the iv mixture in step, adds after the temperature of mixture has been reduced to room temperature.
The average particle size particle size of each liquid crystal structure is passed through the granule image, by optical microscope as seen, be input in the computer at 100 required points, in identical rank, adjust their magnified image, then they are carried out Flame Image Process (software " winROOF " that for example uses a computer is handled).
[spumescence of shampoo and use shampoo after the hair tactile grade that rubs]
They use and arrange as embodiment 1 described similar methods.
[compliance of aligning method and arrangement hair and the standard of no greasy]
＜method 〉
In 10 women panels of expert each was dyed the people's who sends out hair from middle separated into two parts.Part in the hair is used the shampoo composite in arbitrary embodiment or the comparative examples, and another part uses the described contrast shampoo of following prescription, each consumption 3.0mL.The compliance of arrangement back hair and no greasy are based on following described rating fraction and arrange.In form, the total points that 10 panels of expert provide is to draw according to the hierarchical arrangement standard that describes below.
The contrast shampoo
Prescription wt%
Polyoxyethylene alkyl ether sodium sulfate 10%
(the average mol of the EO of adding: 3)
Fatty acid distribution of coconut oil aminopropyl betanin 5%
Sodium chloride 2%
Dimethyl polysiloxane (100000cSt) 1%
Poise C-80M 0.3%
Trimethyl glycine 0.2%
Citric acid 0.2%
Fatty acid distribution of coconut oil single ethanol amide 0.8%
Glycol distearate 1%
Sodium benzoate 0.4%
Essence 0.5%
The surplus of purifying waste water
Total amount 100%
＜rating fraction 〉
+ 2: comparison is good according to shampoo
+ 1: comparison is good slightly according to shampoo
+ 0: be comparable to the contrast shampoo
-1: comparison is poor slightly according to shampoo
-2: comparison is poor according to shampoo
＜standard 〉
◎: gross score 〉=10
Zero: 9 〉=gross score 〉=5
△: 4 〉=gross score 〉=-4
* :-5 〉=gross score
As product for example rinsing or the conditioner of can taking a shower, and non-shower product for example Hairstyling composition or hair care product, these all use after using this shampoo, and each specialist crew who is tried uses those by the mode that she uses every day.
[with respect to the grade of the dispersion stabilization of time]
Use and arrange as embodiment 1 described similar methods.
Figure C20038010320000391
Figure C20038010320000401
Figure C20038010320000411
Figure C20038010320000421
Figure C20038010320000431
Figure C20038010320000441
Embodiment 23-26
According to the described prescription of following table 5, described production routine prepares shampoo composite below adopting.Based on following described rank method, they according to dispersion stabilization, spumescence and the rinsing of liquid crystal structure after hair friction feel arrange.The result also is listed in the table 5.
[production routine]
I. oil-soluble composition, just composition (A), composition (B) and other oil-soluble compositions are heated between 45 ℃ to 80 ℃ dissolving and make oil phase.
Ii. composition (D), composition (G) (joining in the oil phase according to its character), surfactant and other water soluble ingredients under agitation are dissolved in the purified water between room temperature to 80 ℃ and make WaterPhase.
Iii. the oil phase that the i step is obtained joins ii step acquisition WaterMutually, under the oar formula stirs, be cooled to room temperature gradually, and selectable pH value is regulated under the situation of needs, obtains shampoo composite.
Figure C20038010320000461
Embodiment 27-37
According to following described prescription, use similar embodiment 23 described production routines to prepare shampoo composite.The shampoo composite of embodiment 27-30 carries out hierarchical arrangement according to dissolubility, and the shampoo composite of embodiment 31-37 carries out hierarchical arrangement according to dissolubility and emulsus foam.Percentage by weight (wt%) consumption in embodiment separately of methoxy group in the hydroxypropyl emthylcellulose and hydroxyl propoxyl group group is different, and their 2% viscosity in aqueous solution and hierarchical arrangement result are illustrated in table 6 and 7.
