CN102977262A - Resin solution containing amine oxide group and resin composition for hair cosmetic material using the same - Google Patents

Resin solution containing amine oxide group and resin composition for hair cosmetic material using the same Download PDF

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Publication number
CN102977262A
CN102977262A CN2012105480792A CN201210548079A CN102977262A CN 102977262 A CN102977262 A CN 102977262A CN 2012105480792 A CN2012105480792 A CN 2012105480792A CN 201210548079 A CN201210548079 A CN 201210548079A CN 102977262 A CN102977262 A CN 102977262A
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China
Prior art keywords
value
oxidation
resin
solution
resin solution
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CN2012105480792A
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Chinese (zh)
Inventor
川口重兴
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Mitsubishi Chemical Corp
Mitsubishi Kasei Corp
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Mitsubishi Kasei Corp
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Publication of CN102977262A publication Critical patent/CN102977262A/en
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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
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • 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
    • 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
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • 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
    • A61Q5/12—Preparations containing hair conditioners
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate

Abstract

Disclosed are an amine oxide group-containing resin solution and a resin composition for a hair cosmetic preparation, comprising the resin solution. The resin solution and the resin composition are free from a problem of coloring or discoloration with the elapse of time. The amine oxide group-containing resin solution and the resin composition for a hair cosmetic preparation prepared using the resin solution satisfy the requirement that, for a sample solution prepared from the amine oxide group-containing resin solution and comprising 18% by weight of an amine oxide group-containing resin, 10% by weight of water, and 72% by weight of ethanol, the difference (da) between value a (a0) in an Lab color system and the maximum value (amax) of values a after exposure of the sample solution to ultraviolet light is not more than 5, and the requirement that, for the sample solution, the difference (db) between value b (b0) and value b (bm) when the sample solution exhibits the maximum value (amax) is not more than 9.

Description

The hair cosmetic composition resin combination that contains oxidation amido resin solution and use this solution
The application is to be the dividing an application of PCT International Application Serial No. PCT/JP2009/062915 on July 16th, 2009 applying date, original application is application for a patent for invention, the application number that enters country's stage is 200980000281.8, and name is called " the hair cosmetic composition resin combination that contains oxidation amido resin solution and use this solution ".
Technical field
What the present invention relates to contain the oxidation amine resin contains oxidation amido resin solution, specifically, the present invention relates to have suppressed the painted oxidation amido resin solution that contains that occurs through time lapse.Also relate to and use this to contain the hair cosmetic composition resin combination of oxidation amido resin solution preparation.
Background technology
In the past, as the hair cosmetic composition resin, the known oxidation amine resin that contains has shown good water-soluble, can arbitrarily dilute by water, and the consistency of itself and various makeup bases is excellent, also excellent with the affinity of hair, haircuting property, hair washing property, in this case, the hair cosmetic composition resin combination (for example patent documentation 1～5) that multiple use contains the oxidation amine resin has been proposed.
For such hair cosmetic composition resin combination, the outward appearance of product is the very important element of commodity value and quality aspect, for example, pass to occur in time painted or variable color the product grievous injury its commodity value.
In addition, containing the oxidation amine resin is to carry out polymerization or copolymerization manufacturing with commercially available various monomers as raw material, as required, during manufacturing the structural unit of being introduced by raw material monomer is carried out modification or modification.This starting monomer that contains the oxidation amine resin is polymerizability, thus exist its preserve in or transmit medium during, monomer causes the possibility of quality reduction because of polymerization occurs in the stimulation that is subject to light, heat etc.Therefore, in the raw material monomer liquid of selling as product, be added with stopper to prevent monomer generation polymerization in its preservation or transmission.Particularly sometimes because having reactive height, easily the monomer type of polymerization occuring, so contain a large amount of stoppers in the raw material monomer liquid.
The prior art document
Patent documentation
Patent documentation 1: No. 3520674 communiques of Japanese Patent
Patent documentation 2: No. 3620162 communiques of Japanese Patent
Patent documentation 3: No. 3620163 communiques of Japanese Patent
Patent documentation 4: No. 3620164 communiques of Japanese Patent
Patent documentation 5: No. 3620165 communiques of Japanese Patent
Summary of the invention
The existing hair cosmetic composition that contains oxidation amido resin solution and used such resin solution that contains the oxidation amine resin is excellent with water-soluble, haircuting property, the hair washing property of resin combination, but has As time goes on the problem of the painted or variable color of (particularly exposing to the open air in the situation under the outside atmosphere such as ultraviolet, hot) generation.
The objective of the invention is to solve above-mentioned existing problem, a kind of hair cosmetic composition resin combination that contains oxidation amido resin solution and used this resin solution that contains the oxidation amine resin is provided, and there are not the problem that painted or variable color As time goes on occur in described resin solution and resin combination.
The inventor conducts in-depth research repeatedly for solving above-mentioned problem, found that, contain containing oxidation amido resin solution and having used the hair cosmetic composition of this resin solution to occur painted or variable color with resin combination because of uviolizing of oxidation amine resin.And, find the hair cosmetic composition that contains oxidation amido resin solution and used this resin solution by control with the inhibition dosage in the resin combination be a certain amount of below, can solve the problem that As time goes on painted or variable color occur.
The present invention is based on such understanding realization, and its main points are as follows.
[1] a kind of oxidation amido resin solution that contains is characterized in that it contains the oxidation amine resin, and satisfies following condition (1) and (2).
(1) a 0Value and a MaxThe difference da value of value satisfies following formula (i), wherein, and a 0Value is to a value in the Lab color specification system of the sample solution mensuration of firm preparation, and described sample solution is that the described content that contains the oxidation amine resin that contains the preparation of oxidation amido resin solution of use is that 18 % by weight, water-content are that 10 % by weight and ethanol content are the sample solution of 72 % by weight; a MaxValue be described sample solution is sealed in the glass sample plasma bottle processed and irradiation ultraviolet radiation after the maximum value that reaches of a value in the Lab color specification system measured.
da=a max-a 0≦5 ……(i)
(2) b 0Value and b mThe difference db value of value satisfies following formula (ii), wherein, and b 0Value is to the b value in the Lab color specification system of the sample solution mensuration of above-mentioned (1) of firm preparation; b mValue is that said sample solution shows a in above-mentioned (1) MaxB value during value.
db=b m-b 0≦9 ……(ii)
[2] such as [1] the described oxidation amido resin solution that contains, wherein, described resin solution is without anion exchange process.
[3] a kind of oxidation amido resin solution that contains, its be contain the oxidation amine resin contain oxidation amido resin solution, it is characterized in that this contains oxidation amido resin solution, and not contain stopper or level of inhibitor be below the described 750ppm that contains oxidation amido resin content.
[4] a kind of hair cosmetic composition resin combination, wherein, said composition is to use each described oxidation amido resin solution that contains of [1]～[3] to prepare.
[5] a kind of hair cosmetic composition resin combination, it is the hair cosmetic composition resin combination that contains the oxidation amine resin, it is characterized in that, described composition does not contain stopper or level of inhibitor is below the 20ppm.
Of the present inventionly contain oxidation amido resin solution and there is not the problem that As time goes on painted or variable color occur in hair cosmetic composition with resin combination, good order and condition that can its outward appearance of long term maintenance.
Therefore, by the present invention, provide the high hair cosmetic composition resin combination of commodity value that contains oxidation amido resin solution and used this resin solution of long-term storing stability excellence.
Embodiment
The below is elaborated to the embodiment of hair cosmetic composition of the present invention with resin combination.
Wherein, when not specifying, in this specification sheets, " % ", " ppm " refer to " % by weight ", " ppm by weight ".
In addition, " (methyl) vinylformic acid " expression " vinylformic acid " or " methacrylic acid ", " (methyl) acrylate " is also identical therewith with " (methyl) acrylamide ".
Contain oxidation amido resin solution about oxidation amido resin solution and the hair cosmetic composition of containing of the present invention with what use in the resin combination, when using this to contain oxidation amido resin solution with the sample solution irradiation ultraviolet radiation of specific proportioning preparation, aberration is little, does not have painted problem.Perhaps, about the hair cosmetic composition resin combination that contains oxidation amido resin solution and used this resin solution of the present invention, by not containing stopper or level of inhibitor is controlled in below the prescribed value, thereby prevented painted.
[about As time goes on painted mechanism occur]
It is believed that the hair cosmetic composition that contains oxidation amido resin solution and contain this resin solution with resin combination As time goes on painted reason occurs multiple possibility is arranged, wherein, one of adducible reason is uviolizing, through uviolizing, can find that the hair cosmetic composition that contains oxidation amido resin solution and contain this resin solution with resin combination As time goes on painted or variable color has occured.
In addition, as Another reason, can enumerate the hair cosmetic composition that contains oxidation amido resin solution and contain this resin solution and contain stopper with resin combination.It is believed that this stopper is to contain contained stopper in the starting monomer liquid of oxidation amine resin, its seizure or oneself consume the free radical that produces under the stimulation of heat, light etc., the polymerization of inhibition monomer.It is believed that stopper and free radical material or become the substance reaction in free-radical generating source, generate the compound as painted cause material.
When containing oxidation amido resin solution or hair cosmetic composition and containing stopper with resin combination, As time goes on painted concrete mechanism occuring it be unclear that, it is believed that following reason is an important factor.
Namely, in the manufacturing processed that contains the amine oxide resin, use, be contained in the hydrogen peroxide isoreactivity material that contains in the oxidation amido resin solution or other byproduct of reaction, unreacting materials etc. contain various compositions in the oxidation amine resin or the molten oxygen of depositing in heat, the impact of light issues solution estranged, stopper contained in the free radical that produces during decomposition and the monomer as the manufacturing raw material that contains the oxidation amine resin reacts, this stopper becomes the free radical material, in the process of stopper free radical formation polymer etc., produce coloring material, caused containing oxidation amido resin solution, hair cosmetic composition is painted with resin combination.
On the other hand, make in the resin solution in the situation that contains oxidation amine resin resin in addition, do not find As time goes on not occur painted or variable color.
