JP4524752B2 - Permanent wave agent - Google Patents

Description

  The present invention relates to a permanent wave agent. In particular, the present invention relates to a cream (semi-solid) permanent wave agent and an emulsified liquid (hereinafter simply “liquid”) permanent wave agent.

  Conventionally, natural substances (natural substances and substances derived from them) have been used as raw materials for cosmetics (for example, hair care products). For example, plant-derived substances such as phytosterols and phytosterol fatty acid esters are used as cosmetic raw materials.

  Phytosterol has a protective action against external stimuli, an anti-inflammatory action, and a water transpiration inhibiting action. In addition, phytosterol fatty acid esters have high water retention and are also used as emollients. Furthermore, these are all contained in plant foods such as cereals, vegetables, fruits and mushrooms, and are taken from foods on a daily basis, and are highly safe.

  Conventionally, as cosmetics containing such phytosterols and phytosterol fatty acid esters, for example, phytosterols, hydrogenated phytosterols, and cosmetics containing specific phytosterol fatty acid esters (Patent Document 1); sterols (stigmasterol etc.) Hair rinse composition containing an unsaturated fatty acid (such as oleic acid) ester as an active ingredient (Patent Document 2); a cationic surfactant, a higher alcohol, silicone, and a specific oil (such as phytosteryl oleate) Products (Patent Document 3); phytosterols or derivatives thereof (such as oleates), carboxyvinyl polymers, alkyl-modified carboxyvinyl polymers, and cosmetics (Patent Document 4) containing specific silicone oils are known.

  However, the phytosterols or phytosterol fatty acid esters used in the cosmetics are industrially expensive because they are obtained by preparing / separating them individually, and are widely used in cosmetics and skin external preparations. There was a problem to use. Furthermore, since phytosterol has low solubility in oils and crystals are likely to precipitate, its composition is limited and there is a problem in usability as a cosmetic blending raw material.

  Thus, Patent Document 5 proposes a method for producing plant sterol wax, which can produce plant sterol wax efficiently and inexpensively. Furthermore, the same publication includes a plant sterol wax mainly composed of phytosterol, phytosterol fatty acid ester and hydrocarbon as a skin external preparation having excellent usability and stability prepared using this plant sterol wax. A topical skin preparation has been proposed.

  Animal-derived substances such as lanolin are known as other natural cosmetic ingredients. Lanolin can impart a moist feeling, moderate oiliness, gloss and the like to hair and skin. Lanolin is also used as an emulsification aid, a stabilizer, and a softening agent because it is excellent in emulsion stability and emollient.

  However, lanolin has an inherent odor and further causes allergies. Recently, there are safety problems (BSE, etc.) due to animal-derived substances, and they have been avoided.

  Therefore, research and development of lanolin substitute substances have been conducted conventionally. For example, Patent Document 6 describes a lanolin substitute substance composed of an ethylene oxide adduct of plant sterin, a specific mixed ester, and a specific diglyceride. Furthermore, Patent Document 7 describes a lanolin substitute cosmetic raw material comprising a steroid esterified product obtained from a hydroxy fatty acid and phytosterol and a specific alcohol esterified product.

  However, since the lanolin substitute substance described in Patent Document 6 is a synthetic product, it is inferior in safety to natural products and further lacks a mild action and imparts a so-called “human-friendly” function. It has a problem that it is difficult to do.

Further, the lanolin substitute cosmetic raw material described in Patent Document 7 has a problem that it is industrially expensive because it is obtained by carrying out preparation / separation alone.
JP-A-52-79030. Japanese Patent Laid-Open No. 2-6404. JP 2001-139437 A. JP 2002-145722 A. JP 2001-163764 A. JP-A-58-198565. JP-A-9-194345.

  The present invention further develops the invention described in Patent Document 5 and has excellent effects and effects (for example, hydration / emollient property, repair / protection effect on damaged hair, etc.) possessed by the plant-derived substance with less stickiness. An object of the present invention is to easily and inexpensively prepare a highly safe permanent wave agent having no phytosterol or the like. Another object of the present invention is to provide an inexpensive permanent wave agent that does not use lanolins (lanolin itself, liquid lanolin and hard lanolin) and can give the hair the same texture as lanolins. To do.

  In order to achieve the above object, the present inventors have intensively studied, and as a result, it has been found that if a composition prepared by fatty acid esterification of a plant sterol wax is blended, an excellent effect is achieved and the present invention is achieved. Arrived.

That is, the present invention is a component A (hereinafter simply referred to as “A”): distilling off a volatile component by distillation of a by-product obtained when extracting, separating, and purifying tocopherol from a vegetable oil deodorized distillate. A composition prepared by fatty acid esterification, decolorization, and deodorization, which comprises 3% by weight or less of free phytosterol, 55 to 65% by weight of phytosterol fatty acid ester, 3 to 10% by weight of triterpene alcohols, and 6 to 13% by weight of hydrocarbons And a composition containing 3% by weight or less of a fatty acid methyl ester . With A, phytosterol and the like are deposited with a highly safe permanent wave agent that has low stickiness and has the excellent effects and effects (for example, water retention / emollient property, repair / protection of damaged hair, etc.) that the plant-derived substances have. And can be prepared easily and inexpensively.

  The present invention includes A, component B (hereinafter simply “B”): vegetable oil, component C (hereinafter simply “C”): sucrose fatty acid ester and component D (hereinafter simply “D”): liquid higher fatty acid, A permanent wave agent is provided. By containing B, C, and D in addition to A, the same texture as liquid lanolin can be imparted to the hair.

  The present invention provides a permanent wave agent containing A and component E (hereinafter simply “E”): a plant hydrogenated oil. By containing E in addition to A, the hair can have the same texture as lanolin itself.

  The present invention provides a permanent wave agent containing A, B and E. By containing B and E in addition to A, the same texture as hard lanolin can be imparted to the hair.

  The present invention provides the permanent wave agent according to any one of the above, further F (hereinafter simply “F”): higher alcohol, G (hereinafter simply “G”): nonionic surfactant, and H (hereinafter simply “F”). “H”): an anionic surfactant or I (hereinafter simply “I”): a permanent wave agent containing a cationic surfactant. By further containing F, G, and H or I, a creamy permanent wave agent can be obtained.

  The present invention provides a permanent wave agent containing A and G. The present invention provides a permanent wave agent containing A, G and I. By containing G or G and I in addition to A, a liquid permanent wave agent can be obtained.

  According to the present invention, a phytosterol or the like is a highly safe permanent wave agent having less stickiness and having the excellent effects and effects (for example, water retention / emollient property, repairing / protecting action of damaged hair, etc.) possessed by the plant-derived substances. It can be easily and inexpensively prepared without precipitation. Furthermore, according to the present invention, it is possible to provide the permanent wave agent that does not use lanolins (lanolin itself, liquid lanolin and hard lanolin) and can give hair the same texture as lanolins at low cost.

Hereinafter, the present invention will be described in detail.
In the permanent wave agent of the present invention, A: by-product obtained when extracting, separating and purifying tocopherol from the vegetable oil deodorized distillate, the volatile matter is distilled off by distillation, the distillation residue is fatty acid esterified, decolorized, A composition prepared by deodorization , comprising free phytosterol 3% by weight or less, phytosterol fatty acid ester 55-65% by weight, triterpene alcohols 3-10% by weight, hydrocarbons 6-13% by weight, and fatty acid methyl ester A composition containing 3% by weight or less .

  By including (incorporating) A into the permanent wave agent, the following various advantages can be achieved. That is, as a result of A containing a large amount of phytosterol fatty acid ester, A contains less stickiness, and can impart excellent water retention and emollient properties to hair. Furthermore, since A is excellent in uniform mixing and solubility with respect to an oil agent, a permanent wave agent can be easily prepared by using A without precipitation of phytosterol or the like. Furthermore, by containing A, a texture close to sterol wax can be imparted to hair, and damaged hair can be repaired and protected by the polymer component of sterol wax. Furthermore, since A is easily prepared from edible vegetable oils, etc., it is highly safe to use A, and more inexpensive than phytosterols and phytosterol fatty acid esters prepared (or separated) alone. .

  As said vegetable oil deodorized distillate, what is distilled with water vapor | steam when performing steam distillation in the deodorizing process of vegetable oil is mentioned. Examples of vegetable oils used as raw materials include edible vegetable oils such as soybean, rapeseed, cottonseed, corn, and sunflower.

  In the preparation of A, a by-product (residue) obtained when extracting, separating and purifying tocopherol from the above vegetable oil deodorized distillate is used. Examples of methods for extracting, separating and purifying tocopherol from vegetable oil deodorized distillate include the following methods. That is, the vegetable oil deodorized distillate is subjected to modification treatment (esterification, non-saponification, etc.) as necessary, and then tocopherol is extracted with an organic solvent. The extract is then treated with a basic anion exchange resin to adsorb tocopherol onto the resin. Thereafter, by passing an organic solvent containing an acid through the resin, the tocopherol is eluted and separated from the resin to obtain purified tocopherol.