Shampoo composite
Component wt%
Shan Yu base trimethyl ammonium chloride
(behenyltrimethylammonium chloride) 2.0
Behenyl alcohol 5.0
Bentonite 0.5
Hydroxypropyl emthylcellulose 0.2
CAB lauramide 13.0
Lauryl dimethyl amine oxide 1.0
Fatty acid distribution of coconut oil diglycollic amide 3.0
The surplus of purifying waste water
Total amount 100.0
Table 6
Hydroxypropyl emthylcellulose Embodiment 27 Embodiment 28 Embodiment 29 Embodiment 30
Methoxy group (%) 29 28 20 29
Hydroxyl propoxyl group group (%) 9 10 4 0
2% viscosity in aqueous solution (mPas) in the time of 20 ℃ 4000 4000 4000 4000
Dissolubility ◎ ◎ × ×
Table 7
Figure C20038010320000481
Embodiment 38-44
According to the described prescription of following table 8, use similar embodiment 23 described production routines to prepare shampoo composite.Based on following described aligning method, spumescence, foam lubricity, emulsus foam, nothing friction rinsing and dried smooth touch are carried out hierarchical arrangement.The result is also illustrated in the table 8.
Figure C20038010320000501
Embodiment 23-44 hierarchical arrangement method
[the viscosity measurement method of shampoo composite]
Following method 2 is the general experimental techniques in " the cosmetic material standard of Japan ", and the viscosity of each shampoo composite is to use the Brookfield viscometer to measure.
＜measuring condition 〉
Rotor: 3 or No. 4
Rotating speed: per minute 30 changes (30rpm)
＜measuring method 〉
Keeping the temperature of shampoo composite is 25 ± 1 ℃, and rotor is inserted in the compositions lightly.In compositions after static 1 minute, the beginning rotor after subsequently rotation 10 times, is measured viscosity.
[hierarchical arrangement of the long dispersion stability of liquid crystal structure]
＜method 〉
Each shampoo composite for preparing is placed on 40 ℃ of next months, and this temperature is near the unstable temperature (phase transformation point) of liquid crystal structure, and 40 ℃ following three months, the supposition of the storage condition of back was equivalent under the room temperature storage 1 year or longer.By its outward appearance (occur or do not occur being separated) with observe under polarizing microscope, shampoo composite is arranged dispersing uniformity according to following described hierarchical arrangement standard.Product is filled container above-mentioned (1) to be arrived
(9) store in.
＜classification standard 〉
◎: fine
Zero: good
△: general
*: bad
[hierarchical arrangement of the spumescence of shampoo composite and foam lubricity]
＜method 〉
Each shampoo composite is had 10 women panels of expert that are short to middle length and dyed the hair of brown to be used 10 days.In use, the spumescence of shampoo composite and foam lubricity are arranged based on the rating fraction that describes below.In form, the total points that 10 panels of expert provide is to draw according to the hierarchical arrangement standard that describes below.
As product for example rinsing or the conditioner of can taking a shower, and non-shower product for example Hairstyling composition or hair care product, these all use after using this shampoo, and each specialist crew who is tried uses those that she uses every day in the past.
＜rating fraction 〉
+ 2: fine
+ 1: have a few
-1: somewhat bad
-2: very bad
＜standard 〉
◎: gross score 〉=15
◎-zero: 14 〉=gross score 〉=10
Zero: 9 〉=gross score 〉=5
△: 4 〉=gross score 〉=0
△-* :-1 〉=gross score 〉=-4
* :-5 〉=gross score
[hierarchical arrangement of the sensation of hair frictional property after the cleaning shampoo]
Use and arrange with embodiment 1 identical mode.
[deliquescent hierarchical arrangement]
Prepare shampoo composite, after preparing, according to following described hierarchical arrangement standard the liquid situation is arranged immediately.
＜classification standard 〉
◎: uniformly without any precipitation or undissolved coagulation prod
Zero: uniformly,, but the little coagulation prod of slight amount is arranged without any precipitation
△: do not precipitate, but a considerable amount of big coagulation prods are arranged
*: precipitation is arranged, perhaps observe and be separated.
[the foamy hierarchical arrangement of emulsus]
Tress (every tuft 10 grams) is got wet with 5 gram water logging bubbles down at 40 ℃.Use shampoo composite (every tuft 1 gram) respectively, clean this tuft hair then, the emulsus foam of every tuft hair when cleaning compared with the contrast shampoo that does not contain hydroxypropyl emthylcellulose, sensuously arranging based on following arrangement standard.
＜classification standard 〉
Zero: obviously comparison is good according to shampoo
△: comparison is good according to shampoo slightly
*: the same with the contrast shampoo
[hierarchical arrangement of oven dry back silk wiping sense]
The hair of each member in 10 women panels of expert is from middle separated into two parts.Use as the described shampoo composite of embodiment in a part, use the contrast shampoo that does not contain hydroxypropyl emthylcellulose at another part, each consumption is 3mL.Silk wiping sensillary base after drying up is arranged through row in following described hierarchical arrangement mark.In form, the total points that 10 panels of expert provide is to draw according to the standard that describes below.
