JP5454319B2 - Foam modifying copolymer - Google Patents

Description

  The present invention relates to a detergent composition and a cosmetic that are excellent in a foam-modifying effect and a conditioning effect when incorporated in a detergent composition and a cosmetic composition, such as those used in hair cleaners and hair cosmetics. The present invention relates to a copolymer and a copolymer composition, and a cleaning composition, a cosmetic composition, a conditioner composition, and a hair cleaning composition that use them.

For cleaning agents such as shampoos and body soaps, to improve slipping during washing, passing through fingers and combs after washing, smoothness after drying, hair flexibility and smoothness, and other sensations So-called conditioning agents are blended. For example, it is known that shampoo contains cationized hydroxyethyl cellulose, cationized guar gum, dimethyldiallylammonium chloride / acrylamide copolymer as a conditioning agent.
These cationic conditioning agents also contribute to foaming at the time of washing, and are expected to have an effect of improving foaming and improving foam retention.

  However, if various cationic polymers are used in combination to achieve both conditioning performance and foam quality, it may be difficult to achieve both conditioning performance and foam quality. Many.

  On the other hand, in the previous application, the present inventor improved the adsorptivity of silicone to damaged hair by a cationized polymer comprising a cationic monomer having a specific structure and a nonionic monomer having an amide group or a hydroxyl group. The improvement of the conditioning effect by has been clarified. (For example, refer to Patent Documents 1 and 2).

JP 2005-255982 A JP 2007-63543 A

  However, according to the study of the present inventor, the foam quality of these polymers having a high conditioning effect sometimes deteriorated. For example, when a large amount of polymer is mixed in order to enhance the conditioning effect, the foam quality deteriorates, and therefore other cationic polymers may be used in combination for foam modification. However, there has been a problem that the conditioning effect is reduced in combination with other cationic polymers for foam modification.

The present invention is intended to solve the above-described problems, and provides a copolymer excellent in, for example, a foam-modifying effect, a conditioning effect, and a thickening effect. Also, the present invention provides an improved foamy copolymer composition comprising the copolymer of the present invention and an anionic surfactant, and reduces irritation to the skin by not using much anionic surfactant. An object of the present invention is to provide a copolymer composition having an improved foam quality comprising the copolymer of the present invention and a nonionic surfactant.
Another object of the present invention is to provide a copolymer that improves foam quality without reducing the conditioning effect even when a conditioning polymer is used in combination. Still another object of the present invention is to provide a copolymer having a conditioning effect while having a low environmental impact. Furthermore, it aims at providing the copolymer which improves a conditioning effect in a conditioner composition. Furthermore, it aims at providing the copolymer as a thickener, such as raising the viscosity of a surfactant containing composition. Another object of the present invention is to provide a detergent composition, a cosmetic composition and the like excellent in foam quality and conditioning effect by using the above-mentioned copolymer.

  As a result of intensive studies in view of the above problems, the present inventor has achieved excellent foam reforming with a copolymer containing structural units corresponding to the amphiphilic monomer (A) and the hydrophilic monomer (B). The inventors have found that characteristics and conditioning characteristics can be obtained, and have completed the present invention.