More specifically, the following methods 1 to 5 are exemplified.
1: An alcohol extract of an esterified product or an unsaponified product of a low-concentration tocopherol-containing substance by-produced in the purification process of various vegetable oils and fats is treated with an OH basic anion exchange resin, and the boric acid alcohol solution is used as an extraction solvent A method for concentrating and purifying tocopherols to elute mixed coferol by passing through the treated resin (JP-A-49-85222),

2: A natural and synthetic tocopherol substance is made into a solution using a monohydric alcohol having 1 and 4 carbon atoms, and this is treated with a basic anion exchange resin to adsorb the tocopherol substance to the resin, and then formic acid, A method for purifying a tocopherol substance, wherein the tocopherol substance is eluted from the resin with an acetic acid or oxalic acid solution (Japanese Patent Publication No. 38-23638),

3: An aromatic hydrocarbon solution in which an esterified product or an unsaponified product of a low-concentration tocopherol-containing substance by-produced in the purification process of various vegetable oils and fats was dissolved with an aromatic hydrocarbon was replaced with the aromatic hydrocarbon. A method for concentrating and purifying tocopherols by eluting mixed coferol by treating with an OH basic anion exchange resin and passing the treated resin through a boric acid alcohol solution as an elution solvent (Japanese Patent Publication No. 55-25189) Gazette),

4: Dissolving the tocopherol-containing material in a solvent, passing this solution through a basic anion exchange resin to adsorb tocopherols, removing impurities that do not adsorb, and then passing the solvent treated with carbon dioxide as the extraction solvent And tocopherol purification and concentration method for selectively eluting tocopherols (Japanese Patent Publication No. 61-55917),

5: From a low-concentration tocopherol-containing substance produced as a by-product in the vegetable oil refining process, subjecting this to a methyl esterification reaction, treating the reaction product with a strongly basic resin, and subjecting the tocopherol adsorbed to the resin to an elution operation, In the method for separating tocopherol, (1) the methyl esterification reaction is carried out in toluene, (2) the toluene layer of the methyl esterification reaction product is directly treated with a strongly basic resin, and (3) the acid is contained. A method of separating tocopherol that elutes tocopherol adsorbed on the resin using toluene as a developing solvent (Japanese Patent Publication No. 61-57309).

  As another method for extracting, separating and purifying tocopherol from a vegetable oil deodorized distillate, for example, there is a method of isolating a deodorized distillate from a distillate after esterification. More specifically, prior to distillation, the sterols present in the deodorant sludge are esterified with simultaneously present fatty acids, the resulting mixture is distilled to obtain the remaining fatty acids and then tocopherols. And thereby the sterol esters produced during esterification remain in the distillation residue, and then the tocopherols are isolated from the distillate, and the sterols are isolated from the distillation residue after cleavage of the sterol esters And a method of separating tocopherols and sterols from the deodorant sludge by distillation of the deodorant sludge (Patent No. 2648450).

In the present invention, the following method is preferred. That is, first, free fatty acids contained in the deodorized distillate are esterified (methyl esterification, ethyl esterification, etc.) in an organic solvent (toluene, xylene, etc.). Next, the organic solvent phase of the reaction product is treated with a strongly basic anion exchange resin, and then a solution containing an acid (acetic acid, propionic acid, etc.) is passed through the resin to separate the adsorbed tocopherol. .
A of the present invention is prepared from a byproduct (treatment residue) obtained when extracting, separating and purifying tocopherol from the above-mentioned vegetable oil deodorized distillate. Therefore, A can be manufactured at a very low cost.

  When a strongly basic anion exchange resin is used in the separation and purification of tocopherol, such a by-product usually contains sterol and sterol, which are components in non-adsorbed oil that is not adsorbed by the strongly basic anion exchange resin. Fatty acid esters, hydrocarbons and the like are included.

  In the preparation of A of the present invention, the by-product obtained above is distilled to distill off volatile components (fatty acid esters and the like). The distillation is preferably performed at 150 to 160 (particularly 152 to 158) ° C. under 1 to 0.005 (particularly 0.9 to 0.01) Torr, for example.

  Next, a fatty acid is added to the distillation residue, and a component such as phytosterol is converted into a fatty acid ester. Fatty acid esterification can suppress stickiness and facilitate mixing with other ingredients and hair cosmetics. Furthermore, the purification (decolorization, deodorization, etc.) of the post-process A can be facilitated, and the production cost can be reduced. As fatty acid, what is contained in edible oil is preferable. Specifically, as the fatty acid, C16 to C18 fatty acids (particularly oleic acid, linoleic acid, stearic acid, etc.) are preferable. The compounding quantity of a fatty acid may be 60-120 (especially 80-100) weight part with respect to 500 weight part of distillation residues, for example. Fatty acid esterification may be carried out with stirring and mixing as necessary.

  Next, the esterification reaction mixture is decolorized after performing an extraction operation or the like as necessary. Decolorization may be performed using an adsorbent (active clay, acidic clay, silica gel, etc.), an adsorbent resin (duolite XAD-761, XAD-7, etc.), and the like.

Then, A is obtained by deodorizing. Deodorization may be performed, for example, by blowing water at 150 to 160 (especially 152 to 158) ° C. under 10 to 0.1 (especially 8 to 0.5) Torr.
To A, an antioxidant (such as δ-tocopherol and / or n-propyl gallate) may be added as an additive.

  The component composition of A prepared as described above is usually 3% by weight (typically 0.1 to 2.0% by weight) of free phytosterol (stigmasterol, etc.), phytosterol fatty acid ester (oleic acid). Phytosteryl etc.) 55-65 (typically 56.5-62) wt%, triterpene alcohols (trimethylsterol etc.) 3-10 (typically 6-8) wt%, hydrocarbons (squalene, paraffin) Etc.) 6 to 13 (typically 2 to 5) wt%, and fatty acid methyl ester 3 wt% or less (typically 0.1 to 0.7 wt%).

Furthermore, the various physical properties of A are usually measured by an acid value (mgKOH / g) of 2.0 or less (typically 1.0 to 1.7), a saponification value (2 g of sample dissolved in 25 ml of xylene). ) 60-95 (typically 80-90 in), having a iodine value _(gI 2/100 g) 40 to 60 (typically 45 to 55).

Examples of the A-containing permanent wave agent of the present invention include a two-component permanent wave agent consisting of a first agent containing a reducing agent and a second agent containing an oxidizing agent.
In the A-containing permanent wave agent, A is contained in the first agent and / or the second agent.

  The reducing agent contained in the first agent of the A-containing permanent wave agent includes thioglycolic acid, thiolactic acid, dithioglycolic acid and sulfurous acid, and salts thereof (ammonium salt, monoethanolamine salt, sodium salt, etc.), cysteine (Cysteine / cysteine hydrochloride, N-acetylcysteine, etc.), and one or more of these may be used.

  Oxidizing agents included in Part II of the A-containing permanent wave agent include hydrogen peroxide, persulfates (ammonium persulfate, potassium persulfate, sodium persulfate, etc.), perborates (sodium perborate, etc.) Percarbonate (sodium percarbonate, etc.) and bromate (sodium bromate, potassium bromate, etc.), and one or more of these may be used.

  A-containing permanent wave agents include esters, alkali agents, chelating agents, pH adjusters, antioxidants, acids, proteins, polymers, fragrances, paraffins, polyhydric alcohols, solvents, silicones, antiseptics as additives. An agent or the like may be added. The alkaline agent and the antioxidant are preferably blended with the first agent. The pH adjuster is preferably blended with the second agent.

  In the additive, esters have the effect of giving a feeling of use such as flexibility and sliding effect and protecting the skin by forming an oily film. Examples of esters in the additive include fatty acid esters, fatty acid triglycerides, polybasic acid esters, and the like composed of C8 to C18 fatty acids and lower or higher alcohols or polyhydric alcohols. Specifically, the esters include, for example, isopropyl myristate, 2-ethylhexyl palmitate, neopentyl glycol dicaprate as the fatty acid ester, coconut oil fatty acid triglyceride, hydrogenated palm oil fatty acid triglyceride, etc. as the fatty acid triglyceride. Examples of the acid ester include diethoxyethyl succinate.

  In the additive, the alkaline agent has a function of adjusting the strength of the wave. Examples of the alkali agent in the additive include inorganic alkali and organic alkali. Specifically, ammonia, amines, particularly alkanolamine [monoethanolamine (MEA), isopropanolamine (IPA), triisopropanolamine (TIPA), triethanolamine (TEA), 2-amino-2-methyl-1 -Propanol (AMP), 2-amino-2-methyl-1,3-propanediol (AMPD) and the like] or salts thereof, and hydroxide salts (sodium hydroxide, potassium hydroxide, etc.).