＜rating fraction 〉
+ 2: comparison is good according to shampoo
+ 1: comparison is good slightly according to shampoo
+ 0: be comparable to the contrast shampoo
-1: comparison is poor slightly according to shampoo
-2: comparison is poor according to shampoo
＜standard 〉
◎: be better than contrasting shampoo (gross score 〉=10)
Zero: be better than contrasting shampoo (9 〉=gross score 〉=5) slightly
△: with contrast shampoo level identical (4 〉=gross score 〉=-4)
*: be inferior to contrast shampoo (5 〉=gross score)
Embodiment 45-50
Production routine as described in Table 9 is prepared as follows the described shampoo composite of prescription, based on hierarchical arrangement standard as described below,
Stability when storing not having friction rinsing and-5 ℃ of degree is arranged.The result is also illustrated in the table 9.
Shampoo composite
Figure C20038010320000551
[product program]
The water-swellable mineral clay is dispersed in purify waste water (deionized water), then adds detergent surfactant.Further add the mixture and the dissolving modifying agent that prepare through heating mixed liquid crystal constituent in advance.The mixture heated of gained begins to cool down when whole liquid mixtures reach T2 ℃ to T1 ℃.When being cooled to about 40 ℃, liquid mixture adds other composition.Regulate citric acid so that the pH value of shampoo composite is 5.5.
As blending tank, can use vacuum emulsification jar (volume: 20L; " PVT-1-20 ", MizuhoIndustrial Co., Ltd product), according to the chuck cooling means, cooling is the water by carry 15 to 20 ℃ in the chuck of vacuum emulsification jar.According to continuous branch cooling means, use the heat exchanger of an outside.On the other hand, vacuum emulsification jar content constantly circulates, be by the collar extension of vacuum emulsification device being used pipe link to each other, and will be used for externally its pipe that turns back to emulsator being connected to the charging aperture that is installed in vacuum emulsification device top behind the heat exchanger internal cooling and realize at content with the outside heat exchanger through shifting pump.Heat exchanger as the outside can use " UX-005 " (Hisaka works product, heat transfer area " 0.612m 2).The volume of cooling water all is that cooling water enters heat exchanger in 5 to 7 ℃ like this, in 20 to 35 ℃ of outflow heat exchangers of content and cooling water through what adjust from start to end.Use the chuck cooling means to drop to time of 38 ℃ and be approximately 40 minutes, use outside heat exchanger, adopt continuous branch cooling procedure then to use 10 to 12 minutes from T2.
Before temperature change (T1 ℃ to T2 ℃) occurs in from emulsifying to cooling in very short time.During this period of time operation can be described.In embodiment 45 to 47 and 49, only be that the jacket steam heating stops when emulsifying begins, there is not compositions content change (natural cooling), in embodiment 48.On the other hand, the chuck heating stops, and the sodium benzoate of adding is made into 33% aqueous solution (aqueous temperature of sodium benzoate: 15 ℃) fully, adds, and stirs after emulsifying.In embodiment 50, the chuck heating stops, and adds the CAB lauramide of 1/3 amount, and stir (temperature of CAB lauramide is about 15 ℃, and other 2/3 amount adds) after emulsifying before emulsifying.With the crystallization temperature (T ℃) of the shampoo composite of the embodiment of the preparation of product process as described above, use differential scanning calorimetry (DSC) (DSC) (" DSC6100 ", SeikoInstrument, Inc. product) to measure respectively, being proved to be is 74 ℃.Measuring condition-sample size: 31mg (embodiment 45), 29mg (embodiment 46), 32mg (embodiment 47), 32mg (embodiment 48), 33mg (embodiment 49), 31mg (embodiment 50); Temperature scanning speed: 1 ℃/minute.
Further, the shampoo composite (when being cooled to 45 ℃) that therefore a small amount of sampling obtains in its production process.Be cooled to rapidly after 5 ℃,, measure viscosity (No. 3 rotors are measured more than 30 rpms of rotation 10 circles) with the Brookfield viscometer according to the method 2 in the general detection method in " Japanese cosmetic raw material standard ".The result is followed successively by 1.2 to 1.3Pas for the viscosity of the shampoo composite of embodiment 46 to 48, and this shows that cooling effectively finishes.With after, dismounting and clean outside heat exchanger can be observed its heat delivery zone.After cooling, do not find the solid precipitation material.