The present invention has been achieved on the basis of such findings, and the gist thereof is as follows.
[1] and constituting units corresponding to the amphiphilic monomer (A) having a radical polymerizable vinyl group, polyalkylene oxide and a hydrocarbon group having a carbon number of 6 to 30, is represented by the following general formula (1) that the hydrophilic monomer (B) corresponding to the constituting units and including co-polymer and.
^{_{CH 2 = C (R 1)}} -CO-NR 2 R 3 (1)
(In General Formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently represent a hydrogen atom or an alkyl group optionally having a hydroxyl group having 1 to 4 carbon atoms. represents the sum of carbon numbers of R ² and R ³ Ri der 1 to 4, at least either one of R ² and R ³ is an alkyl group having a hydroxyl group.)
[2] The copolymer according to [1], wherein the amphiphilic monomer (A) is represented by the following general formula (2).
^{_{CH 2 = C (R 4)}} -CO- (O) a (NH) 1-a -X- (CH 2 CH (R 5) O) m -Y-R 6 (2)
(In General Formula (2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom, a methyl group, or an ethyl group, and R ⁶ is a carbon that may contain any of a linear, branched, or cyclic structure. A hydrocarbon group having a number of 6 to 30; X and Y each independently represent any divalent linking group or direct bond; a is 0 or 1, and m is 2 to 100.
[3] based on the combined total of all structural units constituting the copolymer, the constituting units corresponding to the structural unit and parent aqueous monomer (B) which corresponds to both amphiphilic monomer (A) is the following ratio The copolymer according to [1] or [2], wherein
Structural units corresponding to both amphiphilic monomer (A): 0.1 to 90 wt%
Structural units corresponding to the parent aqueous monomer (B): 1-99.9 wt%
[4] The copolymer according to any one of [1] to [3], which has a weight average molecular weight of 3,000 to 1,000,000 .
[5 ] A copolymer composition containing 1 to 40% by mass of an anionic surfactant and 0.01 to 40% by mass of the copolymer according to any one of [1] to [4].
[ 6 ] The copolymer composition according to [ 5 ], containing 0.01 to 40% by mass of a cationic conditioning agent.
[ 7 ] A copolymer composition containing 1 to 40% by mass of a nonionic surfactant and 0.01 to 40% by mass of the copolymer according to any one of [1] to [4].
[ 8 ] A copolymer composition containing 1 to 40% by weight of an amphoteric surfactant and 0.01 to 40% by weight of the copolymer according to any one of [1] to [4].
[ 9 ] The copolymer composition according to [ 8 ], containing 1 to 40% by mass of an anionic surfactant.
[ 10 ] A cleaning composition comprising the copolymer composition according to any one of [ 5 ] to [ 9 ].
[ 11 ] A hair cleansing composition comprising the cleaning composition according to [ 10 ].
[ 12 ] A cosmetic composition comprising the copolymer composition according to any one of [ 5 ] to [ 9 ].
[ 13 ] A hair cosmetic comprising the cosmetic composition according to [ 12 ].
[ 14 ] A conditioner composition comprising a cationic surfactant, a higher alcohol, and the copolymer according to any one of [1] to [4].

  When the copolymer of the present invention is a composition containing the copolymer, it can improve the foam quality such as the amount of foam, the speed of foaming and the foam texture. In particular, in a copolymer composition containing an anionic surfactant, foam quality can be improved without reducing the conditioning effect even when a conditioning component is used in combination. Furthermore, even if it uses for the copolymer composition containing a nonionic surfactant, foam quality can be improved. Moreover, the composition containing the copolymer of this invention is excellent also in the conditioning effect. In particular, when used in a copolymer composition together with an amphoteric surfactant, it is possible to improve the feeling during rinsing and the feeling after drying. Furthermore, when the copolymer of the present invention is used in a conditioner composition containing a cationic surfactant and a higher alcohol, the feeling in use can be improved. The copolymer of the present invention also has an effect for thickening.

In the following, the contents of the present invention will be described in detail. However, the description of the constituent elements described below is a representative example of an embodiment of the present invention, and is appropriately modified and implemented without departing from the spirit of the present invention. be able to. In the present specification, “to” is used to mean that the numerical values described before and after it are contained as a lower limit value and an upper limit value. The concentration and viscosity of the present invention are those at 25 ° C. unless otherwise specified.
Further, in the present specification, the “hydrophilic solvent” refers to a solvent having a solubility in water (dissolved mass in 100.0 g of water) at 25 ° C. of 1.0 g or more, a solvent having infinite solubility in water, It is used in a concept that also includes Further, “foam quality” refers to “foam amount”, “rapid foaming speed”, and “foam texture” shown in Examples 10 to 23 of the present specification, and “foam modification” refers to the above “foam quality” It means that at least one of “quality” is improved over the comparative standard sample. “Comparative standard sample” is a sample in which the mass% of the copolymer in the copolymer composition of the sample is replaced with a solvent with respect to the sample to be evaluated. The relationship is similar to Comparative Example 17 with respect to Examples 31-33. In addition, in this specification, “conditioning effect” refers to “rinse feel” and “feel after drying” performed in Examples 31 to 33 of this specification, and “conditioning effect is improved” This means that the “rinse feel” and “feel after drying” are comprehensively improved with respect to the standard sample.

<Copolymer>
The copolymer of the present invention comprises an amphiphilic monomer having a radically polymerizable vinyl group, a polyalkylene oxide, and a hydrocarbon group having 6 to 30 carbon atoms which may contain any of a linear, branched or cyclic structure ( A) a copolymer containing structural units corresponding to the specific hydrophilic monomer (B).