It is not clear in the concrete mechanism that As time goes on occurs to there are differences aspect painted or the variable color to contain oxidation amine resin and other resin, but contain oxidation amido resin solution or use the hair cosmetic composition of this resin solution preparation to use in the resin combination, by the restriction inhibitor concentration, solved because the outside atmospheres such as ultraviolet ray cause painted problem the hair cosmetic composition resin combination that provide photostabilization, has excellent weather resistance.
[about sample solution]
Among the present invention, sample solution for the mensuration of a value in the Lab color specification system, b value, L value contains the water that contains oxidation amine resin, 10 % by weight of 18 % by weight and the ethanol of 72 % by weight, prepares this sample solution by following operation by the oxidation amido resin solution that contains of the present invention.
That is, being generally used for hair cosmetic composition contains the oxidation amine resin with the preparation of resin combination of the present invention and is supplied to the form that contains oxidation amido resin solution after containing the manufacturing process of oxidation amine resin described later.This contain oxidation amido resin solution contain the ethanol that when containing the manufacturing of oxidation amine resin, is commonly used for reaction solvent, as resultant contain oxidation amine resin, byproduct of reaction, from the water of some amounts of the aquae hydrogenii dioxidi that uses as oxygenant, usually, the concentration that contains the oxidation amine resin is that 18～100 % by weight, water concentration are that 0～35.7 % by weight, alcohol concn are 0～80 % by weight, this solution in water/alcohol mixed solvent, be dissolved with concentration ratio sample solution of the present invention contain oxidation amido resin concentration higher contain the oxidation amine resin.
This contains the properties-correcting agent such as unreacting material that oxidation amido resin solution contains denier, byproduct of reaction, polymerization starter (catalyzer), oxidising agent (hydrogen peroxide etc.) or chemical modifier, from stopper of described starting monomer etc.When representing to contain in the oxidation amido resin solution composition with concentration expressed in percentage by weight, these materials all are compositions of the following so-called ppm order of magnitude of radix point, so among the present invention, these materials are considered to contain the impurity in the oxidation amido resin solution.
Therefore, be that 18 % by weight, water are that 10 % by weight and ethanol are the sample solution of 72 % by weight for containing the oxidation amine resin, contain in 18 % by weight and to contain the impurity component that comprises stopper etc. in the oxidation amine resin, these impurity components all count the concentration that contains the oxidation amine resin at the constituent concentration of sample solution.
But, among the embodiment described later, for clear and definite inhibitor concentration and painted relation, concentration during for the stopper (hydroquinone monomethyl ether among the embodiment (following sometimes referred to as " MEHQ ")) that uses in the present invention as the problem material clearly records inhibitor concentration in addition.
Among the present invention, append water and/or the ethanol of necessary amount at the hair cosmetic composition that is used for of being supplied with by the manufacturing process that contains the oxidation amine resin with the oxidation amido resin solution (its have above-mentioned concentration contain oxidation amine resin, water and ethanol) that contains of the manufacturing of resin combination, it is that 18 % by weight, water concentration are that 10 % by weight, alcohol concn are the sample solution of 72 % by weight that preparation contains oxidation amido resin concentration, supplies in the mensuration of colourity.
Therefore, in this sample solution, except containing oxidation amine resin (this contains the oxidation amine resin and contains impurity from described manufacturing process), do not contain solids component, in addition, do not contain for the acid of adjusting pH or alkali, other reagent yet, and the solvent beyond not moisture in fact and the ethanol.Need to prove that " not containing in fact " content that refers in the sample solution herein is below 1 % by weight.
In addition, containing oxidation amido resin concentration containing in the low situation of oxidation amido resin concentration than sample solution by the hair cosmetic composition that is used for that contains that oxidation amido resin manufacture operation supplies with the oxidation amido resin solution that contains of the manufacturing of resin combination, perhaps this solvent that contains oxidation amido resin solution is other solvents, rather than water/alcohol mixed solvent, and appending simply water and/or ethanol can not prepare in the situation of sample solution of afore mentioned rules concentration, can be suitably not affecting under the condition that contains the oxidation amine resin desolventizing or carrying out solvent exchange, prepare thus sample solution.As in this case removal of solvents or the method for solvent exchange, can enumerate and utilize underpressure distillation or soak into method of film etc.
In addition, the oxidation amido resin concentration that contains of sample solution is that 18 % by weight, water are 10 % by weight and ethanol when being 72 % by weight, and its pH does not have notable difference, and usually, pH is 6～9 degree.
[about the mensuration of colourity]
The invention is characterized in to as described above the preparation the sample solution irradiation ultraviolet radiation time, the variation that the colourity of Lab color specification system occurs in time is little.
The method of this sample solution irradiation ultraviolet radiation of subtend is not particularly limited, sample solution can be packed into and shine sunlight, UV-lamp (can use spectral filter in case of necessity) behind the glass sample plasma bottle processed, can also use fast light promotion trier (for example, ア イ ス パ ー UV tstr SUV-W1 (the rugged electric society of rock makes)) etc.Light wavelength, the intensity of shining is not particularly limited, for example can enumerates with 600W/m 2The ultraviolet ray of intensity illumination wavelength 300～400nm.
That is, among the present invention, as described later, to the sample solution irradiation ultraviolet radiation, with a of a value when reaching maximum of Lab color specification system this moment MaxValue and a 0The b of poor (the da value) of value and this moment thereof mThe value and based on L mThe value of value is index, but ultraviolet irradiation condition, illuminating method itself are not particularly limited, and no matter uses which kind of condition, method irradiation ultraviolet radiation, a MaxValue, b mValue, L mValue all can be stipulated with identical method.That is, shown in the embodiment, along with ultraviolet irradiation, a value becomes greatly gradually as described later, reach maximum value after, again diminish.So among the embodiment described later, the result who sample solution is placed on the irradiation of irradiation ultraviolet radiation under the sunlight and adopts the situation of the additive method of UV tstr etc. to obtain is roughly the same, a MaxValue, b mValue, L mValue can be stipulated with identical method.
In addition, reach a MaxThe time of value is different because of the difference of ultraviolet irradiation condition, illuminating method, a MaxValue itself also what can change sometimes because of the difference of this illuminate condition, illuminating method.For example, among the embodiment, compare with the situation of carrying out uviolizing with fast light promotion trier (UV tstr), be placed in the situation of carrying out uviolizing under the sunlight a MaxBe worth on the low side.Its reason is by inference, compares with the situation of using the UV tstr, and the photogenic painted required time of the sun is long, and before a value reached maximum value, the redness that affects a value was faded etc. along with the time.In addition, in the situation of irradiation sunlight, also shone simultaneously the ultraviolet ray light in addition of wavelength 300～400nm, so think that these light are also influential.
But in painted few scope of the present invention of the sample solution that the outside atmospheres such as ultraviolet ray cause, the difference that illuminate condition, illuminating method cause is little.
In addition, as mentioned above, along with ultraviolet irradiation, a value slowly becomes greatly, reach maximum value after, a value diminishes again, so, can increase along with the time and rise in a value, obviously transfer decline to thereafter after, finish to measure, take before this maximum value as a MaxValue.
In addition, the envrionment conditions during about uviolizing can be at normal temperature (specifically 0～60 ℃), sample solution is sealed in the situation of irradiation ultraviolet radiation behind the sample plasma bottle, about the condition that is not stressed and humidity condition.
Embodiment is described as described later carries out like that for the mensuration of the colourity of sample solution, UV visual spectrophotometer V-530 and the color computer card TSV-566 type that for example, can use colour examining colour-difference-metre ND-1001DP type that Japanese electric look industry society makes, Japanese light splitting society to make are measured.
[about aberration]
Among the present invention, take distilled water as standard test specimen, the colourity in the Lab color specification system of measuring with the sample solution of above-mentioned method preparation is satisfied following (i) formula and (ii) formula, preferably also satisfy following (iii) formula.
da=a max-a 0≦5 ……(i)
db=b m-b 0≦9 ……(ii)
dE=(dL 2＋da 2＋db 2) 1/2≦10 ......(iii)
Wherein, dL=L m-L 0
Herein, a 0Value, b 0Value, L 0Value is respectively to a value, b value, L value in the Lab color specification system of the sample solution mensuration of firm preparation, a MaxValue representation is packed sample solution in the glass sample plasma bottle processed into behind the irradiation ultraviolet radiation, the maximum value that a value reaches, b mValue and L mValue is respectively that a value reaches maximum value a MaxB value during value, L value.
In addition, just the sample solution of preparation refers to prepare behind the sample solution 24 hours with interior sample solution, and is the sample solution that does not have initiatively to carry out the state of uviolizing.
Among the present invention, above-mentioned as long as no satisfying (i) formula and (ii) any one in the formula are with regard to there being the problem because of the painted appearance degradation that causes, so be not preferred.
Da value (a Max-a 0) be preferably below 3 db value (b m-b 0) be preferably below 5 dE (=(dL 2+ da 2+ db 2) 1/2) more preferably below 6.In the situation of such value, when making hair cosmetic composition with resin combination (usually containing oxidation amido resin concentration is 0.01～10 % by weight), can the painted problem of basically eliminate.
In the Lab color specification system, general red strong, then a value is large; Yellowing is strong, and then the b value is large.In the cosmetic composition, the variable color that the general red variable color that causes causes than yellowing more needs to avoid.Therefore, da value less value preferably.
Da＜=3, db＜=5, dE＜=6 o'clock are used this to contain oxidation amido resin solution and are made hair cosmetic composition with in the situation of resin combination, and variable color is considerably less, can access high-quality product.
In addition, hair cosmetic composition is made with in the situation of resin combination in da＜=5, db＜=9 o'clock, variable color is slightly arranged, but practical no problem, when da surpass 5, when db surpasses 9, make hair cosmetic composition with in the situation of resin combination, have variable color, become the problem in the practicality.