  In the additive, the chelating agent functions as a stabilizer. Specific examples of the chelating agent in the additive include edetic acid, edetic acid · 2Na, tetrasodium edetate, hydroxyethanediphosphonic acid, sodium oxalate, ethylenediaminetetra (methylenesulfonic acid) · 5Na, aminotri (methylenesulfonic acid) ), Hydroxyethylenediaminetriacetic acid / 3Na, sodium citrate, sodium metaphosphate, sodium polyphosphate, phytic acid and the like.

  Examples of the pH adjuster in the additive include any one, two, or three selected from the group consisting of acids, salts, and alkalis. As the pH adjuster, a pH buffer is preferable.

  Examples of the acid in the pH adjuster include organic acids (polybasic acids, hydroxycarboxylic acids and the like), and inorganic acids (oxo acids and the like). Specific examples of the acid include tartaric acid, citric acid, glycolic acid, lactic acid, and phosphoric acid.

  Examples of the salt in the pH adjuster include organic acid salts (polybasic acid salts, hydroxycarboxylic acid salts, etc.) and inorganic acid salts (oxo acid salts, sulfates, etc.). Specifically, the salts include sodium tartrate, potassium hydrogen tartrate, sodium citrate, potassium citrate, sodium dihydrogen phosphate, sodium monohydrogen phosphate, trisodium phosphate, potassium dihydrogen phosphate, monohydrogen phosphate. Examples include potassium, tripotassium phosphate, ammonium hydrogen carbonate, sodium sulfate and the like.

  Examples of the alkali in the pH adjuster include those exemplified as the alkali agent in the above additive.

  Specific examples of pH buffering agents include tartaric acid and a mixture of sodium tartrate and / or potassium hydrogen tartrate; a mixture of tartaric acid and sodium hydroxide and / or potassium hydroxide; tartaric acid and ammonia, MEA, TIPA, A mixture of any one or more selected from the group consisting of TEA, AMP, and AMPD; a mixture of citric acid and sodium citrate and / or potassium citrate; citric acid and sodium hydroxide and / or Mixture with potassium hydroxide; a mixture of citric acid with one or more selected from the group consisting of ammonia, MEA, TIPA, TEA, AMP, and AMPD; phosphoric acid and sodium dihydrogen phosphate; Any one or two selected from the group consisting of sodium monohydrogen phosphate and trisodium phosphate A mixture of phosphoric acid and sodium hydroxide and / or potassium hydroxide; either one or two selected from the group consisting of phosphoric acid and ammonia, MEA, TIPA, TEA, AMP, and AMPD The mixture with the above etc. are mentioned, You may contain any 1 type of these mixtures, or 2 or more types (all types are included). Preferred are phosphoric acid and sodium monohydrogen phosphate.

Examples of the antioxidant in the additive include cysteamine, BHT, tocopherol, L (+)-ascorbic acid, and the like.
Examples of acids in the additive include salicylic acid and glycyrrhizic acid (salt). In particular, salicylic acid has an effect of suppressing skin irritation.

  Examples of the protein in the additive include hydrolyzed rice protein, hydrolyzed soybean protein, hydrolyzed wheat protein and the like. By adding protein, damage to the hair is prevented and the effect of repair is expressed.

  Examples of the polymer in the additive include a thickener, a gelling agent, and a conditioning agent. Specific examples of the thickener include hydroxymethylcellulose, carboxymethylcellulose, xanthan gum, (acryloyldimethyltaurine ammonium / vinylpyrrolidone) copolymer, and cationized polymer compound.

  Examples of paraffins in the additive include liquid paraffin, paraffin, petrolatum, and microcrystalline wax. By adding paraffin, the effect of repairing and protecting the hair, giving it a slip and gloss is exhibited.

Examples of the polyhydric alcohol in the additive include dihydric alcohol (propylene glycol, dipropylene glycol), polyethylene glycol, glycerin and the like. By adding a polyhydric alcohol, a moisturizing effect and an emulsifying auxiliary effect are exhibited.
Specific examples of the solvent in the additive include lower alcohols (such as isopropanol), aromatic alcohols (such as benzyl alcohol), and N-methylpyrrolidone (NMP).

Examples of silicones in the additive include methylpolysiloxane, highly polymerized methylpolysiloxane, methylphenylpolysiloxane, methylcyclopolysiloxane, polyether-modified silicone, and alkoxy-modified silicone. By adding silicones, the effect of improving the feel and gloss of the finish is exhibited.
Examples of the preservative in the additive include parabens and sodium sorbate solution.

  A creamy permanent wave agent can be obtained by further containing F: a higher alcohol, G: a nonionic surfactant, and H: an anionic surfactant or I: a cationic surfactant in the A-containing permanent wave agent. can get. That is, examples of the creamy permanent wave agent of the present invention include A, F, G and H-containing permanent wave agents, and A, F, G and I-containing permanent wave agents.

  More specifically, in addition to A, in addition to the characteristics of the A-containing permanent wave agent, by combining F, G and H, the effect of improving the firmness and firmness of the hair and improving the after-conditioning property is obtained. Furthermore, an anion-type creamy permanent wave agent added can be obtained. In addition to A, in addition to the characteristics of the A-containing permanent wave agent, F, G, and I are combined to give the hair a soft feeling and reduce hair tangles and tingling. Further, a cationic type cream-like permanent wave agent to which the effect that the finished texture (smoothness, oily feeling, feel, appearance, etc.) is good is further added can be obtained.

  As F, for example, C12-C22 alcohol, specifically cetanol, myristyl alcohol, oleyl alcohol, lauryl alcohol, cetostearyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol, jojoba alcohol, chimyl alcohol, batyl alcohol, hexyldecanol, Examples include isostearyl alcohol and 2-octyldodecanol.

  Examples of G include polyoxyalkylene alkyl ethers, alkylol amides, partial esters of higher fatty acids and polyhydric alcohols, polyoxyethylene (POE) fatty acid esters, and the like.

  In G, examples of the polyoxyalkylene alkyl ether include POEC12-C22 alkyl ether, specifically, POE lauryl ether, POE cetyl ether, POE oleyl ether, POE stearyl ether, POE behenyl ether, and the like.

In G, as alkylolamide, for example, the following formula:
R ¹ CONHCH ₂ CH ₂ OH
[Wherein, R ¹ represents a C8 to C22 alkyl group. ]
And the following formula:
R ¹ CON (CH ₂ CH ₂ OH) ₂
[Wherein, R ¹ is as defined above. ]
The diethanolamide represented by these is mentioned.

  Specific examples of the alkylolamide include coconut oil fatty acid mono- or diethanolamide, lauric acid mono- or diethanolamide, oleic acid mono- or diethanolamide, stearic acid mono- or diethanolamide, and the like.

  In G, examples of the partial ester of a higher fatty acid and a polyhydric alcohol include monoesters or diesters of C6 to C18 fatty acids and C3 to C6 2 to 5 hydric alcohols. Specifically, partial esters of higher fatty acids and polyhydric alcohols include partial esters of higher fatty acids and glycerin (such as glyceryl monocaprate, glyceryl monomyristate, glyceryl monostearate), higher fatty acids and sorbitan. And partial esters such as sorbitan monooleate.

  In G, examples of the POE fatty acid ester include POEC 12 to C18 fatty acid esters. Specifically, examples of the POE fatty acid ester include polyethylene glycol monostearate, POE laurate, POE palmitate, and the like.

Examples of H include higher alcohol sulfates, N-acyl glutamates, sulfonates of higher fatty acid amides, and the like.
In H, examples of the higher alcohol sulfate salts include sulfuric acid monoesters of C8 to C22 alcohols. Examples of the salt include sodium salt, ammonium salt, triethanolamine salt and the like. Specific examples of the higher alcohol sulfate include sodium lauryl sulfate, sodium myristyl sulfate, sodium cetyl sulfate, and the like.

In H, as N-acyl glutamate, for example, the following formula:

[Wherein R ² represents a C12 to C18 aliphatic group. Two Ms represent an alkali metal or substituted or unsubstituted ammonium, one of which may be H, and may be the same or different. ]
The thing represented by is mentioned. Specifically, as N-acyl glutamate, N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine, N-lauroyl glutamic acid (di) sodium, N-stearoyl glutamic acid (di) sodium, N-lauroyl glutamic acid ( Di) sodium and the like.

［式中、Ｒ^３はＣ１０〜Ｃ２２脂肪族基、ｎは１若しくは２を表す。］
にて表されるナトリウム塩が挙げられる。In H, as the sulfonate of higher fatty acid amide, for example, the following formula:

[Wherein R ³ represents a C10 to C22 aliphatic group, and n represents 1 or 2. ]
The sodium salt represented by these is mentioned.

  Specific examples of sodium sulfonates of higher fatty acid amides include lauroyl methyl taurine sodium, palmitoyl methyl taurine sodium, stearoyl methyl taurine sodium, and the like.

  Examples of I include alkyl quaternary ammonium salts and di (polyoxyethylene) alkyl quaternary ammonium salts. Specifically, as I, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium bromide, cetyltrimethylammonium bromide, behenyltrimethylammonium chloride, diPOE chloride And oleylmethylammonium.