<Amphiphilic monomer (A)>
The radical polymerizable vinyl group possessed by the amphiphilic monomer (A) is not particularly limited as long as it is a vinyl group that can be usually radically polymerized, and any radical polymerizable vinyl group can be used. it can.

  The polyalkylene oxide possessed by the amphiphilic monomer (A) has a polyether structure having as a repeating unit a structural unit corresponding to an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide and the like. Here, the alkylene oxide may be a single kind or a combination of plural kinds, and the arrangement thereof may be a random structure or a block structure. Further, the number of carbon atoms of the alkylene moiety in the structural unit corresponding to alkylene oxide is not particularly limited, but preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms. Is used. Among them, the polyalkylene oxide preferably contains at least a structure corresponding to ethylene oxide or propylene oxide as a structural unit of polyalkylene oxide. More preferably, at least ethylene oxide is contained as a structural unit of the polyalkylene oxide. If the proportion of ethylene oxide in the polyalkylene oxide is large, the water solubility becomes high and the water solubility of the copolymer can be improved. More preferably, the proportion of the structural unit corresponding to ethylene oxide with respect to the polyalkylene oxide is 50% by mass or more. It is preferable that it is, More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more.

  The hydrocarbon group possessed by the amphiphilic monomer (A) has 6 to 30 carbon atoms and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. It may be cyclic or cyclic, and may be linear or branched. The carbon number of the hydrocarbon group is preferably 8 or more, more preferably 10 or more, and still more preferably 12 or more. The carbon number of the hydrocarbon group is preferably 24 or less, more preferably 20 or less, and still more preferably 18 or less. More specifically, linear or branched saturated aliphatic groups such as alkyl groups, unsaturated aliphatic groups such as alkenyl groups, cyclic aliphatic groups such as cyclohexyl groups, phenyl groups, benzyl groups, and tosyl groups. And aromatic groups such as a naphthyl group. Those having one or more of the hydrocarbon groups mentioned above may be used. In addition, these hydrocarbon groups may have other substituents via an oxygen atom, a nitrogen atom, a sulfur atom, or the like.

The reason why the hydrocarbon group of the amphiphilic monomer (A) has 6 to 30 carbon atoms is as follows. When a structural unit corresponding to the amphiphilic monomer (A) is included as a structural unit of the copolymer of the present invention, when the surfactant is used in combination, the micelle formed by the surfactant and the amphiphilic monomer are formed. It is considered that a higher-order structure is formed by the interaction of the hydrocarbon group of the monomer (A). The effect improves the stability of the foam and improves the quality of the foam, such as the speed of foaming and the feel of the foam, such as the elasticity and fineness of the foam. Polyalkylene oxide is considered to have a role of imparting hydrophilicity to the monomer and maintaining an appropriate distance between the micelle formed by the surfactant and the copolymer. Thereby, a more stable higher-order structure can be formed, and it is thought that it contributes to stabilization of a bubble.
A more preferred form of the amphiphilic monomer (A) is a structure represented by the general formula (2).

^{_{CH 2 = C (R 4)}} -CO- (O) a (NH) 1-a -X- (CH 2 CH (R 5) O) m -Y-R 6 (2)
In general formula (2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom, a methyl group or an ethyl group, R ⁶ represents a hydrocarbon group having 6 to 30 carbon atoms, and X and Y Each independently represents any divalent linking group or direct bond, a is 0 or 1, and m is 2 to 100.

In general formula (2), a is preferably 1 from the viewpoint of versatility of the monomer.
In the general formula (2), from the viewpoint of water solubility, R ⁵ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. In the copolymer of the present invention, R ⁵ does not need to be single, and a hydrogen atom, a methyl group, or an ethyl group may be mixed, but includes those in which R ⁵ is a hydrogen atom. Among them, the ratio of R ⁵ being a hydrogen atom is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more with respect to the polyalkylene oxide. is there. A large proportion of ethylene oxide is preferable because the water solubility becomes high and the water solubility of the copolymer can be improved. Particularly preferably, R ⁵ is a single hydrogen atom.

In the general formula (2), m is 2 or more, preferably 3 or more, more preferably 4 or more, from the viewpoint of the water solubility of the copolymer. Further, from the viewpoint of the number of functional groups per weight, m is 100 or less, preferably 80 or less, more preferably 60 or less, and still more preferably 40 or less. Here, m represents an average repeating unit of polyalkylene oxide. Therefore, m may include one. R ⁵ does not need to be single, and a hydrogen atom, a methyl group, or an ethyl group may be mixed.