[containing the level of inhibitor in the oxidation amido resin solution]
The hair cosmetic composition that contains oxidation amido resin solution and use this resin solution to prepare of the present invention is characterised in that with resin combination this contains, and oxidation amido resin solution does not contain stopper or level of inhibitor is to contain below the 750ppm of oxidation amido resin content.
There is painted problem in the used level of inhibitor that contains oxidation amido resin solution when containing the 800ppm of oxidation amido resin content in the preparation of hair cosmetic composition with resin combination, is undesirable as the hair cosmetic composition resin combination.This level of inhibitor that contains in the oxidation amido resin solution is more few better, the 750ppm that more preferably contains the oxidation amine resin is following, more preferably 600pprn following, further be preferably 500ppm following, more more preferably 400ppm following, be particularly preferably below the 250ppm.
In addition, herein alleged contain oxidation amido resin solution be as described above by the manufacturing process that contains the oxidation amine resin supply with as hair cosmetic composition with the manufacturing raw material of resin combination contain oxidation amido resin solution, it consists of by containing oxidation amine resin, water and ethanol usually.
[level of inhibitor of 00431[hair cosmetic composition in the resin combination]
And hair cosmetic composition of the present invention is characterised in that with resin combination not containing stopper or level of inhibitor is below the 20ppm.
Hair cosmetic composition is 20ppm when following with the level of inhibitor of resin combination, does not have painted problem, is desirable as the hair cosmetic composition resin combination.Hair cosmetic composition is more few better with the level of inhibitor in the resin combination, is preferably below the 10ppm, more preferably below the 5ppm.
In addition, hair cosmetic composition is identical with the above-mentioned level of inhibitor that contains in the oxidation amido resin solution with respect to the content that contains the oxidation amine resin with stopper in the resin combination, be preferably the 800ppm that contains the oxidation amine resin following, more preferably 750ppm following, more preferably 600ppm following, further be preferably 500ppm following, more more preferably 400ppm following, be particularly preferably below the 250ppm.
In addition, only estimate containing oxidation amido resin solution among the embodiment described later, but usually using by the oxidation amido resin concentration that contains that contains that oxidation amido resin manufacture operation supplies with is that the oxidation amido resin solution that contains about 10～60 % by weight is made the hair cosmetic composition resin combination, the concentration that contains the oxidation amine resin in the said composition of making is generally about 0.1～10 % by weight, contain oxidation amido resin solution and be diluted 1～600 times, so utilize embodiment 1～3 described later contain oxidation amido resin solution the time, certainly can make and satisfy above-mentioned hair cosmetic composition with the level of inhibitor upper limit in the resin combination and do not have the hair cosmetic composition resin combination of coloring problem.
[stopper]
Stopper of the present invention normally contains in the starting monomer of oxidation amine resin contained, and its result for containing stopper of the present invention the containing in the oxidation amido resin solution of preparation in the hair cosmetic composition resin combination, for example can enumerate following substances.
Resorcinol (HQ); 4-methoxyphenol (hydroquinone monomethyl ether: MEHQ); The 4-thanatol; 4-propoxy-phenol; 4-butoxy phenol; 4-heptyloxybenzene phenol; The Resorcinol single-benzyl ether; 1,2-dihydroxy-benzene; The 2-methoxyphenol; 2,5-, two chlorohydroquinones; 2,5 di tert butyl hydroquinone; 2-ethanoyl Resorcinol; The Resorcinol mono benzoate; Isosorbide-5-Nitrae-thioresorcin; 1,2-thioresorcin; TMHQ; PAP; Ortho-Aminophenol; 2-N, the N-dimethyl p-aminophenol; 2-mercapto-phenol: 4-mercapto-phenol; The pyrocatechol single-butyl ether; 4-ethylamino phenol; 2,3-resacetophenone; Pyrogallol-1, the 2-dimethyl ether; The 2-methylbenzene phenyl-sulfhydrate; Tert-butyl catechol; The di-t-butyl oxynitride; Two tert-pentyl oxynitride; 2,2,6,6-tetramethyl--piperidine oxide; 4-hydroxyl-2,2,6,6-tetramethyl--piperidine oxide; 4-oxygenate-2,2,6,6-tetramethyl--piperidine oxide; 4-dimethylamino-2,2,6,6-tetramethyl--piperidine oxide; 4-amino-2,2,6,6-tetramethyl--piperidine oxide; 4-ethanol oxygen base-2,2,6,6-tetramethyl--piperidine oxide; 2,2,5,5-tetramethyl--pyrrolidyl oxide compound; 3-amino-2,2,5,5-tetramethyl--pyrrolidyl oxide compound; 2,2,5,5-tetramethyl--1-oxa--3-nitrogen heterocyclic amyl group-3-oxide compound (2,2,5,5-テ ト ラ メ チ Le-1-オ キ サ-3-ア ザ シ Network ロ ペ Application チ Le-3-オ キ シ); 2,2,5,5-tetramethyl--3-pyrrolidyl-1-oxygen-3-carboxylic acid; 2,2,3,3,5,5,6,6-prestox-Isosorbide-5-Nitrae-diazacyclo hexyl-Isosorbide-5-Nitrae-dioxide; 4-nitrosobenzene phenates; The 2-nitrosophenol; The 4-nitrosophenol; Cupric dimethyldithiocarbamate; Copper diethyl dithiocarbamate; Copper dibutyldithiocarbamate; Cupric salicylate; Methylene blue; Iron; Thiodiphenylamine (PTZ); 3-oxygenate thiodiphenylamine; 5-oxygenate thiodiphenylamine; Phenothiazine dimer; Isosorbide-5-Nitrae-phenylenediamine; N-(Isosorbide-5-Nitrae-dimethyl amyl group)-N '-phenyl-Isosorbide-5-Nitrae-phenylenediamine; N-(1,3-dimethylbutyl)-N '-phenyl-Isosorbide-5-Nitrae-phenylenediamine; N-nitroso-group phenyl oxyamine and their salt; Nitrogen oxide; Nitrosobenzene; Para benzoquinone; The isomer of these materials; Mixture in these materials more than 2 kinds; Among the above-mentioned substance more than a kind with the mixture of molecularity oxygen.
Among these stoppers, it is preferred in the starting monomer that what use is that the phenol that has the stopper of the multiple bond that forms conjugated system, particularly has an aromatic ring is stopper, especially HQ (Resorcinol), MEHQ (hydroquinone monomethyl ether), so the object stopper among the present invention often is that the phenol such as these HQ, MEHQ are stopper, particularly preferably is MEHQ.
Stopper can be a kind in these materials, also can be more than 2 kinds.
Contain oxidation amido resin solution or hair cosmetic composition with in the situation that contains stopper more than 2 kinds in the resin combination, the total content of controlling these stoppers is below the above-mentioned higher limit.
[reducing the method for level of inhibitor]
It is of the present invention that to contain the stopper that oxidation amido resin solution or hair cosmetic composition contain with resin combination be to contain in described later containing in the starting monomer that contains the oxidation amine resin that uses in the oxidation amido resin manufacture operation.
Therefore, contain oxidation amido resin solution or the hair cosmetic composition few to the preparation level of inhibitor are not particularly limited with the method for resin combination, for example can enumerate following operation.
(1) behind the synthesizing oxygen-containing amine resin, carries out activated carbon treatment to containing the oxidation amine resin.
(2) behind the synthesizing oxygen-containing amine resin, process containing the oxidation amine resin with Zeo-karb.
(3) by absorption, distillation, from starting monomer, remove stopper, reduce level of inhibitor or make it not contain stopper, use such starting monomer manufacturing to contain the oxidation amine resin.
(4) use not the starting monomer manufacturing of adding stopper in the starting monomer or having reduced the stopper addition to contain the oxidation amine resin.
(5) Combination of Methods of above-mentioned (1)～(4) carries out.
In addition, in above-mentioned (1) method, the synthetic described oxidation amido resin solution that contains that contains the oxidation amine resin, namely supplied with by the manufacturing process that contains the oxidation amine resin is carried out in the situation of activated carbon treatment, specifically can adopt following (1-1) or method (1-2) and condition.
(1-1) make the method that contains the post of oxidation amido resin solution by being filled with gac
(condition)
Wash-out SV (air speed)=0.1～0.8 hour -1
Temperature: 10～60 ℃
(1-2) add gac to containing in the oxidation amido resin solution, carry out the method for solid-liquid separation after the stirring
(condition)
Contain oxidation amido resin solution: gac=1:10 to 2:1 (volume ratio)
Temperature: 10～80 ℃
Churning time: 1～10 hour
In addition, can also enumerate as the method for above-mentioned (2) spent ion exchange resin to synthetic containing the oxidation amine resin, namely describedly contain the method that oxidation amido resin solution is processed by what the manufacturing process that contains the oxidation amine resin supplied with, but the oxidation amido resin solution that contains of the present invention is preferably without anion exchange process.Usually, contain oxidation amido resin solution and often contain the oxygenants such as hydrogen peroxide that are used as oxidising agent in its manufacturing process.On the other hand, usually, the main chain of anionite-exchange resin or functional group are subject to the attack of the oxygenants such as hydrogen peroxide, occur to decompose etc., cause the generation of these disengaging thing, the reduction of resin life.Therefore, the problem through exist the impurity such as disengaging thing of sneaking into anionite-exchange resin to cause containing in the oxidation amido resin solution of anion exchange process has detrimentally affect etc. to smell, color, so be not preferred.
[manufacture method that contains the oxidation amine resin]
The manufacture method that contains the oxidation amine resin of the present invention is not particularly limited, the for example hydrophilic monomer (following sometimes be called " (A) composition " or " hydrophilic monomer (A) ") by will containing oxidation amido monomer and hydrophobic monomer (following sometimes be called " (B) composition " or " hydrophobic monomer (B) ") polymerization or the copolymerization used as required can be used as thus and describedly contains the manufacturing of oxidation amido resin solution and contain the oxidation amine resin.