  In the A, F, G and H-containing permanent wave agent, F, G and H are contained in the first agent and / or the second agent.

  In the composition of the A, F, G and H-containing permanent wave agent, A is 0.01 to 10.0 (particularly 0.05 to 5.0)% by weight and F is 0 in the first agent or the second agent. 0.1 to 20.0 (particularly 0.5 to 15.0)% by weight, G is 0.05 to 15.0 (particularly 0.1 to 10.0)% by weight, and H is 0.05 to 10.0. (Especially 0.1 to 5.0)% by weight is preferred.

  When A is less than the above lower limit, the above-described blending effect of A may not be obtained sufficiently. On the other hand, when A exceeds the above upper limit, the hair protecting action becomes too strong, and the hair may not be sufficiently smooth. When F, G, or H is less than the above lower limit amount, the above-described combination (combination) effect with F, G, and H may not be sufficiently obtained. If F exceeds the above upper limit, the hair may become stiff, oily and sticky. If G exceeds the above upper limit, the oil component may flow too strongly and the hair feel may be reduced. When H exceeds the above upper limit amount, the oil component may flow too strongly, the hair feel may be lowered, and the effect of reducing irritation may not be sufficient.

In the A, F, G, and I-containing permanent wave agent, F, G, and I are contained in the first agent and / or the second agent.
In the composition of the A, F, G and I-containing permanent wave agent, A is 0.01 to 10.0 (particularly 0.05 to 5.0)% by weight, and F is 0 in the first agent or the second agent. 0.1 to 20.0 (particularly 0.5 to 15.0)% by weight, G is 0.05 to 15.0 (particularly 0.1 to 10.0)% by weight, and I is 0.05 to 10.0. (Especially 0.1 to 5.0)% by weight is preferred.

  If I is less than the above lower limit, the combination (combination) effect with F, G and I described above may not be sufficiently obtained. If I exceeds the above upper limit, the oil component may flow too strongly, the hair feel may be lowered, and the irritation reducing effect may not be sufficient.

  According to the present invention, a liquid permanent wave agent can also be prepared. For example, a liquid permanent wave agent can be obtained by further containing G in the A-containing permanent wave agent. That is, examples of the liquid permanent wave agent of the present invention include A and G-containing permanent wave agents. More specifically, in addition to A, in addition to the characteristics of the A-containing permanent wave agent, in addition to G, a nonionic liquid permanent wave agent capable of imparting excellent elasticity to the hair can be obtained. .

In the A and G-containing permanent wave agent, G may be contained in the first agent and / or the second agent.
In the composition of the A and G-containing permanent wave agent, in the first agent or the second agent, A is 0.0001 to 10.0 (particularly 0.001 to 5.0)% by weight, and G is 0.05 to 15 0.0 (particularly 0.01-10.0) wt% is preferred.

  If A is less than the above lower limit, the above-mentioned blending effect of A may not be sufficiently obtained. Conversely, if the above upper limit is exceeded, the hair protecting action becomes too strong and sufficient hair smoothness cannot be obtained. There is. When G is less than the lower limit, the above-described combination (combination) effect of A and G may not be obtained sufficiently. If G exceeds the above upper limit, the oil component may flow too strongly and the hair feel may be reduced.

  By further containing I in the A and G-containing permanent wave agent, another aspect of the liquid permanent wave agent can be obtained. That is, examples of the liquid permanent wave agent according to another aspect of the present invention include A, G, and I-containing permanent wave agents. More specifically, in addition to A and G, by further combining I, a cationic liquid permanent wave agent capable of imparting excellent softness to hair can be obtained.

  In the A, G and I-containing permanent wave agent, G and I may be contained in the I agent and / or the II agent.

  In the composition of the A, G and I-containing permanent wave agent, in the first agent or the second agent, A is 0.0001 to 10.0 (particularly 0.001 to 5.0)% by weight, and G is 0.05. To 15.0 (particularly 0.01 to 10.0)% by weight, and I is preferably 0.05 to 10.0 (particularly 0.1 to 5.0)% by weight.

  If A is less than the above lower limit, the above-mentioned blending effect of A may not be sufficiently obtained. Conversely, if the above upper limit is exceeded, the hair protecting action becomes too strong and sufficient hair smoothness cannot be obtained. There is. When G and I are less than the above lower limit, the above-described combination (combination) effect of A, G and I may not be sufficiently obtained. If G exceeds the above upper limit, the oil component may flow too strongly and the hair feel may be reduced. If I exceeds the above upper limit, the oil component may flow too strongly, the hair feel may be lowered, and the irritation reducing effect may not be sufficient.

  As another aspect of the present invention, a permanent wave agent containing A, B, C and D can be mentioned. In addition to the characteristics of the A-containing permanent wave agent, the A, B, C, and D-containing permanent wave agent of the present invention can further impart a texture similar to that of liquid lanolin to the hair. The inventor has found that a mixture of A, B, C and D is very similar to liquid lanolin. That is, the mixture composed of A, B, C and D has a liquid form / appearance very similar to liquid lanolin, and can impart a texture very similar to liquid lanolin to hair. In particular, the blend of A, B, and D can impart the same smoothness of hair as liquid lanolin. The combination of A and C can provide the same emollient, water retention, moist feeling, softening effect, gloss and moisturizing effect as liquid lanolin.

  B is an edible vegetable oil (rice germ oil, olive oil, safflower oil, soybean oil, sunflower oil, rapeseed oil, palm oil, jojoba oil, macadamia nut oil, castor oil, camellia oil, avocado oil from the viewpoint of safety, etc. Wheat germ oil, Meadow home oil, etc.) are preferred.

  C is preferably a full ester or a partial ester of sucrose and a C12 to C22 fatty acid (sucrose hexaerucate, sucrose oleate, sucrose stearate, sucrose palmitate, etc.).

  The “liquid” higher fatty acid of D means one having fluidity at room temperature. By being liquid, it can be set to the same form as liquid lanolin. Examples of liquid higher fatty acids include C16-C22 fatty acids that are liquid at room temperature, specifically oleic acid, linoleic acid, linolenic acid, and branched fatty acids (such as isostearic acid), with branched fatty acids being particularly preferred.

  The A, B, C and D-containing permanent wave agent of the present invention includes a two-component permanent wave agent consisting of a first agent containing a reducing agent and a second agent containing an oxidizing agent.

  In the A, B, C and D-containing permanent wave agent, A, B, C and D are contained in the first agent and / or the second agent.

  The reducing agent contained in the first agent of the A, B, C, and D-containing permanent wave agent and the oxidizing agent blended in the second agent were those described and exemplified in the A-containing permanent wave agent, respectively. You can. The A, B, C, and D-containing permanent wave agent may contain other additives. The additive may be those described and exemplified as the additive in the A-containing permanent wave agent.

  By adding F, G, and H or I to the A, B, C and D-containing permanent wave agent, a creamy permanent wave agent can be obtained. That is, as the creamy permanent wave agent of the present invention, A, B, C, D, F, G and H containing permanent wave agents and A, B, C, D, F, G and I containing permanent wave agents are available. Can be mentioned.

  More specifically, by combining F, G and H in addition to A, B, C and D, the hair has better moisturizing feeling, smoothness, softness and firmness, and after-conditioning is improved. An anionic type cream-like permanent wave agent to which the effect of. In addition to A, B, C and D, F, G and I are combined to give the hair a soft feeling, improve the moisturizing feeling, smoothness, firmness and firmness in use. Thus, a cationic type cream-like permanent wave agent to which the effects of reducing hair tangling and tingling and improving the finish texture (smoothness, oiliness, feel, appearance, etc.) is obtained.

  In A, B, C, D, F, G, and H-containing permanent wave agent, and A, B, C, D, F, G, and I-containing permanent wave agent, for any of F, G, H, and I, It may be contained in the first agent and / or the second agent.

  In the composition of the A, B, C, D, F, G and H-containing permanent wave agent, in the first agent or the second agent, A is 0.01 to 10.0 (particularly 0.02 to 5.0). Wt%, B is 0.01 to 20.0 (particularly 0.02 to 15.0) wt%, C is 0.001 to 5.0 (particularly 0.01 to 3.0) wt%, and D is 0 0.001 to 5.0 (particularly 0.01 to 3.0) wt%, F is 0.1 to 20.0 (particularly 0.5 to 15.0) wt%, and G is 0.05 to 15.0 (Especially 0.1 to 10.0) wt%, H is preferably 0.05 to 10.0 (particularly 0.1 to 5.0) wt%.