In the general formula (2), R ⁶ is a hydrocarbon group having 6 to 30 carbon atoms, which may be linear, branched, or cyclic, By setting the number to 6 or more, hydrophobic interaction with micelles formed by the surfactant tends to occur, and the foam quality and the like tend to be improved. The carbon number is preferably 8 or more, more preferably 10 or more, Preferably it is 12 or more. Also there is a tendency to maintain the miscibility with water-soluble by the number of carbon atoms in R ⁶ and 30 or less carbon atoms is preferably 24 or less, more preferably 20 or less, more preferably is 18 or less .

In order that the hydrocarbon group in R ⁶ of the general formula (2) interacts with the micelle formed by the surfactant and contributes to stabilization of the foam, etc., a structure similar to the hydrocarbon group of the surfactant is required. It is preferable to have. Therefore, it is preferable to select an optimal hydrocarbon group depending on the surfactant to be used. In general, R ^{6 in the} general formula (2) is preferably a linear or branched alkyl group. A chain alkyl group is preferred.

Specific examples of the hydrocarbon group represented by R ⁶ in the general formula (2) include linear or branched saturated aliphatic groups such as alkyl groups, unsaturated aliphatic groups such as alkenyl groups, and cyclic groups such as cyclohexyl groups. Aromatic groups such as aliphatic group, phenyl group, benzyl group, tosyl group, naphthyl group and the like can be mentioned. Note that these hydrocarbon groups may have other substituents via an oxygen atom, a nitrogen atom, a sulfur atom, or the like.

  In the general formula (2), X and Y are any divalent linking groups or direct bonds as long as the water solubility and hydrophobicity of the amphiphilic monomer (A) are not significantly changed. May be selected, but is preferably a nonionic linking group or a direct bond. Nonionic linking groups include linking groups containing heteroatoms such as —NH—, —O—, —S—, —CO—, —COO—, —CONH—, alkylene groups, cycloalkylene groups, and arylenes. And hydrocarbon groups such as groups, and combinations thereof. At this time, the hydrocarbon group may have a substituent such as an alkoxyl group, an alkyl group, or an aryl group. The most preferable as X and Y is a direct bond.

The amphiphilic monomer (A) represented by the general formula (2) is not particularly limited as long as it is included in this formula.
Hexanoxy polyethylene glycol- (meth) acrylate, octoxy polyethylene glycol- (meth) acrylate, 2-ethylhexoxy polyethylene glycol- (meth) acrylate, lauroxy polyethylene glycol- (meth) acrylate, stearoxy polyethylene glycol- (meta ) Acrylates, alkyl polyethylene glycol- (meth) acrylates such as behenyloxypolyethylene glycol- (meth) acrylate;
Alkyl polyethylene glycol-polypropylene glycol- (meth) acrylates such as octoxypolyethylene glycol-polypropylene glycol- (meth) acrylate, lauroxy polyethylene glycol-polypropylene glycol- (meth) acrylate;
Alkylphenoxypolyethyleneglycol- (meth) acrylates such as phenoxypolyethyleneglycol- (meth) acrylate and nonylphenoxypolyethyleneglycol- (meth) acrylate;
Examples include alkylphenoxy polyethylene glycol-polypropylene glycol- (meth) acrylates such as phenoxy polyethylene glycol-polypropylene glycol- (meth) acrylate and nonylphenoxy polyethylene glycol-polypropylene glycol- (meth) acrylate.
(Here, “(meth) acryl” represents acrylic and methacrylic).
Of these, alkyl polyethylene glycol- (meth) acrylates are preferable from the viewpoint of interaction with the surfactant.

  More specific examples of alkyl polyethylene glycol- (meth) acrylates include hexanoxypolyethylene glycol (2)-(meth) acrylate, octoxypolyethylene glycol (4)-(meth) acrylate, and 2-ethylhexoxypolyethylene. Glycol (4)-(meth) acrylate, Lauroxy polyethylene glycol (4)-(meth) acrylate, Lauroxy polyethylene glycol (20)-(meth) acrylate, stearoxy polyethylene glycol (9)-(meth) acrylate, steer Examples include loxypolyethylene glycol (30)-(meth) acrylate and behenyloxypolyethylene glycol (20)-(meth) acrylate.