In addition, in this case, also can use nitrogenous precursor monomer (following " nitrogenous precursor monomer (b) " or " (b) composition " of sometimes being called) to replace containing oxidation amido monomer (following " containing oxidation amido monomer (a) " or " (a) composition " of sometimes being called), after making its polymerization or copolymerization, by carrying out oxidation, introduce the oxidation amido; After can also making the monomer polymerization or copolymerization with reactive functional, with have concurrently can with the compound reaction of the active group of this functional group reactions and oxidation amido, introduce thus the oxidation amido, such method also can be made the oxidation amine resin that contains of the present invention.In addition, hereinafter, replace containing above-mentioned nitrogenous precursor monomer (b) that oxidation amido monomer (a) uses or sometimes be called " the oxidation amido is introduced and used monomer " with the monomer of reactive functional.
Contain the oxidation amine resin as the aspect of performance of hair cosmetic composition with the resin combination composition from what obtain, preferably for being to contain oxidation amido monomer (a) or oxidation amido introducing monomer more than 30 % by weight in the hydrophilic monomer (A) of polymerization, more preferably containing the introducing of oxidation amido monomer (a) or oxidation amido is more than 50 % by weight with monomer shared ratio in whole hydrophilic monomers (A).This ratio more preferably 80 % by weight above, be particularly preferably more than 95 % by weight.
＜contain oxidation amido monomer (a) 〉
As (a) composition contain oxidation amido monomer, for example can enumerate the monomer shown in the following general formula (I)～(IV).
Figure BDA00002597770300111
Figure BDA00002597770300121
In the formula, R 1Expression hydrogen atom or methyl, R 2And R 3Represent that independently of one another carbonatoms is that 1～24 alkyl, carbonatoms are that 6～24 aryl or carbonatoms are 7～24 aralkyl, R 4And R 5The expression carbonatoms is that 1～24 alkyl, carbonatoms are that 6～24 aryl or carbonatoms are 7～24 aralkyl.X represents that divalent connects base, and m represents 0～1 integer, and n represents 0～4 integer.P represents 0～3 integer, and Y represents-C (R 11) R 12-,-NR 13-,-S-or-O-, R 6～R 13In at least one represents CH independently of one another 2=C (R 1)-(X) m-, other R 6～R 13Represent that independently of one another hydrogen atom, carbonatoms are that 1～24 alkyl, carbonatoms are that 6～24 aryl or carbonatoms are 7～24 aralkyl.A and b represent 1～10 integer independently of one another.In addition, X, R 4, R 5, R 7, R 8, R 9, R 10X more than 2, R are arranged in a plurality of situations 4, R 5, R 7, R 8, R 9, R 10Can be the same or different.
Monomer shown in the above-mentioned general formula (I) can be enumerated (methyl) vinylformic acid N, the N-dimethylaminoethyl, (methyl) vinylformic acid N, the N-lignocaine ethyl ester, (methyl) vinylformic acid N, N-dimethylamino propyl ester, (methyl) vinylformic acid N, N-diethylin propyl ester, N, N-dimethylaminoethyl (methyl) acrylamide, N, N-diethyllaminoethyl (methyl) acrylamide, N, N-dimethylamino-propyl (methyl) acrylamide, N, N-diethylin propyl group (methyl) acrylamide, N, N-dimethylamino propionate, to dimethylamino methyl vinylbenzene, to dimethylaminoethyl vinylbenzene, to the diethylin vinyl toluene, amine oxide to diethyllaminoethyl vinylbenzene etc.; Perhaps maleic anhydride, itaconic anhydride, crotonic anhydride etc. contain acid anhydrides and the N of unsaturated group, and N-dimethyl-1,3-propanediamine, aniline etc. contain the reaction product with the material of the reaction active groups of acid anhydrides; Methacrylic dehydrated glycerides etc. contain monomer and the N of epoxy group(ing), and N-dimethyl-1,3-propylene diamine etc. contain the reaction product with the material of the reaction active groups of epoxy group(ing); Deng the amine oxide compound.In addition, can also enumerate monomer and hydroxyethyl-N that glycidyl methacrylate etc. contains epoxy group(ing), N-dimethyl oxidation amine is such contains monomer and the hydroxyethyl-N that contains isocyanate group with the resultant that contains the amine oxide thing of the active group of epoxy reaction, (methyl) vinylformic acid 2-isocyanate group ethyl ester etc., and N-dimethyl oxidation amine etc. contains the resultant that contains the amine oxide thing with the active group of isocyanic ester radical reaction.
Monomer shown in the above-mentioned general formula (II) can be enumerated the 2-vinyl pyridine, the 3-vinyl pyridine, 4-vinylpridine, 2-methyl-5-vinylpyrine, 3-methyl-5-vinyl pyridine, 4-methyl-5-vinyl pyridine, 6-methyl-5-vinyl pyridine, 2-methyl-4-vinylpridine, 3-methyl-4-vinylpridine, 2-dodecyl-5-vinyl pyridine, 2-dodecyl-4-vinylpridine, 2-(tertiary butyl)-5-vinyl pyridine, the alkyl of 2-(tertiary butyl)-4-vinylpridine etc., aryl, the amine oxide compounds such as the affixture of alkylaryl.
Monomer shown in the above-mentioned general formula (III) can be enumerated 1-vinyl imidazole, 2-methyl isophthalic acid-vinyl imidazole, 4-methyl isophthalic acid-vinyl imidazole, 5-methyl isophthalic acid-vinyl imidazole, 2-dodecyl-1-vinyl imidazole, 4-(the tertiary butyl)-amine oxide compounds such as 1-vinyl imidazole.
Monomer shown in the above-mentioned general formula (lV) can be enumerated the amine oxide compounds such as 4-vinyl morpholine, 2-methyl-4-vinyl morpholine, 4-allyl group morpholine, 1-vinyl piperidines, 4-methyl-4-vinyl piperidines, 2-dodecyl-1-vinyl piperazine, methacrylic acid 2-methylpiperazine base ethyl ester.
In these monomers, the most preferably monomer shown in the general formula (I), the especially most preferably R in the general formula (I) 2And R 3That carbonatoms is the monomer of 1～4 alkyl.
＜nitrogenous precursor monomer (b) 〉
As the nitrogenous precursor monomer before (b) composition oxidized, can enumerate the monomer shown in the following logical formula V～(VIII).
Figure BDA00002597770300131
Figure BDA00002597770300141
R in the formula 1～R 10, a, b, m, n, p, X, Y definition identical with the definition in the above-mentioned formula (I)～(IV).
The not oxidized hydrophilic monomer that can directly be used as (A) composition of above-mentioned (b) composition.
＜other hydrophilic monomer (c) 〉
As other (A) composition, introduce with the monomer except the above-mentioned oxidation amidos such as oxidation amido monomer (a), nitrogenous precursor monomer (b) that contain, can also use other hydrophilic monomers (c).As these hydrophilic monomers, can enumerate nonionic, anionic property, cationic or with having negatively charged ion and cationic two ionic ampholytic monomers in a part concurrently.
Among such monomer, as non-ionic monomer, can enumerate by (methyl) Hydroxyethyl Acrylate, polyoxyethylene glycol (methyl) acrylate, single (methyl) acrylate of methoxyl group poly-(ethylene glycol/propylene glycol), polyoxyethylene glycol two (methyl) acrylate, (methyl) vinylformic acid such as N-polyalkylene oxide (methyl) acrylamide or (methyl) acrylamide and carbonatoms are monomer and (methyl) vinyl cyanide that 2～4 oxirane is derived, the N-N-cyclohexylmaleimide, N-phenylmaleimide, NVP, N-(methyl) acryloyl morpholine, the hydrophilic monomers such as acrylamide.
As the anionic property monomer, can enumerate the unsaturated carboxylic acid monomers such as (methyl) vinylformic acid, toxilic acid, maleic anhydride, methylene-succinic acid, fumaric acid, butenoic acid; The half ester of unsaturated multi-anhydride (such as succinyl oxide, Tetra hydro Phthalic anhydride etc.) and (methyl) acrylate that contains hydroxyl (such as (methyl) Hydroxyethyl Acrylate etc.); Styrene sulfonic acid, (methyl) vinylformic acid sulfo group ethyl ester etc. have sulfonic monomer; The acid phosphinylidyne oxygen base ethyl ester of (methyl) vinylformic acid (acidphosphoxyethyl (meth) acrylate) etc. has the monomer of phosphate etc.
These anionic property unsaturated monomers can be directly use with the form of acid, also can partly neutralize or use after the neutralization fully, can also be directly are used for copolymerization, then carry out part and neutralize or neutralize fully with the form of acid.As in and the time alkali that uses, such as the amine compound such as the alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, ammoniacal liquor, monoethanolamine, diethanolamine, trolamine, Trimethylamine 99 are arranged.
As cationic monomer, can enumerate (methyl) vinylformic acid N, the N-dimethylaminoethyl, (methyl) vinylformic acid N, the N-lignocaine ethyl ester, (methyl) vinylformic acid N, N-dimethylamino propyl ester, (methyl) vinylformic acid N, N-diethylin propyl ester, N, N-dimethylaminoethyl (methyl) acrylamide, N, N-diethyllaminoethyl (methyl) acrylamide, N, N-dimethylamino-propyl (methyl) acrylamide, N, N-diethylin propyl group (methyl) acrylamide, to dimethylamino methyl vinylbenzene, to dimethylaminoethyl vinylbenzene, to the diethylin vinyl toluene, to diethyllaminoethyl vinylbenzene etc. through cationic agent (methyl chloride for example, monobromethane, the halogenation alkanes such as methyl iodide, the sulfuric acid dialkyl esters such as methyl-sulfate, N-(3-chlorine-2-hydroxyl propyl group)-N, N, the Epicholorohydrin affixture of the tertiary amine inorganic acid salts such as N-trimethyl ammonium chloride, hydrochloric acid, Hydrogen bromide, sulfuric acid, the inorganic salt of phosphoric acid etc., formic acid, acetic acid, the carboxylic acids such as propionic acid etc.) cationic monomer of cationization.