The shampoo composite that obtains like this after 24 hours, is similarly measured their viscosity in placement under 25 ℃ ± 2 ℃ conditions.The result is expressed as follows: 3.2Pas (embodiment 45), 2.4Pas (embodiment 46), 2.6Pas (embodiment 47), and 2.4Pas (embodiment 48).
[hierarchical arrangement of not having friction shampoo rinsing]
10 women of 20 years old to 40 years old that hair had been dyed, everyone uses shampoo composite to clean, and washes off with hot water then.At this moment according to following listed hierarchical arrangement standard the hair frictional property is arranged.
＜classification standard 〉
◎: 9 or more women's answer " nothing friction "
The women answered " not having friction " in zero: 6 to 8
△: 3 to 5 women answer " not having friction "
*: 2 or the answer of women still less " nothing friction ".
[hierarchical arrangement of 5 ℃ of following bin stabilities]
Each shampoo composite is filled into container described above (1) in (9).Container is positioned in the thermostat, and the control temperature is placed after one month at-5 ± 1 ℃, places them in 22 to 26 ℃ the environment 3 days.With whole another containers of transferring to of the shampoo composite in each container, for example in the Petri dish, observe outward appearance, arrange according to right-5 ℃ of following bin stabilities of following listed hierarchical arrangement standard.
＜classification standard 〉
◎: in arbitrary container, both be not separated and also do not observed solid deposits
Zero: in some containers, observe by crystal settling cause slightly gorgeous
△: in some containers, observe the solid deposits that with the naked eye to see
*: in some containers, observe a large amount of solid block precipitation that can with the naked eye see or observe and be separated.
Table 9
Figure C20038010320000581
Embodiment 51
Use with embodiment 46 similar programs and be prepared as follows the listed shampoo composite of prescription.
Component wt%
INCROQUAT TMC-80 ECONOL TM22 2.0
Behenyl alcohol 5.0
Behenic acid monoglyceride (HLB4.3) 0.3
Shan Yu ether (EO10) (HLB 9) 0.3
Fatty acid distribution of coconut oil diglycollic amide 3.0
CAB lauramide 13.0
Alkyl (8-16) glucoside 1.0
Bentonite 0.3
Lauric acid dimethyl amine oxide 1.0
Dimethyl polysiloxane 1.8
Amino modified polysiloxane 0.2
Propylene glycol 5.0
Sodium benzoate 0.9
Arginine 0.5
Citric acid 0.5
Essence 0.5
The surplus of purifying waste water
Total amount 100.0%
Character
Viscosity 5Pas
Proportion 1.02 (25 ℃)
pH 5.8
Shampoo composite has thixotropy.
The X-ray analysis result of the shampoo composite of all embodiment can be observed diffraction pattern clocklike.When observing diffraction pattern under polarizing microscope, their structure image shows visual anisotropy.Further, under the freezing point scanning electron microscope, can observe refrigerated broken sample.Can find that as a thin layer being one is positioned on another, the shampoo composite of all embodiment that obtain with product program described above is proved and contains the liquid crystal structure that is dispersed in wherein.
Commercially produced product below using in described in the above embodiment and the comparative examples.
※ stearyl trimethyl ammonium chloride: " ARQUARD T833 " (Lion Corporation product)
This business-like product is the stearyl trimethyl ammonium chloride, meet " Japanese cosmetic raw material standard " (being abbreviated as " JSCI " hereinafter), aqueous solution form with about 33% purity exist (residue is the JSCI dehydrated alcohol: 29%, JSCI purifies waste water: 38%).In form, the amount of stearyl trimethyl ammonium chloride as described herein is based on that purity calculates.
※ Shan Yu base trimethyl ammonium chloride: " ARQUARD 22-80 " (Lion Corporation product)
This business-like product Shi Shan Yu base trimethyl ammonium chloride meets JSCI, exists with the solid form of about 80% purity.In form, the amount of mountain as described herein Yu base trimethyl ammonium chloride is based on that purity calculates.
Appendix 2 referring to " Japanese cosmetic raw material standard ".