Among these, lauroxy polyethylene glycol (4)-(meth) acrylate, lauroxy polyethylene glycol (20)-(meth) acrylate, stearoxy polyethylene glycol (9)-(meth) acrylate, stearoxy polyethylene glycol (30)- (Meth) acrylate and the like are further preferred examples.
(Here, the numbers appended to the polyalkylene glycol represent the average number of repeating units of the alkylene glycol.)
In addition, an amphiphilic monomer (A) may be used individually by 1 type, or may use 2 or more types together.

  Such an amphiphilic monomer (A) is preferably contained at a ratio of 0.1% by mass or more with respect to all the structural units constituting the copolymer of the present invention. More preferably, it is 1 mass% or more, More preferably, it is 3 mass% or more, Furthermore, it is preferable that it is 5 mass% or more. By setting it as 0.1 mass% or more, the quantity which interacts with the micelle which surfactant forms becomes sufficient, and foam quality etc. can be improved. The amphiphilic monomer (A) is preferably 90% by mass or less, more preferably 70% by mass or less, and still more preferably 50% by mass with respect to all the structural units constituting the copolymer of the present invention. % Or less is preferable. By setting it as 90 mass% or less, the solubility to hydrophilic solvents, such as water, an alcohol solvent, and an acetone solvent, can be maintained.

<Hydrophilic monomer (B)>
The copolymer of the present invention contains a structural unit corresponding to the hydrophilic monomer (B) represented by the following general formula (1), but the hydrophilic monomer represented by the general formula (1) The structural unit corresponding to (B) has an amide bond or a hydroxyl group in some cases, and has an effect of imparting hydrophilicity to the copolymer due to the hydrophilicity derived therefrom. Thereby, the water solubility of the higher order structure formed with the surfactant can be maintained.

^{_{CH 2 = C (R 1)}} -CO-NR 2 R 3 (1)

In General Formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently represent a hydrogen atom or an alkyl group that may have a hydroxyl group having 1 to 4 carbon atoms. , R ² and R ³ have a sum of 1 or more and 4 or less.

In the general formula (1), R ¹ is preferably a hydrogen atom because of high water solubility.
In the general formula (1), ^{R 2} and ^{R 3} are each independently a hydrogen atom, or an alkyl group which may have a hydroxyl group having 1 to 4 carbon atoms, and, for ^{R 2} and ^{R 3} carbons The sum of the numbers is 1 or more and 4 or less. That is, one of R ² and R ³ is an alkyl group that may have at least a hydroxyl group having 1 to 4 carbon atoms. At this time, it is preferable that at least one of R ² and R ³ has an alkyl group having a hydroxyl group.

In the general formula (1), although the sum of the number of carbon atoms of R ² and R ³ is 1 to 4, it is preferable sum of the number of carbon atoms is 2 or more. More preferably, the sum of the carbon number is 3 or less. Most preferably, it is 2 or less. Furthermore, it is preferable that either one of R ² and R ³ is a hydrogen atom. Thereby, hydrogen bonding property can be improved, interaction between copolymers can be improved, and foam quality etc. can be improved.

The hydrophilic monomer (B) represented by the general formula (1) is not particularly limited as long as it is included in this formula. For example, N-methyl (meth) acrylamide, N-ethyl (meta) ) Alkyl acrylamides such as acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide; Dialkyl acrylamides such as N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide; N -Hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide Hydroxyalkyl (meth) acrylamides such as Where "(meth) acrylic" means acrylic and methacrylic). Among these, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N are preferable. -Diethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide. More preferred are N, N-dimethyl (meth) acrylamide and N- (2-hydroxyethyl) (meth) acrylamide. Most preferred is N- (2-hydroxyethyl) (meth) acrylamide.
In addition, a hydrophilic monomer (B) may be used individually by 1 type, or may use 2 or more types together.

  Such a hydrophilic monomer (B) is contained in a proportion of 1% by mass or more as a constituent unit of the copolymer with respect to all the constituent units constituting the copolymer of the present invention. It is preferable. More preferably, it is 10 mass% or more, More preferably, it is 30 mass% or more, Furthermore, it is preferable that it is 50 mass% or more. If it is less than 1% by mass, the water solubility is not sufficient and the foam quality tends to decrease. Moreover, 99.9 mass% or less is preferable, More preferably, it is 99 mass% or less, More preferably, it is preferable that it is 97 mass% or less, More preferably, it is 95 mass% or less. If it exceeds 99.9% by mass, the amphiphilic monomer (A) of the copolymer component is less than 0.1% by mass, which is not preferable.