As the both sexes unsaturated monomer, can use the properties-correcting agent such as halogenated acetic acids sodium or halogenated acetic acids potassium as properties-correcting agent described cationic monomer to be made zwitter-ion is that monomer uses.
＜hydrophobic monomer (B) 〉
As hydrophobic monomer (B), can enumerate carbonatoms and be 1～24 alcohol (methyl) alkyl acrylate, vinylbenzene, p-methylstyrene, the hydrophobic vinyl monomers such as chloro-styrene, vinyl methyl ether, vinyl cyclohexyl ether, vinyl-acetic ester, ethyl maleate, dibutyl maleinate, (methyl) glycidyl acrylate, (methyl) acrylic acid fluoroalkyl, the silicone macromolecule monomer etc. that contains free-radical polymerised unsaturated group are contained macromonomer of unsaturated group etc.
It is the example of (methyl) acrylate of 1～24 alcohol as above-mentioned carbonatoms, can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) acryllic acid propyl ester, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, the secondary pentyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid 1-ethyl propyl ester, (methyl) vinylformic acid 2-methyl butyl ester, (methyl) vinylformic acid isopentyl ester, (methyl) vinylformic acid tert-pentyl ester, (methyl) vinylformic acid 3-methyl butyl ester, (methyl) vinylformic acid peopentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid 2-methyl pentyl ester, (methyl) vinylformic acid 4-methyl pentyl ester, (methyl) vinylformic acid 2-ethyl butyl ester, (methyl) vinylformic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) vinylformic acid 2-heptyl ester, (methyl) vinylformic acid 3-heptyl ester, (methyl) Octyl acrylate, (methyl) vinylformic acid 2-monooctyl ester, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid 3, the own ester of 3,5-trimethylammonium, (methyl) decyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) aliphatic acrylate, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid eicosyl ester, (methyl) vinylformic acid docosyl ester, (methyl) vinylformic acid tetracosyl ester, (methyl) acrylic methyl cyclohexyl, (methyl) isobornyl acrylate, (methyl) vinylformic acid norborneol ester, (methyl) vinylformic acid benzyl ester, (methyl) vinylformic acid styroyl ester etc.
Among these, preferred carbonatoms is that (methyl) acrylate, particularly carbonatoms of 1～24 alcohol is (methyl) acrylate of 1～18 alcohol.
＜(A)/(B) polymerization ratio of composition 〉
As the preferable amount of the hydrophobic monomer of (B) composition, according to the hydrophobicity degree of (B) composition, the purposes that contains the oxidation amine resin that obtains, use form and different.Usually, below 85 % by weight of this consumption for whole monomers of being used for polymerization, and the water miscible scope of the resin after not damaging polymerization.
Hair cosmetic composition roughly is divided into typing with resin combination and uses and nurse (conditioning) usefulness.
Use the resulting oxidation amine resin that contains to use in the situation of resin as typing, for (A) composition of the manufacturing that is used for containing the oxidation amine resin and (B) ratio of composition, preferred (A) composition is that 15～90 % by weight, (B) composition are 85～10 % by weight.When (A) composition is less than 15 % by weight, smoothness and the transparent variation of the epithelium that is sometimes consisted of by multipolymer, and become and be insoluble in water, be difficult to during hair washing clean and remove.In addition, when (A) composition is greater than 90 % by weight, sometimes can not fully finalize the design.
Typing has the form of spraying, mousse, gel etc. with hair cosmetic composition.
For example use in the situation that contains the oxidation amine resin that obtains with the form of resin with spraying, be used for containing the oxidation amine resin manufacturing (A) composition and (B) ratio of composition to be preferably (A) composition be that 15～90 % by weight, (B) composition are 85～10 % by weight, more preferably (A) composition is that 30～80 % by weight, (B) composition are 70～20 % by weight.
Use in the resulting situation that contains the oxidation amine resin with the form of resin with mousse, owing to the ratio of the water that is used as solvent is large, so require wetting ability higher, be used for containing the oxidation amine resin manufacturing (A) composition and (B) ratio of composition to be preferably (A) composition be that 30～90 % by weight, (B) composition are 70～10 % by weight, more preferably (A) composition is that 40～80 % by weight, (B) composition are 60～20 % by weight.
Use in the resulting situation that contains the oxidation amine resin with the form of resin with gel, identical with mousse, because the ratio of water is large, so require suitable wetting ability, and from considering with the aspect of the affinity of gel matrix, be used for containing the oxidation amine resin manufacturing (A) composition and (B) ratio of composition to be preferably (A) composition be that 40～90 % by weight, (B) composition are the 60-10 % by weight, more preferably (A) composition is that 50～80 % by weight, (B) composition are 50～20 % by weight.
On the other hand, use in the situation that contains the oxidation amine resin that obtains with the form of resin with nursing, consider smooth thoughts and feelings, the easy cleaning of hair, the requirement wetting ability is high, be used for containing the oxidation amine resin manufacturing (A) composition and (B) ratio of composition to be preferably (A) composition be that 30～100 % by weight, (B) composition are 70～0 % by weight, more preferably (A) composition is that 50～100 % by weight, (B) composition are 50～0 % by weight.
＜polymerization process 〉
As the manufacture method that contains the oxidation amine resin of the present invention, can adopt following method:
(1) with nitrogenous precursor monomer (b) oxidation shown in the described logical formula V～(VIII), uses the method that oxidation amido monomer carries out polymerization or copolymerization that contains that has obtained;
(2) use the nitrogenous precursor monomer (b) shown in the described logical formula V～(VIII), carry out polymerization or copolymerization, the polymer with nitrogen that obtains is carried out the method for oxidation;
(3) use monomer with reactive functional to carry out polymerization or copolymerization after, make it with have concurrently can be with the method for the substance reaction of the active group of this functional group reactions and oxidation amido etc.,
The preferred method of above-mentioned (2) wherein.
Containing the oxidation amine resin can in the presence of radical polymerization initiator, obtain above-mentioned monomer component polymerization by known methods such as solution polymerization, mass polymerization, suspension polymerizations usually.Be particularly suitable for obtaining by solution polymerization.
In addition, as polymer solvent, can use separately or the organic solvents such as mixing use acetone, butanone, methyl iso-butyl ketone (MIBK), methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, sec-butyl alcohol, ethyl acetate, propyl acetate, butylacetate more than 2 kinds.
As radical polymerization initiator, can use 2,2 '-Diisopropyl azodicarboxylate (AIBN), 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (4-methoxyl group-2, the 4-methyl pentane nitrile), 2,2 '-azo-bis-iso-dimethyl, 2,2 '-azo two (2-methylbutyronitrile), 1, the superoxide such as azo-compound, benzoyl peroxide, dicumyl peroxide, ditertiary butyl peroxide, lauroyl peroxide such as 1 '-azo two (1-hexanaphthene formonitrile HCN) etc.
The usage ratio of these polymerization starters is 0.01～5 % by weight with respect to the monomer component that is used for reaction usually.
For polymerization, usually under the inert gas atmospheres such as nitrogen, argon, carried out 1～20 hour in 30 ℃～120 ℃, preferred 40 ℃～100 ℃.
＜oxidation 〉
Utilize the method manufacturing of above-mentioned (2) to contain in the situation of oxidation amine resin, add oxygenant in the precursor polymer solution that obtains to the monomer component polymerization, carry out 0.1～100 hour, preferred 1～50 hour oxidation 20 ℃～100 ℃ scope, obtain thus containing the oxidation amine resin.
As oxygenant, can use the oxygenants such as superoxide or ozone.As superoxide, can enumerate hydrogen peroxide, ammonium persulphate, Sodium Persulfate, peracetic acid, metachloroperbenzoic acid, benzoyl peroxide, tertbutyl peroxide etc., usually use hydrogen peroxide, hydrogen peroxide uses with the form of the aqueous solution usually.
The consumption of these oxygenants is the ratio of 0.2～3 times of molar equivalent, particularly 0.5～2 times of molar equivalent with respect to oxidable functional group contained in the precursor polymer preferably.
Reaction obtains contains oxidation amido resin solution and can be process residual superoxide and just be used for the hair cosmetic composition resin combination, also can process rear use with known method.
Specifically, can enumerate the interpolation reductive agent processes, utilizes processing, the activated carbon treatment of ion exchange resin, utilizes the processing of metal catalyst etc.
The resin solution that obtains can directly use, and uses after also can utilizing as required the known method such as heavily heavy, solvent distillation removal to isolate to contain the oxidation amine resin.In addition, the isolated oxidation amine resin that contains can further be made with extra care by heavily heavy, solvent cleaning, membrane sepn, adsorption treatment etc. as required.
The weight-average molecular weight that contains the oxidation amine resin that so obtains (the polystyrene conversion value of trying to achieve by gel permeation chromatography) is 5000～1000000, is preferably 10000～500000, more preferably 20000～300000.Be generally used for resin that hair cosmetic composition uses as the typing time spent, preferred molecular weight is less, as the nursing time spent, preferred molecular weight is larger, and as the typing time spent, weight-average molecular weight is preferably 5000～300000, as the nursing time spent, weight-average molecular weight is preferably 20000～1000000.
[hair cosmetic composition resin combination]
Can use the oxidation amido resin solution that contains that as above obtains to prepare the hair cosmetic composition resin combination.As hair cosmetic composition resin combination of the present invention, as long as use the oxidation amido resin solution preparation that contains of the present invention, said composition also can contain other known compounds that is usually used in hair cosmetic composition.
For example, use the oxidation amido resin solution that contains of the present invention can make the hair cosmetic composition resin combinations such as shampoo, Rinsing, hair conditioner, setting agent, permanent wave solution.
At this moment, known polymkeric substance and the above-mentioned oxidation amine resin that contains that in the past used can be share.
Hair cosmetic composition of the present invention can be the arbitrarily form such as liquid, breast frost, emulsion, gel, mousse with resin combination.
Hair cosmetic composition with the content that contains the oxidation amine resin in the resin combination according to hair cosmetic composition with the kind of the form of resin combination and purpose or the polymkeric substance that share and amount and different, but hair cosmetic composition preferably is set in about 0.01～10 % by weight as mentioned above like that with the oxidation amido resin content that contains in the resin combination.