Use derives from the unprocessed sinapic acid raw material of sarson seed oil, and this product is to come synthetic by long-chain amine.The distribution of lengths of the alkyl chain of long-chain amine is expressed as follows:
C 16Or shorter≤2%
C 18 ≤6％
C 20 ≤6％
C 2287% to 93%
C 24 ≤3％
※ VARISOFT TA100: " ARQUARD 218P-75E " (Lion Corporation product)
This business-like product is a VARISOFT TA100, meets JSCI, exists with the pasty state form of about 75% purity.In form, the amount of VARISOFT TA100 as described herein is based on that its purity calculates.By the way, this chemical compound is alkyl (thiazolinyl) C18F0: the C18F1=75 that quaternary ammonium salt comprises it: 25.
※ butyl guanidine acetamide lauramide aqueous solution: " C12A4G " (Lion Corporation product)
The purity of aqueous solution about 32%.In form, the amount of butyl guanidine acetamide lauramide aqueous solution as described herein is based on that its purity calculates.
※ spermol: " Lorol C16 " (Cognis Japan Ltd. product)
The product that meets JSCI.Its chain length distributes approximately as follows:
C 140 to 3%
C 16 ≥95％
C 180 to 5%
※ stearyl alcohol: " CONOL 30SS " (New Japan Chemical Co., Ltd. product)
The product that meets JSCI.
※ hydrogenated rapeseed oil: " Stenol 1822SR " (Cognis Japan Ltd. product)
The product that meets JSCI.Its chain length distributes approximately as follows:
C 16Or shorter 〉=1.5%
C 1840 to 46%
C 208 to 14%
C 2242 to 48%
C 24 ≤0.5％
※ behenyl alcohol: " LANETTE 22 " (Cognis Japan Ltd. product)
The product that meets JSCI.Solid.
This product derives from Cortex cocois radicis gel oil, and its alkyl chain length distributes approximately as follows:
C 16 ≥0.5％
C 185 to 15%
C 2010 to 20%
C 2270 to 80%
C 24 ≤1％
※ stearic acid: " Stearic Acid 100 " (New Japan Chemical Co., Ltd. product)
The product that meets JSCI.
The single glyceryl stearate of ※: " RIKEMAL S-100 " (Riken Vitamin Co., Ltd. product)
The product that meets JSCI.White solid.Fusing point 62-68 ℃, HLB 4.3
The single Gan You of ※ behenic acid ester: " RIKEMAL B-100 " (Riken Vitamin Co., Ltd. product)
The product that meets JSCI.White solid.Fusing point 74-80 ℃, HLB 4.2
※ Shan Yu ether (EO 10): " EMALEX BHA-10 " (Ni hon Emulsion Co., Ltd. product)
The product that meets JSCI.White solid.HLB 9
※ hard paraffin (EO 10): " Solid Paraffin " (Nippon Seiro Co., Ltd. product)
Meet JSCI " high melting point paraffin ".
※ diglycol stearate: " Genapol PMS " (Clariant (Japan) Ltd. product)
The diglycol stearate that meets JSCI comprises C 16And C 18, composite rate is 6: 4.
This raw material is joined mode in the relevant shampoo: in order to improve its dispersibility in shampoo, the aqueous solution of POE sodium alkylether sulphate (20wt%), fatty acid distribution of coconut oil diglycollic amide (25wt%) is mixed with into dispersion with raw material (25wt%) down at about 80 ℃ in advance with water (30wt%), then this dispersion is joined in the shampoo solution.
※ fatty acid distribution of coconut oil diglycollic amide: " CDE-100 " (Kawaken Fine ChemicalsCo., Ltd. product)
Meet JSCI " fatty acid distribution of coconut oil diglycollic amide ".
※ POE (20) castor oil hydrogenated: " CW-20-90 " (Aoki Oil Industrial Co., Ltd. product)
The polyoxyethylene hydrogenated Oleum Ricini that meets JSCI is the aqueous solution form of about 90% purity.In form, the amount of POE as described herein (20) castor oil hydrogenated is based on that its purity calculates.
※ polyoxyethylene laurel ether sodium sulfate: " POE sodium alkylether sulphate " (Lion Corporation product)
Polyxyethylated (12,13) the ether sodium sulfate solution (3E.O.) that meet JSCI are the aqueous solutions of about 27% purity.In form, the amount of POE sodium alkylether sulphate described herein is based on that its purity calculates.