<Other structural units>
The copolymer of the present invention comprises a structural unit corresponding to a radical polymerizable vinyl group, a polyalkylene oxide, and an amphiphilic monomer (A) having a hydrocarbon group having 6 to 30 carbon atoms, the above general formula ( Although it is a copolymer containing the structural unit corresponding to the hydrophilic monomer (B) represented by 1), it may contain a structural unit corresponding to another vinyl monomer. Other vinyl monomers include anionic monomers such as acrylic acid, methacrylic acid, maleic anhydride,
Cationic monomers such as quaternary ammonium group-containing (meth) acrylic ester, quaternary ammonium group-containing (meth) acrylamide,
Esters of alcohols having 1 to 22 carbon atoms and (meth) acrylic acid, amides of alkylamines having 1 to 22 carbon atoms and (meth) acrylic acid, ethylene glycol, 1,3-propylene glycol and the like ( Monoesters with (meth) acrylic acid, further esters in which the hydroxyl groups of these monoesters are etherified with methanol, ethanol, etc., polyalkylene glycol group-containing (meth) acrylic esters other than general formula (2), (meth) acrylic Nonionic monomers such as ilmorpholine, amphoteric monomers such as betaine group-containing (meth) acrylic ester and betaine group-containing (meth) acrylamide, amine oxide group-containing (meth) acrylic ester, amine oxide group-containing ( And semipolar monomers such as (meth) acrylamide.

  Specific examples of cationic vinyl monomers include (meth) acrylic acid alkyltrimethylammonium halides, (meth) acrylamide alkyltrimethylammonium halides, (meth) acrylic acid alkyldialkylamines, (meth) acrylamide alkyldialkylamines. Etc.

  The ratio of the structural unit corresponding to the other vinyl monomer to the total structural units constituting the copolymer can be determined as appropriate without departing from the gist of the present invention. For example, it can be appropriately determined within a range that does not inhibit the solubility of the copolymer in water and the foaming or the like when used in a detergent composition. In order to achieve sufficient interaction between the water solubility of the copolymer and the micelles formed by the surfactant, the content is preferably 30% by mass or less, more preferably 20% by mass or less in the copolymer.

  As described above, the copolymer of the present invention can contain a constituent unit of a cationic vinyl monomer as a constituent unit corresponding to another vinyl monomer. If a cationic functional group is present in the coalescence, when a cationic conditioning polymer is used in combination as a copolymer composition, it may hinder the formation of a complex between the cationic conditioning polymer and the anionic surfactant. Those having a small amount of cationic vinyl monomer are preferred. Specifically, it is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less, based on all structural units constituting the copolymer of the present invention. It is more preferable if these are not substantially included.

The content of the structural unit corresponding to the amphiphilic monomer (A) in the copolymer, the structural unit corresponding to the hydrophilicity (B), and the structural unit derived from other vinyl monomers is polyethylene glycol. Or IR absorption of amide bond sites, polyethylene glycol or amide bond sites, ¹ H-NMR of alkyl groups, or ¹³ C-NMR thereof.

  The weight average molecular weight of the copolymer of the present invention is preferably 3,000 to 1,000,000. By setting the weight average molecular weight to 3,000 or more, moderate viscosity can be imparted and foaming is improved. More preferably, it is 5,000 or more, More preferably, it is 8,000 or more. By setting it to 1,000,000 or less, the viscosity can be kept moderate, and handling in production becomes easier. More preferably, it is 500,000 or less, More preferably, it is 200,000 or less. The weight average molecular weight of the copolymer of the present invention can be measured by gel permeation chromatography (for example, using water / methanol / acetic acid / sodium acetate as a developing solvent).

  The weight average molecular weight can be adjusted, for example, by controlling the degree of polymerization of the copolymer. The degree of polymerization can be controlled by the amount of polymerization initiator, polymerization concentration, reaction temperature, and the like. The molecular weight and viscosity can also be controlled by increasing or decreasing the addition amount of a crosslinking agent such as a polyfunctional acrylate. However, if a crosslinking agent is added too much, the molecular weight and viscosity will increase rapidly, and there are aspects that are difficult to control in industrial production. For this reason, it is most preferable not to contain a crosslinking agent.