Hair cosmetic composition is with among the purposes of resin combination, setting agent comprise aerosol hair spray, pump formula hair with propellant, spumescence hair with propellant, moisten the known hairdressing product take alcohols such as water and/or ethanol, Virahols as solvent such as a sprays, style keeping liquid, setting agent, hair-cream, hair oil.In this case, hair cosmetic composition is with in the resin combination, and containing the oxidation amine resin can use separately, also can be used with polymkeric substance with the known typing of cationic, anionic property, nonionic and the both sexes commonly used.
For example, as can be with the hair cosmetic composition (mousse) of foam state ejection the time, hair cosmetic composition is composed as follows with resin combination: containing the oxidation amine resin is that 0.01～10 % by weight, known typing polymkeric substance are that 0～15 % by weight, nonionic surfactant are that 0.1～5 % by weight, liquefied gas (propellant) are that 3～25 % by weight and the water-soluble solvent take water as main body are 60 % by weight～surplus (wherein, the content of water in hair cosmetic composition is more than 60 % by weight).
As in the situation of gel, hair cosmetic composition is composed as follows with resin combination: containing the oxidation amine resin is that 0.01～10 % by weight, known typing polymkeric substance are that 0～15 % by weight, gel matrix are that 0.1～3 % by weight, water are 72 % by weight～surplus.
As in the situation of hair propellant, hair cosmetic composition is composed as follows with resin combination: containing the oxidation amine resin is that 0.01～10 % by weight, known typing polymkeric substance are that 0～15 % by weight, solvent are that 30～80 % by weight, propellant are 10～70 % by weight.
As the known typing polymkeric substance that can share, for example ether (trade(brand)name: LEOGUARD G (manufacturing of LION society) of hydroxylated cellulose and glycidyl trimethyl ammonium chloride can be enumerated in the cation property copolymer aspect, trade(brand)name: polymkeric substance JR-30M-125 and polymkeric substance JR-30M-400 (associating carbide society (Union Carbide Corporation) makes)), the quaternary ammonium compound of vinyl pyrrolidone-copolymer of dimethylaminoethyl methacrylate (trade(brand)name: GAFQUAT734 and 755 (manufacturing of GAF society)), dimethyl diallyl ammonium chloride polymkeric substance (trade(brand)name: MERQUAT100 (manufacturing of Merck society)), dimethyl diallyl ammonium chloride acrylamide copolymer (trade(brand)name: MERQUAT550 (manufacturing of Merck society)) etc.
Multipolymer (the multipolymer (trade(brand)name: GANTREZ (manufacturing of ISP society)) of trade(brand)name: DIAHOLD (manufacturing of Mitsubishi Chemical's (strain) society), trade(brand)name: PLAS-SIZE (mutual induction chemistry society makes), maleic acid mono alkyl ester and ethylene methacrylic ether etc. such as (methyl) vinylformic acid and alkyl methacrylate can be enumerated in anionic property polymkeric substance aspect.
Multipolymer (trade(brand)name: LUVISKOL (manufacturing of BASF society)) such as Polyvinylpyrolidone (PVP) (trade(brand)name: PVP (manufacturing of ISP society)), vinyl pyrrolidone and vinyl-acetic ester etc. can be enumerated in nonionic polymkeric substance aspect.The amphiphilic polymers aspect can be enumerated such as alkylmethacrylate polymer (trade(brand)name: YUKAFORMERAM-75W (manufacturing of Mitsubishi Chemical's (strain) society)) etc.
As the nonionic surfactant that can be used for mousse, such as enumerating sorbitan fatty acid esters, glycerol fatty acid ester, polyoxyethylene sorbitan fatty acid esters, cithrol, Voranol EP 2001, polyoxyethylene alkyl phenyl ether, polyoxyethylenated castor oil, polyoxyethylene hydrogenated castor oil, fatty acid alkyl amide etc.
The propellant that in addition, can be used for sprays or mousse have the compression gases such as the liquefied gas such as liquified petroleum gas, dimethyl ether, halon and air, carbon dioxide, nitrogen etc.
Hair cosmetic composition is with among the purposes of resin combination, comprises as the hair cosmetic composition of purpose to give nursing function: shampoo, Rinsing, permanent wave solution equal solvent are the hair cosmetic composition of the alcohols such as water and/or ethanol, Virahol; Perhaps the hair conditioner equal solvent be water and (or) alcohols such as ethanol, Virahol or alcohols and/or boiling point be the hair cosmetic composition of 50 ℃～300 ℃ hydro carbons.Identical with described setting agent, as the nursing function imparting agent, hair cosmetic composition can use separately with containing the oxidation amine resin in the resin combination, and perhaps the known nursing with cationic, anionic property, nonionic and the both sexes commonly used is used with polymkeric substance.
For example, use hair cosmetic composition with in the situation of resin combination as shampoo, can in the tensio-active agent base material of known anionic property, both sexes or nonionic, add use and contain the oxidation amine resin.Herein, example for the tensio-active agent base material, as the anionic surfactant, can enumerate N-cocoyl-N-methyl-Beta-alanine sodium, the N-myristoyl-N-methyl-N-such as Beta-alanine sodium fatty acid acyl-N-methyl-β-propylamine hydrochlorate etc.; As the amphoterics base material, can enumerate AMONYL 380LC, dimethyl empgen BB, two (2-hydroxyethyl) empgen BB, cyclohexyl dodecyl amine oxide, dimethyl dodecyl amine oxide, two (2-hydroxyethyl) dodecyl amine oxide etc.; In addition, as the nonionic surfactant base material, can enumerate Stearic acid diethanolamine salt, cocoanut fatty acid diethanolamide, sorbitanic sesquioleate, polyoxyethylene stearyl base ether etc.
Use hair cosmetic composition with in the situation of resin combination as Rinsing, can in known cationic surfactant, add use and contain the oxidation amine resin.For the example of cationic surfactant base material, can enumerate chlorination stearyl trimethyl ammonium, Varisoft TA 100, chlorination stearyl dimethyl benzyl ammonium etc. herein.
Use hair cosmetic composition with in the situation of resin combination as permanent wave solution, can in the oxygenant such as known bromic acid salt, peroxyboric acid class and Thiovanic acid and the reductive agents such as salt, halfcystine thereof, add to use and contain the oxidation amine resin.
Use hair cosmetic composition with in the situation of resin combination as hair conditioner, can add to use and contain the oxidation amine resin, thereby share or substitute these materials with cationization polymkeric substance such as known cationic surfactant base material and/or cationic polypeptide, cationic Mierocrystalline cellulose, cationic polysiloxane.Herein, as the cationic surfactant base material, the cationic surfactant base material of for example enumerating as being used for the example of Rinsing also can be used for hair conditioner.
For above-mentioned setting agent or nursing function imparting agent, all can outside described various compositions, add as required other any compositions of the scope that does not affect effect of the present invention.As any composition, for example can enumerate following substances, but be not limited to following substances.
The hydro carbons such as whiteruss, Vaseline, solid alkane, squalane, olefin oligomer;
The straight chain alcohols such as ethanol, dodecanol, cetyl alcohol, stearyl alcohol, V-1326, tetradecyl alcohol, oleyl alcohol, cetostearyl alcohol;
The alcohols such as branched-chain alcoho such as glycerine list stearyl ether (monostearyl glycerine ether), 2-decyl tetradecanol, Wool wax alcohol, cholesterol, plant sterol, hexyl dodecanol, isooctadecanol, Standamul G;
Lauric acid, styracin, Palmiticacid, stearic acid, 22 carbon (mountain Yu) acid, oleic acid, 1, senior fatty acid and the derivatives thereof such as 2-hydroxystearic acid, undecylenic acid, the acid of appropriate that, lanolin fatty acid, Unimac 5680, linolic acid, linolenic acid, gamma-linolenic acid, pentacosa alkene acid;
Department of botany's polymers such as carrageenin, pectin, fine jade fat, Wen Quince seed (quince seed, marmelo), brown alga glycocoll (brown alga essence), starch (rice, corn, potato, wheat), Potenlini;
The department of microbiology polymers such as xanthan gum, dextran, amylopectin;
The animal such as collagen, gelatin is the water-soluble polymers such as polymer;
The cellulose-based polymers such as methylcellulose gum, ethyl cellulose, methylhydroxypropylcellulose, Natvosol, Ushercell, hydroxypropylcellulose, Xylo-Mucine (CMC), crystalline cellulose, Mierocrystalline cellulose end;
The alginic acid such as sodiun alginate, Protanal Ester SD-LB is the semi-synthetic water-soluble polymers such as polymer;
The ethene base system polymers such as polyvinyl alcohol, polyvinyl methyl ether, Polyvinylpyrolidone (PVP), carboxyvinyl polymer (carboxyvinyl polymer);
PEG 20000,4000000, the polyoxyethylene such as 600000 are polymer;
The synthesizing water-solubility polymers such as polymine;
Wilkinite, silicic acid AlMg (magnesium aluminum silicate, VEEGUM), the inorganic water-soluble polymer such as ラ ボ Na イ ト, hectorite, anhydrous silicic acid;
The silicones such as volatile silicone oils, silicone resin, silicone rubber, alkyl sex change silicone;
N-lauroyl-Pidolidone list sodium, N-coco-nut oil fatty acid-Pidolidone list trolamine, N-myristoyl-Pidolidone list sodium, the N-mixed fatty acid acyl group-N-fatty acid acyl-Pidolidone salt such as Pidolidone list sodium;
N-lipid acid-N methyl taurine the salt such as lauric acid N-methyltaurine sodium, coco-nut oil fatty acid N-methyltaurine sodium;
The salt of the N-lipid acid sarkosine condensess such as sodium lauroyl sareosine, cocounut oil acylsarcosine sodium;
The tensio-active agents such as acyl group sodium sarcosinate, acyl glutamate, acyl-beta-Sodium L-alaninate, acyl taurine salt, dodecyl sulfate, dodecyl dimethylamino acetic acid trimethyl-glycine, alkyltrimethylammonium chloride, polyoxyethylene hydrogenated castor oil;
1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid, 1-hydroxyl ethane-1, the metal ion encapsulants such as 1-di 2 ethylhexyl phosphonic acid tetra-na salt, Zonon D, trisodium ethylenediaminetetraacetate, sequestrene Na4, Trisodium Citrate, sodium polyphosphate, sodium-metaphosphate, glyconic acid;
3-(4 '-methylbenzene methylene radical)-d, l-camphor, 3-α-tolylene-d, l-camphor, urocanic acid, the urocanic acid ethyl ester, 2-phenyl-5-Jia base benzoxazole, 2,2 '-hydroxy-5-methyl base phenyl benzotriazole, 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, the dibenzyl hydrazine, two methoxybenzoyl methane, 4-methoxyl group-4 '-tertiary butyl phenyl phenacyl ketone, 5-(the inferior norcamphyl of 3,3-dimethyl-2-)-3-pentane-2-ketone, phenylformic acid system, anthroic acid system, Whitfield's ointment system, styracin system, the various UV light absorber such as benzophenone series;
The emulsifying agents such as Zerol, sorbitanic monopalmitate, PCE, polyoxyethylenesorbitan monolaurate;
(gathering) ethylene glycol, (gathering) propylene glycol, glycerine, 1,3-butyleneglycol, maltose alcohol, Sorbitol Powder, chondroitin sulfate, hyaluronic acid, Atelocollagen, cholesterol-1, the wetting Agent for Printing Inkss such as 2-hydroxystearic acid ester, Sodium.alpha.-hydroxypropionate, bile salt, dl-pyrrolidone carboxylic acid salt, short chain soluble collagen matter;
Japanese cypress phenol, Hexachlorophene, benzalkonium chloride, neko and than antiseptic-germicides such as thiophenols;
The vasodilators such as carpronium Chloride;
The refrigerant sense imparting agents such as peppermint alcohols;
The excitement imparting agents such as niacin benzyl ester;
The vitaminss such as vitamin A, B, C, D, E;
The fungicidal preservatives such as chlorhexidine gluconate, isopropyl methyl phenol, p-Hydroxybenzoate;
The sequestrants such as proteolysate, amino acid, plant extract elite, EDTA-Na;
The pH adjusting agents such as succsinic acid, sodium succinate, trolamine:
Propellant, metal ion capturing agent, mould inhibitor, sterilant, opacifying agent, conditioning agent, thickening material, antioxidant, solubilizing agent, rosin, hydrotropic agent, hair growth promoter, crude drug, pigment, the spices such as the liquified petroleum gas in the situation of suds booster, whipping agent, bubble stabilizer, aerosol product, dme.