  If A is less than the above lower limit amount, the above-mentioned blending effect of A may not be sufficiently obtained. Conversely, if the above upper limit amount is exceeded, the hair protecting action becomes too strong and sufficient hair smoothness cannot be obtained. There is. When B, C, or D is less than the above lower limit amount, the same texture as liquid lanolin may not be sufficiently imparted to the hair. When B exceeds the above upper limit, the hair is squeezed strongly and a rich feeling may not be obtained sufficiently. When C exceeds the above upper limit, the hair is too moist and the smoothness may decrease. When D exceeds the above upper limit, emollient properties and hair protecting action may be weakened. When F, G, or H is less than the above lower limit amount, the above-described combination (combination) effect with F, G, and H may not be sufficiently obtained. If F exceeds the above upper limit, the hair may become stiff, oily and sticky. If G exceeds the above upper limit, the oil component may flow too strongly and the hair feel may be reduced. When H exceeds the above upper limit amount, the oil component may flow too strongly, the hair feel may be lowered, and the effect of reducing irritation may not be sufficient.

  In the composition of A, B, C, D, F, G, and I-containing permanent wave agent, in the first agent or the second agent, A is 0.01 to 10.0 (particularly 0.02 to 5.0). Wt%, B is 0.01 to 20.0 (particularly 0.02 to 15.0) wt%, C is 0.001 to 5.0 (particularly 0.01 to 3.0) wt%, and D is 0 0.001 to 5.0 (particularly 0.01 to 3.0) wt%, F is 0.1 to 20.0 (particularly 0.5 to 15.0) wt%, and G is 0.05 to 15.0 (Especially 0.1 to 10.0) wt%, I is preferably 0.05 to 10.0 (particularly 0.1 to 5.0).

  When F, G, or I is less than the above lower limit amount, the aforementioned combination (combination) effect with F, G, and I may not be sufficiently obtained. If F exceeds the above upper limit, the hair may become stiff, oily and sticky. If G exceeds the above upper limit, the oil component may flow too strongly and the hair feel may be reduced. If I exceeds the above upper limit, the oil component may flow too strongly, the hair feel may be lowered, and the irritation reducing effect may not be sufficient.

  As another aspect of the present invention, a permanent wave agent containing A and E can be mentioned. In addition to the characteristics of the A-containing permanent wave agent, the A- and E-containing permanent wave agent of the present invention can further impart the same texture and function as lanolin itself. The inventor has found that a mixture of A and E is very similar to lanolin. That is, the mixture of A and E has a form / appearance very similar to lanolin, and can impart moisturizing feeling, smoothness, gloss, rich feeling, etc. to hair very similar to lanolin. Furthermore, functions such as wettability, emollient property, and hair protecting action can also be imparted.

  E is preferably a hydrogenated vegetable oil (hydrogenated rice bran oil, partially hydrogenated rice bran oil, palm hydrogenated oil, palm partially hydrogenated oil, hydrogenated soybean oil, etc.) from the viewpoint of safety, and hydrogenated rice bran oil or palm partially hydrogenated oil is preferable. Particularly preferred.

The A and E-containing permanent wave agents of the present invention include a two-component permanent wave agent composed of a first agent containing a reducing agent and a second agent containing an oxidizing agent.
In the A and E-containing permanent wave agent, A and E are contained in the first agent and / or the second agent.

  The reducing agent contained in the first agent of the A and E-containing permanent wave agents and the oxidizing agent blended in the second agent may be those described and exemplified in the A-containing permanent wave agent. The A and E-containing permanent wave agents may contain other additives. The additive may be those described and exemplified as the additive in the A-containing permanent wave agent.

  A creamy permanent wave agent can be obtained by further containing F, G, and H or I in the A and E-containing permanent wave agent. That is, examples of the creamy permanent wave agent of the present invention include A, E, F, G, and H-containing permanent wave agents, and A, E, F, G, and I-containing permanent wave agents.

  More specifically, by combining F, G and H in addition to A and E, the hair has the effect of improving the moisturizing feeling, smoothness, coating protection, firmness and firmness, and improving after-conditioning properties. Furthermore, an anion-type creamy permanent wave agent added can be obtained. In addition to A and E, by combining F, G and I, the hair is given a soft feeling, and the hair has a moisturizing feeling, smoothness, coating protection, firmness and firmness. A cationic type cream-like permanent wave agent to which the effects of reducing hair tangling and tingling sensation and having a good finish is added.

  A, E, F, G, and H-containing permanent wave agent, and A, E, F, G, and I-containing permanent wave agent, and F, G, H, and I are all agents I and / or II. It may contain.

  In the composition of the A, E, F, G, and H-containing permanent wave agent, in the first agent or the second agent, A is 0.01 to 10.0 (particularly 0.05 to 5.0)% by weight, E Is 0.001 to 5.0 (particularly 0.005 to 3.0)% by weight, F is 0.1 to 20.0 (particularly 0.5 to 15.0)% by weight, and G is 0.05 to 15%. 0.0 (particularly 0.1 to 10.0)% by weight, and H is preferably 0.05 to 10.0 (particularly 0.1 to 5.0)% by weight.

  If A is less than the above lower limit, the above-mentioned blending effect of A may not be sufficiently obtained. Conversely, if the above upper limit is exceeded, the hair protecting action becomes too strong and sufficient hair smoothness cannot be obtained. There is. When E is less than the above lower limit, the same texture and effect as lanolin may not be sufficiently imparted to the hair. If E exceeds the above upper limit, the film property becomes too strong, and oily smoothness may not be obtained sufficiently. When F, G, or H is less than the above lower limit amount, the above-described combination (combination) effect with F, G, and H may not be sufficiently obtained. If F exceeds the above upper limit, the hair may become stiff, oily and sticky. If G exceeds the above upper limit, the oil component may flow too strongly and the hair feel may be reduced. When H exceeds the above upper limit amount, the oil component may flow too strongly, the hair feel may be lowered, and the effect of reducing irritation may not be sufficient.

  In the composition of the A, E, F, G, and I-containing permanent wave agent, in the first agent or the second agent, A is 0.01 to 10.0 (particularly 0.05 to 5.0)% by weight, E Is 0.001 to 5.0 (particularly 0.005 to 3.0)% by weight, F is 0.1 to 20.0 (particularly 0.5 to 15.0)% by weight, and G is 0.05 to 15%. 0.0 (particularly 0.1 to 10.0)% by weight, and I is preferably 0.05 to 10.0 (particularly 0.1 to 5.0)% by weight.

  When F, G, or I is less than the above lower limit amount, the aforementioned combination (combination) effect with F, G, and I may not be sufficiently obtained. If F exceeds the above upper limit, the hair may become stiff, oily and sticky. If G exceeds the above upper limit, the oil component may flow too strongly and the hair feel may be reduced. If I exceeds the above upper limit, the oil component may flow too strongly, the hair feel may be lowered, and the irritation reducing effect may not be sufficient.

  As another aspect of the present invention, a permanent wave agent containing A, B and E can be mentioned. In addition to the characteristics of the A-containing permanent wave agent, the A, B and E-containing permanent wave agent of the present invention can further impart the same texture and function as hard lanolin. The inventor has found that a mixture of A, B and E is very similar to hard lanolin. That is, the mixture composed of A, B and E has a form / appearance very similar to hard lanolin, and can impart a texture very similar to hard lanolin to hair. Specifically, the same luster, coating feeling, firmness and firmness as hard lanolin can be imparted. In particular, the blending of A and B can give the hair the same smoothness as hard lanolin.

The A, B and E-containing permanent wave agents of the present invention include a two-component permanent wave agent comprising a reducing agent-containing first agent and an oxidizing agent-containing second agent.
In the A, B, and E-containing permanent wave agent, A, B, and E are contained in the first agent and / or the second agent.

  The reducing agent contained in the first agent of the A, B, and E-containing permanent wave agent and the oxidizing agent blended in the second agent may be those described and exemplified in the A-containing permanent wave agent. . The A, B, and E-containing permanent wave agent may contain other additives. The additive may be those described and exemplified as the additive in the A-containing permanent wave agent.

  By adding F, G, and H or I to the A, B and E-containing permanent wave agent, a creamy permanent wave agent can be obtained. That is, examples of the creamy permanent wave agent of the present invention include A, B, E, F, G, and H-containing permanent wave agents, and A, B, E, F, G, and I-containing permanent wave agents.

  More specifically, in addition to A, B, and E, by combining F, G, and H, the effect of improving the hair condition and improving the after-conditioning property of the hair is improved. An anionic type creamy permanent wave agent is obtained. In addition to A, B and E, by combining F, G and I, the hair is given a soft feeling, and the hair is protected against coating and firmness and firmness. A cationic type cream-like permanent wave agent to which the effect of reducing the feeling of squealing and having a good finish is added.

  In the A, B, E, F, G, and H-containing permanent wave agent and the A, B, E, F, G, and I-containing permanent wave agent, F, G, H, and I are all the I agent and / or Or you may contain in a II agent.