※ tetradecene sodium sulfonate: " tetradecene sodium sulfonate " (Lion Corporation product)
The tetradecene sodium sulfonate solution that meets JSCI is the aqueous solution of about 35% purity, contains hydroxy alkyl sulfonic acid sodium.In form, the amount of described tetradecene sodium sulfonate is based on that its purity calculates.
※ CAB lauramide: " ENAGICAL N30B " (Lion Corporation product)
The CAB lauramide solution that meets JSCI is the aqueous solution of about 30% purity.In form, the amount of CAB lauramide as described herein is based on that its purity calculates.
※ lauryl dimethyl aminoacetate betanin: " OVAZOLIN LB-SF " (Toho ChemicalIndustry Co.Ltd. product)
What meet JSCI is the aqueous solution of about 35% purity.In form, the amount of lauryl dimethyl aminoacetate betanin as described herein is based on that its purity calculates.
※ lauryl hydroxy sulfo lycine: " ANPHITOL 20HD " (Kao CORPORATION product)
The lauryl hydroxy sulfo lycine that meets JSCI is the aqueous solution of about 30% purity.In form, the amount of lauryl dimethyl aminoacetate betanin as described herein is based on that its purity calculates.
The ※ alkyl gathers (8-16) glucoside: " PLANTACARE 818UP " (Cognis Japan Ltd. product)
Poly-(8-16) glucoside of alkyl that meets JSCI is the liquid of about 52% purity.In form, the amount of poly-(8-16) glucoside of alkyl as described herein is based on that its purity calculates.
This product derives from Cortex cocois radicis gel oil, and its alkyl chain length distributes as follows:
C 824 to 30%
C 1015 to 22%
C 1237 to 42%
C 1412 to 18%
C 16 ≤4％
The ※ bentonite: " KUNIPIA F " (KUNIMINE INDUSTRIES CO.LTD. product)
The product that meets JSCI.
The synthetic bentonite of ※: " SUMECTON SA " (KUNIMINE INDUSTRIES CO.LTD. product)
The product that meets JSCI.
※ lauryl dimethyl amine oxide: " Aromox DM12D-W " (Lion Corporation product)
The lauryl dimethyl amine oxide solution that meets JSCI is the aqueous solution of about 33% purity.In form, the amount of lauryl dimethyl amine oxide as described herein is based on that its purity calculates.
※ dimethyl (gathering) siloxanes (100000cSt): " LEOFLOW DMS-55 " (LionCorporation product), refractive index: 1.404
Obtain dispersion by emulsifying in water and the highly polymeric methyl polysiloxane of dispersion, meet JSCI, viscosity is 100000cSt, and mean molecule quantity is 130000, meets POE (15) cetyl ether of JSCI.The concentration of dimethyl (gathering) siloxanes is about 55%.The about 0.5 μ m of the average particle size particle size of the dimethyl polysiloxane in aqueous dispersion.In form, the amount of dimethyl polysiloxane as described herein is based on that its purity calculates.
※ dimethyl polysiloxane (1000000cSt): " BY22-050A " (Dow Corning ToraySilicone Co., Lt d. product), refractive index: 1.404
※ dimethyl (gathering) siloxanes (10000000cSt): " BY22-055A " (Dow Corning ToraySilicone Co., Lt d. product), refractive index: 1.400
※ amino modified (gathering) siloxanes: " SM8704C " (Dow Corning Toray SiliconeCo., Ltd. product)
The ammonia dimethyl siloxane aqueous dispersion that meets JSCI, the concentration of wherein amino modified (gathering) siloxanes is about 40%.The about 0.1 μ m of average particle size particle size of amino modified (gathering) siloxanes in dispersion.In form, the amount of amino modified (gathering) as described herein siloxanes is based on that its purity calculates.Refractive index: 1.405.
(gathering) siloxanes (polyoxyethylene-methyl (gathering) silicone copolymers) that ε ※ is polyether-modified: " SH3775M " (Dow Corning Toray Silicone Co., Ltd. product) refractive index: 1.423.
The product that meets JSCI.
The ※ Poise C-80M: the name of " XE-511K " (Lion Corporation product) in JSCI is called " O-[hydroxyl-3-(trimethyl ammonium)-propyl group] hydroxyethyl-cellulose chloride ".
The ※ hydroxypropyl cellulose: " HPC-SL " (Nippon Soda Co., Ltd.)