Embodiment
The below enumerates Production Example and embodiment, is described more specifically the present invention.
In addition, hereinafter, " part " refers to " weight part ", and " % ", " ppm " refer to respectively " % by weight " " ppm by weight ".
In addition, used starting monomer is that the beautiful sun of Mitsubishi (strain) makes, and is as follows with respect to the MEHQ concentration of each monomer weight.
Dimethylaminoethyl methacrylate: 2000ppm
Lauryl methacrylate: 1000ppm
Tert-butyl Methacrylate: 200ppm
In addition, the MEHQ concentration of resin solution of above-mentioned raw materials monomer, manufacturing etc. obtains with following methods analyst.
The analytical procedure of＜MEHQ concentration 〉
Gas chromatograph: " the HP6850 series GC system " that uses society of Hewlett-Packard to make, measure under following condition and specification.
Post: " HP-1 " that society of Hewlett-Packard makes
Injection temperature: 250 ℃
Column temperature: be warmed up to 130 ℃ with 7 ℃/minute speed from 60 ℃, be warmed up to 250 ℃ with 15 ℃/minute speed from 130 ℃.
Carrier gas: helium 15ml/ minute
Detector: FID
[manufacturing of resin solution]
Production Example 1: the manufacturing of resin solution P-1
In five mouthfuls of flasks using Glass tubing and whipping appts with reflux cooler, dropping funnel, thermometer, nitrogen replacement, add 50 parts of dimethylaminoethyl methacrylates, 25 parts of lauryl methacrylates, 25 parts of Tert-butyl Methacrylates and 200 parts of dehydrated alcohols, add 0.2 part 2,2 '-azo-bis-iso-dimethyl, stir on one side, under nitrogen gas stream, be heated to 80 ℃ on one side, reacted 8 hours, and obtained copolymer solution.Take polystyrene as reference material, to analyze by GPC (gel permeation chromatography), the weight-average molecular weight of this multipolymer of obtaining (polystyrene conversion) is 100000.
Then, use dropping funnel, drip in the solution obtained above and the equimolar hydrogen peroxide of dimethylaminoethyl methacrylate that adds (using 34% hydrogen peroxide) with 1 hour time, and then, under nitrogen gas stream, in boiling point reflux 12 hours, carry out the oxidizing reaction of dimethylamino.In addition, the terminal point of above-mentioned oxidizing reaction is confirmed by the amine pH-value determination pH of reaction solution.In addition, observed the absorption of N-O by infrared absorption spectrum, proved to have generated the oxidation amido.
At last, add dehydrated alcohol, with solution composition be adjusted into that resin is 30%, water is 7%, ethanol is 63%, obtains resin solution P-1.
The MEHQ concentration of this resin solution P-1 is 390ppm, and the MEHQ concentration of per unit resin solid composition is 1300ppm.
Production Example 2: the manufacturing of resin solution P-2
After similarly carrying out copolyreaction and oxidizing reaction with Production Example 1, make reaction solution in following condition by being full of the activated carbon column of ethanol, remove MEHQ.
(condition)
Temperature: room temperature (20～35 ℃)
Wash-out SV:0.25hr-1
The composition of post effluent liquid is adjusted into that resin is 30% thereafter,, water is 7%, ethanol is 63%, obtains resin solution P-2.
The MEHQ of this solution P-2 is below detectability.
Production Example 3: the manufacturing of resin solution P-3
Similarly add monomer, solvent, polymerization starter with Production Example 1, carry out copolymer reaction, then in the copolymer solution that obtains, add and the equimolar Monochloro Acetic Acid sodium of dimethylaminoethyl methacrylate, and then, stirred 12 hours, and carried out the bisexual ion purification reaction of dimethylamino.
With this solution pressure filtration, remove the sodium-chlor of generation after, with solution composition be adjusted into that resin is 30%, water is 7%, ethanol is 63%, obtains resin solution P-3.
The MEHQ concentration of this resin solution P-3 is 390ppm, and the MEHQ concentration of per unit resin solid composition is 1300ppm.
Production Example 4: the manufacturing of resin solution P-4
Use the dimethylaminoethyl methacrylate that replaces Production Example 1 to use as the dimethylaminoethyl methacrylate of 200ppm with respect to the MEHQ concentration of monomer weight, in addition, under the condition identical with Production Example 1, obtain multipolymer.Utilizing the weight-average molecular weight of this multipolymer that the analytical method identical with manufacturing side 1 obtain is 100000.
Next, utilize the method identical with Production Example 1 to carry out oxidizing reaction, confirm generated the oxidation amido after, the interpolation dehydrated alcohol, with solution composition be adjusted into that resin is 30%, water is 7%, ethanol is 63%, obtains resin solution P-4.
The MEHQ concentration of this resin solution P-4 is 34ppm, and the MEHQ concentration of per unit resin solid composition is 113ppm.
[light fastness stability test]
Embodiment 1,2, comparative example 1,2, reference example 1
Resin solution P-1～the P-3 that uses Production Example 1～3 to obtain prepares with the proportioning shown in the table 2, respectively the sample solution of the composition shown in the preparation table 2.
The sample solution that 40ml is obtained is sealed in respectively in the glass sample plasma bottle processed (capacity 50ml), at 14 days sunlights of outdoor irradiation.Wherein, when carrying out reference example 1, from embodiment 1,2 and comparative example 1,2 different test days, with identical sample plasma bottle at 4 days sunlights of outdoor irradiation.The about 100J/cm of ultraviolet accumulated light that brings of 4 days solar light irradiations in this reference example 1 as calculated 2, with in other examples that calculate 7 days ultraviolet accumulated light about equally.
Utilize the variation of the colourity of following method to so to sample plasma bottle irradiation sunlight the time to measure.
＜determination of colority method 〉
Be the glass cuvette processed (cell) of 10mm with the sample solution optical length of packing into, the colour examining colour-difference-metre ND-1001DP type that uses Japanese electric look industry society to make is measured, is calculated take distilled water as standard test specimen, obtains the measured value of Lab color specification system.According to L, a, b value, dL, da, db value over time, obtain a Max, b m, L mValue and da, db, dL utilize following formula to calculate variable color degree dE value.
dE=(dL 2＋da 2＋db 2) 1/2
The larger colour-change that shows of dE before and after the rayed is larger.
A value, b value, L value see Table 1 over time.
In addition, a 0, b 0, L 0, a Max, b m, L m, da, db, dL and dE value see Table 2.
In addition, also recorded the pH of the sample solution of preparation in the table 2.
[table 1]
※ 1:a MaxValue
※ 2:b mValue
※ 3:L mValue
※ 4: the MEHQ concentration of the sample solution of reference example 1 is identical with the sample solution of comparative example 2, in the comparative example 2, and expression a MaxThe 7th day the about 100Jcm of ultraviolet accumulated light of value 2, can the 4th day value of the ultraviolet reference example 1 of equal accumulated light be considered as a with having shone therewith Max
[table 2]
Figure BDA00002597770300271
[the light fastness stability test that utilizes fast light promotion trier to carry out]
Embodiment 3, comparative example 3
The resin solution P-4, the P-1 that use Production Example 4 and Production Example 1 to obtain prepare with the proportioning shown in the table 4, respectively the sample solution of the composition shown in the preparation table 4.