  In the composition of the A, B, E, F, G, and H-containing permanent wave agent, in the first agent or the second agent, A is 0.01 to 10.0 (particularly 0.02 to 5.0)% by weight. , B is 0.001 to 5.0 (particularly 0.005 to 3.0) wt%, E is 0.01 to 15.0 (particularly 0.02 to 10.0) wt%, and F is 0.1 ˜20.0 (particularly 0.5 to 15.0) wt%, G is 0.05 to 15.0 (particularly 0.1 to 10.0) wt%, and H is 0.05 to 10.0 (particularly 0.1 to 5.0)% by weight is preferred.

  If A is less than the above lower limit, the above-mentioned blending effect of A may not be sufficiently obtained. Conversely, if the above upper limit is exceeded, the hair protecting action becomes too strong and sufficient hair smoothness cannot be obtained. There is. If B or E is less than the above lower limit, the hair may not be sufficiently imparted with the same texture as hard lanolin. If B exceeds the above upper limit, the hair is squeezed strongly and a rich feeling may not be obtained sufficiently. If E exceeds the above upper limit, the film property becomes too strong, and oily smoothness may not be obtained sufficiently. When F, G, or H is less than the above lower limit amount, the above-described combination (combination) effect with F, G, and H may not be sufficiently obtained. If F exceeds the above upper limit, the hair may become stiff, oily and sticky. If G exceeds the above upper limit, the oil component may flow too strongly and the hair feel may be reduced. When H exceeds the above upper limit amount, the oil component may flow too strongly, the hair feel may be lowered, and the effect of reducing irritation may not be sufficient.

  In the composition of A, B, E, F, G, and I-containing permanent wave agent, in the first agent or the second agent, A is 0.01 to 10.0 (particularly 0.02 to 5.0)% by weight. , B is 0.001 to 5.0 (particularly 0.005 to 3.0) wt%, E is 0.01 to 15.0 (particularly 0.02 to 10.0) wt%, and F is 0.1 To 20.0 (particularly 0.5 to 15.0)% by weight, G is 0.05 to 15.0 (particularly 0.1 to 10.0)% by weight, and I is 0.05 to 10.0 (particularly) 0.1 to 5.0)% by weight is preferred.

  When F, G, or I is less than the above lower limit amount, the aforementioned combination (combination) effect with F, G, and I may not be sufficiently obtained. If F exceeds the above upper limit, the hair may become stiff, oily and sticky. If G exceeds the above upper limit, the oil component may flow too strongly and the hair feel may be reduced. If I exceeds the above upper limit, the oil component may flow too strongly, the hair feel may be lowered, and the irritation reducing effect may not be sufficient.

Hereinafter, the present invention will be described specifically by way of examples.
[Preparation of component A]
Preparation Example 1
Deodorized distillate 2000 g (total tocopherol content 10.3%, acid value 81) obtained as a by-product by soybean oil deodorization treatment in the presence of 130 g of sulfuric acid in a mixed solvent of 1000 ml of methanol and 1000 ml of toluene for 1 hour under reflux The oily material was separated and washed 4 times with 500 ml of water. The acid value was 1 by the methyl esterification reaction. Then, after cooling to room temperature, the precipitated crystals were separated by filtration. Filtration removed 8.9 g of crystals.

  Next, 2,000 ml of a strongly basic anion exchange resin Amberlite IRA958 was packed in a column to form an OH type, which was then replaced with toluene, and a toluene solution of the methyl esterified oil prepared above was passed through. Subsequently, 4,000 ml of toluene was flowed to wash the resin, and toluene was distilled off to obtain 1,670 g of non-adsorbed oil. The adsorbed tocopherol was eluted by flowing 4,000 ml of 10% acetic acid methanol solution to obtain 257 g of tocopherol concentrated oil.

  Next, 80 g of oleic acid was added to 500 g of the residue obtained by distilling off the fatty acid methyl ester contained in the non-adsorbed oil by vacuum distillation, and the mixture was reacted at 200 ° C. for 24 hours under a nitrogen stream. 5 L of hexane was added to the reaction mixture and dissolved by stirring, and 2 L of 80% methanol water added with 10 g of sodium hydroxide was added to remove excess oleic acid. Subsequently, the hexane phase was washed successively with 2 L of 70% methanol water and 4 times with 3 L of water. After adding 45 g of activated clay and 30 g of activated carbon and stirring under reflux for 1 hour, the mixture was cooled to room temperature, filtered and concentrated.

  Next, 0.44 g of δ-tocopherol and 0.06 g of propyl gallate were added to the concentrated solution, and 30 mL of water was blown in for 2 hours at a vacuum degree of 10 Torr to 0.1 Torr and a temperature of 150 to 160 ° C. By the above operation, 487 g of pale yellow to light brown pasty oil was obtained. This oil has an acid value of 0.8 and a saponification value of 83.7, and the results of gas chromatography analysis show that the proportions of sterol, sterol fatty acid ester, and hydrocarbon are 1.7%, 61.0%, and 7. 3%.

Preparation Example 2
In the presence of 130 g of sulfuric acid, 2000 g of deodorized distillate (total tocopherol content 9.8%, acid value 78) obtained as a by-product by deodorization treatment of vegetable oil (a mixture of soybean oil and leaf seed oil 1: 1) Methyl esterification was performed for 1 hour under reflux with a mixed solvent of 000 ml and 1,000 ml of toluene, and the oily substance was separated and washed four times with 500 ml of water. The acid value was 1 by the methyl esterification reaction. Then, after cooling to room temperature, the precipitated crystals were separated by filtration. Filtration removed 9.2 g of crystals.

  Next, 2,000 ml of a strongly basic anion exchange resin Duolite A113 was packed in a column to obtain an OH type, which was then replaced with toluene, and a toluene solution of the methyl esterified oil prepared above was passed through. Subsequently, 4,000 ml of toluene was flowed to wash the resin, and toluene was distilled off to obtain 1,650 g of non-adsorbed oil. The adsorbed tocopherol was eluted by flowing 4,000 ml of 10% acetic acid methanol solution to obtain 248 g of tocopherol concentrated oil.

  Next, 82 g of oleic acid and 20 g of linoleic acid were added to 510 g of the residue obtained by distilling off the fatty acid methyl ester contained in the non-adsorbed oil by vacuum distillation, and reacted at 200 ° C. for 24 hours in a nitrogen stream. 5 L of hexane was added to the reaction mixture and dissolved by stirring, and 2 L of 80% methanol water added with 10 g of sodium hydroxide was added to remove excess oleic acid and linoleic acid. Subsequently, the hexane layer was washed successively with 2 L of 70% methanol water and 4 times with 3 L of water. After adding 45 g of activated clay and 30 g of activated carbon and stirring under reflux for 1 hour, the mixture was cooled to room temperature, filtered and concentrated. Next, 30 mL of water was blown in over 2 hours at a degree of vacuum of 10 Torr to 0.1 Torr and a temperature of 150 to 160 ° C. By the above operation, 504 g of pale yellow to light brown pasty oil was obtained. This oil had an acid value of 0.1 and a saponification value of 74.8, and the proportions of sterol, sterol fatty acid ester and hydrocarbon were 1.9%, 62.1% and 9.0%.

[A GPC analysis and capillary GC analysis of A]
The GPC analysis of Preparation Example 1 and the GC analysis of Preparation Example 2 were performed under the following measurement conditions and measurement methods. The measurement results (charts) are shown in FIGS. 1 and 2, respectively. The compound name added to each peak in the GPC analysis chart diagram means that the compound is included in the peak.

(GPC analysis)
-Preparation of standard solution 10-25 mg of each standard substance shown in Table 1 is precisely weighed in a 50 mL volumetric flask, dissolved in chloroform by adding chloroform, and made up to 50 mL. This solution is used as each standard solution.

-Preparation of sample solution Weigh accurately 200 mg of sample substance (Preparation Example 1) in a 50 mL volumetric flask, dissolve with toluene, and make up to 50 mL. This solution is used as a sample solution.

GPC analysis conditions Column: K-801 (manufactured by Shodex, exclusion limit molecular weight: 1500)
K-802 (manufactured by Shodex, exclusion limit molecular weight: 5000)
Eluent: Chloroform flow rate: 0.5 mL / min
Temperature: 35 ° C
Detection: Light scattering detector (GAS1.0 NEB. 40 ° C EVA.80 ° C)

-GPC analysis method 20 μL of standard solution and sample solution are injected according to the above analysis conditions. The retention time of each standard substance is confirmed from the analysis result of each standard solution. The retention time of each peak obtained from the analysis result of the sample solution is collated with the retention time of the standard substance to obtain a component contained in each peak. The area percentage ratio of each peak is defined as the component content of each peak.

  In the GPC chart (FIG. 1), the main components and their concentration in the region where the retention time is about 20 to 30 minutes are shown in Table 2 below.

(GC analysis)
-Preparation of internal standard solution Weigh accurately 25 mg of cholesteryl n-decylate (SIGMA: C-4633) into a 50 mL volumetric flask, add 20 mL of hexane and dissolve with heating. While returning to room temperature, add chloroform and make up to 50 mL.