※ hydroxypropyl emthylcellulose (1): " METOLOSE 60SH-4000 " (Shin-Etsu ChemicalCo., Lt d. product), methoxyl group: 29wt%, propoxyl: 10wt%, 2% viscosity in aqueous solution: 4000mPas in the time of 20 ℃
※ hydroxypropyl emthylcellulose (2): " METOLOSE 60SH-10000 " (Shin-Etsu ChemicalCo., Lt d. product), methoxyl group: 29wt%, propoxyl: 10wt%, 2% viscosity in aqueous solution: 10000mPas in the time of 20 ℃
※ hydroxypropyl emthylcellulose (3): " METOLOSE 60SH-1500 " (Shin-Etsu ChemicalCo., Ltd. product), methoxyl group: 29wt%, propoxyl: 10wt%, 2% viscosity in aqueous solution: 1500mPas in the time of 20 ℃
※ hydroxypropyl emthylcellulose (4): " METOLOSE 60SH-400 " (Shin-Etsu ChemicalCo., Ltd. product), methoxyl group: 29wt%, propoxyl: 6wt%, 2% viscosity in aqueous solution: 400mPas in the time of 20 ℃
※ xanthan gum: " MONART GUM DA " (CP Kelco Aps product)
※ height polymerization PEG (Polyethylene Glycol): " POLYOX WSR 60K-CG " (Union CarbideCorporation product)
※ PEG (Polyethylene Glycol) distearate (150EO): " EMA LEX 6300D1-ST " (NihonEmulsion Co., Ltd. product)
※ dimethyl diallyl ammonium chloride-acrylamide copolymer: " KAYACRYL RESINMN-50 " (Nippon Kayaku Co., Ltd. product)
Dimethyl diallyl ammonium chloride-acrylamide copolymer the solution that meets JSCI is the aqueous solution of purity about 5.5%.
The ratio of monomer diallyldimethylammonChloride Chloride and acrylamide is approximately 1: 1.In form, the amount of dimethyl diallyl ammonium chloride-acrylamide copolymer as described herein is based on that its purity calculates.
※ propylene glycol: " propylene glycol " (Asahi Class Co., Ltd. product)
The ※ sorbitol: " the D-sorbitol solution " (Towa Chemical Industry Co., Ltd. product) sorbitol solution of meeting JSCI is the aqueous solution of about 60% purity.In form, the amount of sorbitol as described herein is based on that its purity calculates.
※ hydrolytic collagen solution: " PROMOIS W-52 " (Seiwa Kasei Co., Ltd. product) meets the product of JSCI.
※ hydrolyzed silk protein solution: " PROMOIS SILK 1000 " (Seiwa Kasei Co., Ltd. product)
The product that meets JSCI.
※ hydrolyzed wheat protein: " CROPEPTIDE W " (Croda Japan K.K. product)
The product that meets JSCI.
※ hydrolyzed wheat peptide A: " GLUADIN WLM " (Cognis Japan Ltd. product), molecular weight: 500
※ hydrolyzed wheat peptide B: " GLUADIN WLM " (Cognis Japan Ltd. product), molecular weight: 2000 to 5000
※ yellow 5: " yellow 5 " (Daiwa Dyestuff Mfg.Co., Ltd. product)
※ yellow 203: " Quinoline Yello-WS-G " (Chuo Synthetic ChemicalCo., Ltd. product)
※ redness 106: " red 106 " (Kishi Kasei Co., Ltd. product)
※ brown 201: " brown 201 " (Kishi Kasei Co., Ltd. product)
※ green 3: " green 3 " (Kishi Kasei Co., Ltd. product)
※ green 201: " green 201 " (Koyokagaku Co., Ltd. product)
※ methyl parahydroxybenzoate (Yoshitomi Fine Chemicals, Ltd. product) meets the product of JSCI.
※ sodium benzoate: the sodium benzoate (BF Goodrich Kalama Inc. product) that meets JSCI
※ methylchloroisothiazandnone-Methylisothiazolinone solution JSCI names " KATHON " (Rohmand Haas Japan K.K. product).In form, the addition of solution was narrated.
※ glycine (Ajinomo to Co., Inc. product) meets the product of JSCI.
※ arginine (Ajinomo to Co., Inc. product) meets the product of JSCI.
※ glutamic acid (Ajinomo to Co., Inc. product) meets the product of JSFD (japanese food additive standard).
※ citric acid: " monohydrate potassium " that " Kessho Kuensan L " defines in JSCI (FusoChemical Co., Ltd. product)
※ 2-pyrrolidone-5-carboxylic acid (Ajinomoto Co., Inc. product) meets the product of JSCI.