The sample solution that 6ml is obtained is sealed in respectively in the glass sample plasma bottle processed (volume 10ml), and (ア イ ス パ ー UV tstr SUV-W1 (the rugged electric society of rock makes) is with 600W/m with fast light promotion trier 2The ultraviolet ray 0 minute, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes of intensity illumination wavelength 300～400nm.
Colourity when utilizing following method to measure so to the sample plasma bottle irradiation ultraviolet radiation changes.
＜determination of colority method 〉
Be the glass cuvette processed of 10mm with the sample solution optical length of packing into, the UV visual spectrophotometer V-530 and the color computer card TSV-566 type that use Japanese light splitting society to make, measure, calculate take distilled water as standard test specimen, obtain the measured value of Lab color specification system.According to L, a, b value, dL, da, db value over time, obtain similarly to Example 1 a Max, b m, L mValue and da, db, dL obtain variable color degree dE value.
A value, b value, L value see Table 3 over time.
In addition, a 0, b 0, L 0, a Max, b m, L m, da, db, dL and dE value see Table 4.
In addition, also recorded the pH of the sample solution of preparation in the table 4.
[table 3]
Figure BDA00002597770300281
※ 1a MaxValue
※ 2b mValue
※ 3L mValue
[table 4]
By the above results as can be known:
In the comparative example 1, use MEHQ concentration to prepare sample solution as the resin solution P-1 of 390pprn (the MEHQ concentration of per unit resin solid composition is 1300ppm), the MEHQ that contains 234ppm in the sample solution, da=6.2, db=9.7, dE=12.9 are painted large;
That use in the comparative example 2 is the resin solution P-2 that does not contain MEHQ, but MEHQ has been added in the outside, and the MEHQ concentration of sample solution is 234ppm, and da=7.5, db=17.1, dE=19.7 are painted large.
Relative therewith, use the resin solution P-2 that does not contain MEHQ to prepare sample solution among the embodiment 1, do not contain MEHQ in the sample solution, da=1.7, db=0.5, dE=4.1 do not have painted.
In addition, that embodiment 2 uses is the resin solution P-2 that does not contain MEHQ, and MEHQ has been added in the outside, and the MEHQ concentration of sample solution is 22ppm, but because MEHQ concentration is low, so da=2.7, db=2.5, dE=5.0 do not have painted substantially.
So, contain MEHQ concentration in the oxidation amido resin solution by control, can prevent painted.
In addition, what reference example 1 used is not to contain oxidation amido resin solution, but betaines resin solution P-3, and MEHQ concentration is 234ppm (be 1300ppm with respect to the resinoid MEHQ concentration of trimethyl-glycine), da=1.82, db=3.76, dE=5.6 almost do not have painted problem.
Use MEHQ concentration to prepare sample solution as the resin solution P-4 of 34ppm (the MEHQ concentration of per unit resin solid composition is 113ppm) among the embodiment 3, contain 20ppmMEHQ in the sample solution, da=1.6, db=2.2, dE=3.2 do not have painted.
Use MEHQ concentration to prepare sample solution as the resin solution P-1 of 390ppm (the MEHQ concentration of per unit resin solid composition is 1300ppm) in the comparative example 3, contain 234ppmMEHQ in the sample solution, da=16.0, db=14.9, dE=26.6, painted obvious.
In addition, in the determination of colority of embodiment, use, utilize the measuring method of the colour examining colour-difference-metre ND-1001DP that Japanese electric look industry society makes and utilize UV visual spectrophotometer V-530 that Japanese light splitting society makes and the measuring method of color computer card TSV-566 type has carried out following comparison.
For the sample that contains oxidation amido resin solution (45 kinds of samples that colored state is different), similarly obtain the measured value of Lab color specification system with above-mentioned two measuring methods.The mean value of poor (absolute value) of the measured value that two measuring methods obtain is as follows: for the L value, poor mean value is 1.1; For a value, poor mean value is 0.09; For the b value, poor mean value is that the standard deviation of difference of the measured value that obtains of 0.4, two measuring method is as follows, and for the L value, described standard deviation is ± 0.99, and for a value, described standard deviation is ± 0.22, and for the b value, described standard deviation is ± 0.61.
By these results as can be known, use arbitrarily measuring method, the measured value of the L value among the present invention, a value and b value all can not produce large poor.
The specific embodiment of top reference describes the present invention in detail, but for a person skilled in the art, obviously can carry out without departing from the spirit and scope of the present invention various changes and modifications.
The application is based on the application of the Japanese patent application (Japanese Patent Application 2008-187443) of application on July 18th, 2008, at this, with the form of reference its content is introduced this specification sheets.
Utilizability on the industry
Use the hair cosmetic composition of the present invention that contains oxidation amido resin solution preparation of the present invention with resin combination As time goes on the problem of painted or variable color not to occur, can the good state of its outward appearance of long term maintenance.
The high hair cosmetic composition resin combination of commodity value that therefore, the resin solution that contains the oxidation amido of long-term storing stability excellence can be provided according to the present invention and use this resin solution.Therefore, the value of industry of the present invention is obvious.

Claims (12)

1. one kind contains oxidation amido resin solution, it is characterized in that:
Describedly contain oxidation amido resin solution not contain stopper or level of inhibitor be below the described 750ppm that contains oxidation amido resin content,
Wherein, described containing in the oxidation amine resin as hydrophilic monomer (A), comprise the Component units that contains oxidation amido monomer (a) from following general formula (I)～(IV):
In the formula, R 1Expression hydrogen atom or methyl, R 2And R 3Represent that independently of one another carbonatoms is that 1～24 alkyl, carbonatoms are that 6～24 aryl or carbonatoms are 7～24 aralkyl, R 4And R 5The expression carbonatoms is that 1～24 alkyl, carbonatoms are that 6～24 aryl or carbonatoms are 7～24 aralkyl; X represents that divalent connects base, and m represents 0～1 integer, and n represents 0～4 integer, and p represents 0～3 integer, and Y represents-C (R 11) R 12-,-NR 13-,-S-or-O-, R 6～R 13In at least one represents CH independently of one another 2=C (R 1)-(X) m-, other R 6～R 13Represent that independently of one another hydrogen atom, carbonatoms are that 1～24 alkyl, carbonatoms are that 6～24 aryl or carbonatoms are 7～24 aralkyl, a and b represent 1～10 integer independently of one another, in addition, and at X, R 4, R 5, R 7, R 8, R 9, R 10X more than 2, R are arranged in a plurality of situations 4, R 5, R 7, R 8, R 9, R 10Can be the same or different;
Perhaps comprise following Component units, it is from the monomer that the nitrogenous precursor monomer (b) shown in the following logical formula V～(VIII) is carried out after the oxidation:
Figure FDA00002597770200021
In the formula, R 1～R 10, X, m, n, p, Y, a and b definition identical with the definition in the described general formula (I)～(IV),
And hydrophilic monomer (A) is that described hydrophilic monomer (A) is 15～90 % by weight with the part by weight of hydrophobic monomer (B), and described hydrophobic monomer (B) is 85～10 % by weight.
2. the oxidation amido resin solution that contains as claimed in claim 1, wherein, described hydrophobic monomer (B) is that carbonatoms is (methyl) acrylate of 1～24 alcohol.
3. the oxidation amido resin solution that contains as claimed in claim 1 or 2 wherein, is the described oxidation amido monomer (a) that contains more than 30 % by weight of described hydrophilic monomer (A).
4. the oxidation amido resin solution that contains as claimed in claim 1 or 2, wherein, the described oxidation amido resin solution that contains satisfies following condition (1) and (2),
(1) a 0Value and a MaxThe difference da value of value satisfies following formula (i), wherein, and a 0Value is to a value in the Lab color specification system of the sample solution mensuration of firm preparation, and described sample solution is that the described content that contains the oxidation amine resin that contains the preparation of oxidation amido resin solution of use is that 18 % by weight, water-content are that 10 % by weight and ethanol content are the sample solution of 72 % by weight; a MaxValue be described sample solution is sealed in the glass sample plasma bottle processed and irradiation ultraviolet radiation after the maximum value that reaches of a value in the Lab color specification system measured;
da=a max-a 0≦5……(i)
(2) b 0Value and b mThe difference db value of value satisfies following formula (ii), wherein, and b 0Value is to the b value in the Lab color specification system of the sample solution mensuration of above-mentioned (1) of firm preparation; b mValue is that said sample solution shows a in above-mentioned (1) MaxB value during value,
db=b m-b 0≦9……(ii)。
5. the oxidation amido resin solution that contains as claimed in claim 4, wherein, the described oxidation amido resin solution that contains also satisfies following condition (3),
(3) dL value and described da value and db value satisfy following formula (iii), and wherein, described dL value is L 0Value and L mWhat be worth is poor, L 0Value is to the L value in the Lab color specification system of the sample solution mensuration of described (1) of firm preparation, L mValue is a of described sample solution in showing described (1) MaxL value during value,
dE=(dL 2＋da 2＋db 2) 1/2≦10......(iii)。
6. the oxidation amido resin solution that contains as claimed in claim 5 wherein, is the described oxidation amido monomer (a) that contains more than 30 % by weight of described hydrophilic monomer (A).
7. the oxidation amido resin solution that contains as claimed in claim 1 or 2, wherein, the described pH that contains oxidation aminoresin solution is 6～9.
8. the oxidation amido resin solution that contains as claimed in claim 1 or 2, wherein, the described oxidation aminoresin solution that contains is without anion exchange process.
9. the oxidation amido resin solution that contains as claimed in claim 1 or 2, wherein, described stopper is the hydroquinone monomethyl ether.
10. hair cosmetic composition resin combination, wherein, said composition be right to use require 1～9 each describedly contain the preparation of oxidation amido resin solution.
11. hair cosmetic composition resin combination as claimed in claim 10, it contains the oxidation amine resin, it is characterized in that, described composition does not contain stopper or level of inhibitor is below the 20ppm.
12. hair cosmetic composition resin combination as claimed in claim 11, wherein, described stopper is the hydroquinone monomethyl ether.
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