-Preparation of standard solution 10-25 mg of each standard substance shown in Table 1 above is precisely weighed in a 50 mL volumetric flask, dissolved in toluene by adding toluene, and made up to 50 mL. Take 5 mL of the solution into a 25 mL screw vial. Thereto, 5 mL of the internal standard solution prepared above is added to obtain each standard solution.

-Preparation of sample solution Weigh accurately 200 mg of sample material (Preparation Example 2) in a 50 mL volumetric flask, dissolve with toluene, and make up to 50 mL. Take 5 mL of the solution into a 25 mL screw vial. Then, 5 mL of the internal standard solution prepared above is added to obtain a sample solution.

-GC analysis conditions Equipment: GC-17A
Column: DB-1HT (manufactured by J & W, 15 m, 0.25 mm ID, 0.10 μm filmticness)
Carrier gas: He92kPa
Temperature rising program: 150 ° C. to 250 ° C. (5 ° C./min.)+250° C. to 350 ° C. (10 ° C./min.)
Injection method: Split method (split ratio 45: 1, temperature 350 ° C.)
Detector: FID (temperature 350 ° C)

GC analysis method 2 μL each of standard solution and sample solution are injected according to the above analysis conditions. The area of phytosterol is the sum of the four peaks of brassicasterol, campesterol, stigmasterol, and sitosterol, and the area of fatty acid ester of phytosterol is four from each sterol that is a C-16 fatty acid ester. And the four peaks derived from each sterol, which is a C-18 fatty acid ester, are combined. The hydrocarbons are a combination of squalene and paraffin. Each obtained area and the weight at the time of solution preparation are applied to the following formula, and the content of each component in the sample is calculated.

Preparation Example 3
From the by-product (residue) obtained when extracting, separating and purifying tocopherol from the vegetable oil deodorized distillate, the fatty acid ester was distilled off by distillation. Next, 80 g of oleic acid was added to 500 g of the distillation residue and reacted at 200 ° C. for 24 hours under a nitrogen stream. 5 L of hexane was added to the reaction mixture, and the solubilized component was dissolved by stirring. To this, 2 L of 80% aqueous methanol containing 10 g of sodium hydroxide was added to remove excess oleic acid. Subsequently, the hexane phase was washed successively with 2 L of 70% methanol water and 4 times with 3 L of water. To this hexane phase, 45 g of activated clay and 30 g of activated carbon were added, stirred under reflux for 1 hour, cooled to room temperature, filtered and concentrated. Next, 30 mL of water was blown in at 150 to 160 ° C. for 2 hours under 10 to 0.1 Torr. By the above operation, 487 g of pale yellow to light brown pasty oil was obtained. The acid value was 0.2 and the saponification value was 73.1.

[Preparation of plant sterol wax]
About 1,700 g of by-products obtained by extracting, separating and purifying tocopherol from the vegetable oil deodorized distillate are charged into a distillation machine, and the fatty acid ester is distilled as a fraction at about 150 to 160 ° C. under about 1.0 to 0.001 Torr. 1120 g was distilled off. About 2300 ml of hexane was added to the distillation residue and stirred. After removing the insoluble matter by filtration, about 60 g of activated clay was added and stirred for 30 minutes, followed by filtration and concentration. Next, about 30 ml of water was blown in at about 150 to 160 ° C. under about 10 to 0.1 Torr over 2 hours. By the above operation, about 550 g of pale yellow to light brown pasty oil was obtained. This oil had an acid value of about 0.3 and a saponification number of about 48.5, and the proportions of sterol, sterol fatty acid ester and hydrocarbon were about 19%, about 41% and about 16%.

[Preparation of primary bases 1-9]
According to the composition shown in Table 3, each composition component was uniformly stirred and mixed to prepare each primary base.

[Preparation of secondary bases 1-39]
In accordance with the composition shown in Tables 4 to 8, each compounding component is uniformly stirred and mixed with heating as necessary to obtain secondary bases 1 to 15 for anionic type creamy permanent wave agents, cationic type creamy permanent wave. Secondary bases 16 to 33 for agents, secondary bases 34 to 36 for nonionic liquid permanent wave agents, and secondary bases 37 to 39 for cationic type liquid permanent wave agents were prepared, respectively.

In Tables 6 and 7, 1), 2), and 3) represent the following.
1): [cetyltrimethylammonium bromide 70% by weight + ethanol 30% by weight] mix. .
2): [stearyl trimethylammonium chloride 63 wt% + isopropanol 33 wt% + water 4 wt%] mix. .
3): [80% by weight of behenyltrimethylammonium chloride + 20% by weight of isopropanol] mix. .
In Table 8, 1) and 2) represent the following.
1): [30% by weight of lauryl chloride trimethylammonium + 70% by weight of water] mix. .
2): [50% by weight of cetyltrimethylammonium chloride + 36% by weight of isopropanol + 14% by weight of water] mix. .

[Preparation of Permanent Wave Agent I]
According to the composition of Table 9 to Table 12, it was prepared as follows. That is, the cream-like permanent wave agent is first stirred and emulsified with purified secondary water heated to about 80 ° C if necessary, and then added to a secondary base heated to about 80 ° C and uniformly dissolved, and cooled to 45 ° C or lower. Thereafter, a reducing agent and an alkaline agent (ammonium thioglycolate aqueous solution, aqueous ammonia, ammonium hydrogen carbonate, etc.) were gradually added. Next, a chelating agent (1-hydroxyethane-1,1-diphosphonic acid solution) was mixed. After replenishing water, the mixture was stirred and mixed uniformly.

  On the other hand, the liquid permanent wave agent is added with a reducing agent and an alkaline agent (aqueous ammonium thioglycolate solution, aqueous ammonia, ammonium hydrogen carbonate, etc.) to purified water, and then a chelating agent (1-hydroxyethane-1,1-diphosphonic acid solution). ) Was mixed. Thereafter, a secondary base was added, and the mixture was stirred and mixed uniformly after the replenishment water was prepared.

  As described above, anionic type creamy permanent wave agent first agent (Examples 1-4, Comparative Examples 1-8, Controls 1-3), cation type creamy permanent wave agent I agent (Examples 5-5) 9, Comparative Examples 9-18, Controls 4-6), Nonionic Type Liquid Permanent Wave Agent First Agent (Example 10, Comparative Examples 19 and 20), and Cationic Type Liquid Permanent Wave Agent First Agent (Example 11, Comparative examples 21 and 22) were prepared.

[Preparation of Permanent Wave Agent II]
According to the composition of Table 9 to Table 12, it was prepared as follows. That is, the cream-like permanent wave agent is first stirred and emulsified with purified secondary water heated to about 80 ° C if necessary, and then added to a secondary base heated to about 80 ° C and uniformly dissolved, and cooled to 45 ° C or lower. I left. An oxidizing agent (hydrogen peroxide solution, sodium bromate, etc.) and a pH adjuster were gradually added. Next, a chelating agent (1-hydroxyethane-1,1-diphosphonic acid solution) was mixed. After replenishing water, the mixture was stirred and mixed uniformly.

  On the other hand, the liquid permanent wave agent is added with an oxidizing agent (hydrogen peroxide solution, sodium bromate) and a pH adjuster to purified water, and then mixed with a chelating agent (1-hydroxyethane-1,1-diphosphonic acid solution). did. Thereafter, a secondary base was added, and the mixture was stirred and mixed uniformly after the replenishment water was prepared.

  As described above, anionic type creamy permanent wave agent II (Examples 1-4, Comparative Examples 1-8, Controls 1-3), cationic type creamy permanent wave agent II (Examples 5-5) 9, Comparative Examples 9-18, Controls 4-6), Nonionic Type Liquid Permanent Wave Agent II Agent (Example 10, Comparative Examples 19 and 20), and Cationic Type Liquid Permanent Wave Agent II Agent (Example 11, Comparative examples 21 and 22) were prepared.

[Permanent wave agent evaluation tests]
For the creamy permanent wave agent, the first agent was applied to the hair, combed and allowed to stand for 10 minutes at room temperature. After leaving, it was rinsed slowly with warm water of about 40 ° C. to wipe off moisture. Next, the II agent was applied to the hair, combed and allowed to stand for 10 minutes at room temperature. Further, after standing, it was rinsed and dried with a dryer.

For the liquid permanent wave agent, the first agent was applied to the hair and combed, and the hair was wound around a rod and left at room temperature for 7 minutes. Next, the permanent wave agent II was applied with an applicator and allowed to stand for 7 minutes, and then the agent II was again applied with an applicator and allowed to stand for 7 minutes. Thereafter, the rod was removed, rinsed, and dried with a dryer.
Thereafter, sensory evaluation was performed by 10 panelists. The most frequent evaluation results are shown in Tables 9-12.

  However, the “hair repairing / protecting action” was performed by treating the hair three times with a hair color, a bleaching agent or a permanent agent, then performing the above-mentioned wave treatment, and performing sensory evaluation with 10 panelists. The “production cost” was evaluated based on the purchase price of the raw material.