※ phosphoric acid (Junsei Chemical Co., Ltd. product)
※ triisopropanolamine (Mitsui Kagaku Fine Chemicals Inc. product)
※ essence
Use the essence of following formulation.
wt％
Fructus Citri Limoniae oil 5%
Oleum Citri sinensis 10%
Flos Pelargonii oil 3%
Oleum lavandula angustifolia 6%
Oleum Santali albi 1%
lilial 5％
nopyl acetate 1％
Coriandrol 2%
Benzyl benzoate 2%
Benzyl salicylate 3%
Alpha, beta-lonone 2%
methylionone 3％
helional 2％
hedion 8％
Iso E Super 3％
Cis-3-hexenol 0.3%
ligandral 0.3％
triplal 0.4％
Cyclamen aldehyde 1.5%
Jasminolene 6%
beltfix 3％
galaxolido 5％
tonalid 6％
bendalid 1％
bacdanol 0.5％
cashmeran 2％
Astrotone 1%
Fruit based 3%
Rhodinyl 3%
Jasmine base 1%
Mugestbase 3％
Amber base 1%
Aldehyde C-9 10% 2 inferior propylene glycol solution 2%
N-capric aldehyde 10% 2 inferior propylene glycol solution 1%
Methyl nonyl aldehyde 10% 2 inferior propylene glycol solution 2%
Two inferior propylene glycol surpluses
Total amount 100%

Claims (9)

1. shampoo composite, contain:
(A) cationic surfactant,
(B) not siliceous oil component,
(C) amphoteric surfactant and optional anion surfactant and
(D) water swelling clay mineral,
The scope from 0.35 to 0.90 of weight rate wherein (B ')/[(A)+(B ')], (B ') is meant to be included in the described composition (B) and by himself and can forms the oil component of liquid crystal structure with described composition (A), the total amount of described amphoteric surfactant and optional anion surfactant accounts for the 5wt% at least of the gross weight of described compositions, the amount of described anion surfactant account for composition total weight less than 5wt%, the described liquid crystal structure that is made of composition (A) and composition (B) is dispersed in the compositions.
2. shampoo composite as claimed in claim 1, the mean diameter of wherein said liquid crystal structure are that 0.05 μ m is extremely less than 20 μ m.
3. shampoo composite as claimed in claim 1 or 2, wherein said water swelling clay mineral amount accounts for the 0.01-5wt% of composition total weight.
4. shampoo composite as claimed in claim 1 or 2 further contains: (E) amine oxide.
5. shampoo composite as claimed in claim 1 or 2, further contain: (F) refractive index is less than 1.46 silicone derivative.
6. shampoo composite as claimed in claim 1 or 2, further contain: (G) as viscosity increasing agent, contain the unitary hydroxypropyl emthylcellulose of following formula:
Figure C2003801032000002C1
Wherein molecular end and R each represent hydrogen atom or methyl or hydroxypropyl, it contains 25 and arrives the methoxyl group of 35wt% and 5 to 15wt% propoxyl, collateral condition is that the total amount of hydroxyl, described methoxyl group and described propoxyl is 100wt%, and measuring its 2wt% viscosity in aqueous solution down at 20 ℃ is 2100 to 35000mPas.
7. shampoo composite as claimed in claim 1 or 2 is used for going up the hair of color.
8. prepare the method for shampoo composite as claimed in claim 1, comprise the following step:
The water swelling clay mineral that disperses or swell in the water is mixed with the water of the anion surfactant that contains amphoteric surfactant and choose wantonly,
The water that will contain described water swelling clay mineral and described amphoteric surfactant and optional anion surfactant mixes under the mixing temperature of the crystallized temperature of the component that is not less than described formation liquid crystal structure with the component of the formation liquid crystal structure that comprises cationic surfactant (A) and not siliceous oil component (B), from described mixing temperature cooling mixture, thereby make this shampoo composite, wherein said liquid crystal structure is dispersed in the described aqueous phase that contains detergent surfactant.
9. method as claimed in claim 8, wherein the gained mixture is by the continuous drawing of piecemeal, cancellation and returns the gained mixture and repeat said drawing, cancellation and return from mixing temperature and cool off.
CNB200380103200XA 2002-11-15 2003-11-14 Shampoo composition Expired - Lifetime CN100435772C (en)

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