  In Tables 9 to 12, in the column of “no stickiness”, “◎” represents “almost none”, “◯” represents “some”, and “Δ” represents “normal”. In the columns of “emollient” and “restoration / protection of hair”, “◎” represents “excellent”, “◯” represents “excellent”, and “Δ” represents “normal”. In the column of “low manufacturing cost”, “◎” represents “very low cost”, “◯” represents “low cost”, and “x” represents “high cost”. In the “Hair smoothness”, “Hair luster”, “Hair richness”, “Hair film feeling”, and “Hair elasticity” in Examples 10 and 11, ◎ is “Control” “○” means “is superior to the permanent wave agent containing no lanolins but inferior to the control”, and “Δ” is “same as the permanent wave agent not containing lanolins”. In Examples 10 and 11, “Hair elasticity” and “Hair softness” in the columns indicate “very good” and “good”, respectively.

From the results in Tables 9 to 12, the following is clear.
In the “A-containing permanent wave agent” of the present invention, an anionic type creamy permanent wave agent (Example 1), a cationic type creamy permanent wave agent (Example 5), a nonionic liquid permanent wave agent (Example 10) and Compared to each of the cation type liquid permanent wave agent (Example 11), an anionic type cream permanent wave agent (Comparative Example 1) and a cation type cream permanent wave agent (Comparison 1) containing a plant sterol wax instead of component A The nonionic liquid permanent wave agent (Comparative Example 19) and the cation type liquid permanent wave agent (Comparative Example 21) are all slightly sticky.

  In the “A-containing permanent wave agent” of the present invention, an anionic type creamy permanent wave agent (Example 1), a cationic type creamy permanent wave agent (Example 5), a nonionic liquid permanent wave agent (Example 10) and Compared to each of the cation type liquid permanent wave agent (Example 11), an anionic type cream permanent wave agent (Comparative Example 2) and cation type cream permanent wave agent (Comparative) containing phytosteryl oleate instead of component A Example 10), the nonionic liquid permanent wave agent (Comparative Example 20) and the cation type liquid permanent wave agent (Comparative Example 22) all have inferior hair repair / protective action and high production costs.

  Compared to the anionic cream permanent wave preparation (Control 1) and the cationic cream permanent wave preparation (Control 4) containing liquid lanolin, instead of liquid lanolin [component A + vegetable oil + sucrose fatty acid ester + liquid Higher Fatty Acid] The anionic type creamy permanent wave agent of the present invention (Example 2) and the cationic type creamy permanent wave agent (Example 6) blended with the mixture are both the same or higher in terms of hair smoothness and gloss. Excellent. This shows that the [component A + vegetable oil + sucrose fatty acid ester + liquid higher fatty acid] mixture is very useful as an alternative to liquid lanolin.

  On the other hand, instead of liquid lanolin, an anionic type cream permanent wave preparation (Comparative Example 3) and a cationic type cream permanent wave preparation (Comparative Example) containing a mixture of [plant sterol wax + vegetable oil + sucrose fatty acid ester + liquid higher fatty acid] 11) are both inferior to Controls 1 and 4 in hair smoothness and gloss, respectively, and are only as good as permanent wave agents that do not contain liquid lanolin, and may not be sufficient as an alternative to liquid lanolin. I understand.

  Furthermore, an anionic cream permanent wave preparation (Comparative Example 6) and a cationic cream permanent wave preparation (Comparative Example) containing a mixture of [phytosteryl oleate + vegetable oil + sucrose fatty acid ester + liquid higher fatty acid] instead of liquid lanolin It can be seen that 15) is inferior to Controls 1 and 4 in terms of the smoothness of the hair, is only as high as a permanent wave agent containing no liquid lanolin, and is insufficient as a substitute for liquid lanolin.

  Compared with each of the anionic type creamy permanent wave agent (control 2) and cation type creamy permanent wave agent (control 5) blended with lanolin, the present invention blended a mixture of [component A + plant hardened oil] instead of lanolin. The anionic type creamy permanent wave agent (Example 3) and the cationic type creamy permanent wave agent (Examples 7 and 8) are excellent in the smoothness and richness of the hair. From this, it can be seen that the [component A + plant hydrogenated oil] mixture is very useful as an alternative to lanolin.

  On the other hand, each of the anionic type creamy permanent wave agent (Comparative Example 4) and the cationic type creamy permanent wave agent (Comparative Examples 12 and 13) in which a mixture of [plant sterol wax + plant hardened oil] is used instead of lanolin, It can be seen that the smoothness of the hair is inferior to that of Controls 2 and 5, respectively, only to the same extent as the permanent wave agent containing no lanolin, and is not sufficient as a substitute for lanolin.

  Furthermore, anionic type creamy permanent wave agent (Comparative Example 7) and cation type creamy permanent wave agent (Comparative Examples 16 and 17) each containing a mixture of [phytosteryl oleate + hardened vegetable oil] instead of lanolin, It can be seen that it is superior to the permanent wave agent containing no lanolin in hair smoothness and richness, but inferior to the controls 2 and 5 containing lanolin, respectively, and is insufficient as a substitute for lanolin.

  Compared to each of the anionic type creamy permanent wave preparation (control 3) and cationic type creamy permanent wave preparation (control 6) containing hard lanolin, instead of hard lanolin, a mixture of [component A + vegetable oil + plant hardened oil] The blended anionic type creamy permanent wave agent of the present invention (Example 4) and cationic type creamy permanent wave agent (Example 9) are both superior to the same degree or more in terms of hair film feel and firmness. This indicates that the [component A + vegetable oil + plant hardened oil] mixture is very useful as an alternative to hard lanolin.

  On the other hand, each of the anionic type cream permanent wave agent (Comparative Example 5) and the cationic type cream permanent wave agent (Comparative Example 14) containing a mixture of [plant sterol wax + vegetable oil + plant hardened oil] instead of hard lanolin is used. It is superior to the permanent wave agent that does not contain hard lanolin, but inferior to the respective controls 3 and 6 that contain hard lanolin, in the feeling of hair coating and the firmness and firmness. From the above, it can be seen that the [plant sterol wax + vegetable oil + plant hardened oil] mixture is insufficient as a substitute for hard lanolin.

  Furthermore, in place of hard lanolin, both an anionic type creamy permanent wave agent (Comparative Example 8) and a cationic type creamy permanent wave agent (Comparative Example 18) containing a mixture of [phytosteryl oleate + vegetable oil + plant hardened oil] In terms of hair coating and firmness, it is only as good as a permanent wave agent that does not contain hard lanolin. From the above, it can be seen that the [phytosteryl oleate + vegetable oil + plant hardened oil] mixture is insufficient as a substitute for hard lanolin.

  As described above, the [component A + vegetable oil + sucrose fatty acid ester + liquid higher fatty acid] mixture, the [component A + plant hardened oil] mixture, and the [component A + vegetable oil + plant hardened oil] mixture are liquid lanolin, lanolin, and Very useful as an alternative to hard lanolin. Therefore, by blending the above three kinds of blends appropriately with the permanent wave agent I and / or II, each texture of liquid lanolin, lanolin and hard lanolin is blended in a desired ratio. Permanent wave agents can be prepared.

  For example, a [Component A + Vegetable Oil + Sucrose Fatty Acid Ester + Liquid Higher Fatty Acid] mixture in a permanent wave agent I and a [Component A 10 vegetable hardened oil] mixture in a permanent wave agent II. In waving agents, the texture of both liquid lanolin and lanolin can be imparted to the hair.

The GPC analysis chart figure of the preparation example 1 is shown. The GC analysis chart figure of the preparation example 2 is shown.

Claims (7)

A permanent wave agent comprising A.
A: extracting a tocopherol from vegetable oils deodorized distillate, separating, distilling off the volatile matter by-products obtained during the purification by distillation, the distillation residue fatty acid-esterified, bleaching, a composition is prepared by deodorizing A composition containing 3% by weight or less of free phytosterol, 55 to 65% by weight of phytosterol fatty acid ester, 3 to 10% by weight of triterpene alcohol, 6 to 13% by weight of hydrocarbons, and 3% by weight or less of fatty acid methyl ester . B, C, and D are contained, The permanent wave agent of Claim 1 characterized by the above-mentioned.
B: Vegetable oil.
C: Sucrose fatty acid ester.
D: Liquid higher fatty acid. The permanent wave agent according to claim 1, comprising E.
E: Plant hydrogenated oil. B and E are contained, The permanent wave agent of Claim 1 characterized by the above-mentioned.
B: Vegetable oil.
E: Plant hydrogenated oil. The permanent wave agent according to any one of claims 1 to 4, comprising F, G, and H or I.
F: Higher alcohol.
G: Nonionic surfactant.
H: Anionic surfactant.
I: Cationic surfactant. The permanent wave agent according to claim 1 containing G.
G: Nonionic surfactant. The permanent wave agent according to claim 6 containing I.
I: Cationic surfactant.

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