<Method for producing copolymer>
The copolymer according to the present invention can be produced, for example, by mixing monomers that give respective structural units and copolymerizing them by a method such as solution polymerization, suspension polymerization, or emulsion polymerization. It can also be produced by carrying out an addition reaction after copolymerization using a monomer precursor.

  The solvent used in the polymerization reaction is not particularly limited as long as the raw material monomer of the copolymer of the present invention is normally dissolved or dispersed to such an extent that it can be copolymerized. It is preferable to conduct the polymerization reaction. Specific examples of the hydrophilic solvent used in the polymerization reaction include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, and the like. Alcohol-based solvents, water and the like. These may be used alone or in combination of two or more. It is preferable to use an alcohol solvent or water.

  Any polymerization initiator may be used as long as it can be usually used for radical polymerization. Specific examples include 2,2′-azobisisobutyronitrile, 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate, 2,2 '-Azobis (2-methylbutyronitrile), 1,1'-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (2-methyl-N- (2-hydroxyethyl) -propionamide), Azo compounds such as 2,2′-azobis (2-amidinopropane) dihydrochloride, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide Peroxides such as de, persulfate or the like thereof redox, can be used without particular limitation. The polymerization initiator is preferably used in the range of 0.01 to 5% by mass with respect to all monomers.

  The polymerization reaction can be performed, for example, under an inert gas atmosphere such as nitrogen or argon, preferably at 30 to 120 ° C., more preferably at 40 to 100 ° C., usually for 1 to 30 hours. After completion of the polymerization, the produced copolymer may be isolated from the reaction solution by an appropriate means such as solvent distillation or addition of a poor solvent. This copolymer can be used as it is or after further purification to produce the cleaning composition according to the present invention. Purification can be performed by combining appropriate means such as reprecipitation, solvent washing, and membrane separation as required.

  The weight average molecular weight of the copolymer of the present invention is preferably 3,000 to 1,000,000. By setting the weight average molecular weight to 3,000 or more, moderate viscosity can be imparted and foaming is improved. More preferably, it is 5,000 or more, More preferably, it is 8,000 or more. By setting it to 1,000,000 or less, the viscosity can be kept moderate, and handling in production becomes easier. More preferably, it is 500,000 or less, More preferably, it is 200,000 or less. The weight average molecular weight of the copolymer of the present invention can be measured by gel permeation chromatography (for example, using water / methanol / acetic acid / sodium acetate as a developing solvent).

  The weight average molecular weight can be adjusted, for example, by controlling the degree of polymerization of the copolymer. The degree of polymerization can be controlled by the amount of polymerization initiator, polymerization concentration, reaction temperature, and the like. The molecular weight and viscosity can also be controlled by increasing or decreasing the addition amount of a crosslinking agent such as a polyfunctional acrylate. However, if a crosslinking agent is added too much, the molecular weight and viscosity will increase rapidly, and there are aspects that are difficult to control in industrial production. For this reason, it is most preferable not to contain a crosslinking agent.

<Use of effects>
The copolymer of the present invention is excellent in various effects as evaluated in the examples of the present specification, such as a foam modifying effect, a conditioning effect, and a thickening effect. In the copolymer of the present invention, the use of the above effect and a preferred embodiment for enhancing the effect will be described below.

1. Utilization of foam modifying effect The copolymer of the present invention has an excellent foam modifying effect when used in, for example, cleaning agents and cosmetics. In addition, what consists of the copolymer of this invention, Comprising: When it mix | blends as a component of a copolymer composition, what is improved in a foam quality may be called a copolymer for foam modification.

1-1. When used with an anionic surfactant The preferred form of the copolymer of the present invention is as described above, but a more preferred form for obtaining a copolymer composition having an excellent foam-modifying effect is anionic. It is a copolymer composition containing a surfactant. It is preferable to contain an anionic surfactant since foaming can be further improved. Thus, in the form used as a copolymer composition together with an anionic surfactant, among them, the more preferred form of the copolymer of the present invention for the foam modifying effect is as follows.

  The amphiphilic monomer (A) is preferably contained in an amount of 1% by mass or more as a constituent unit of the copolymer. More preferably, it is 5 mass% or more, More preferably, it is 10 mass% or more, Furthermore, it is preferable that it is 15 mass% or more. By setting it as 1 mass% or more, interaction with the micelle which a surfactant forms increases and foam quality improves. Moreover, 50 mass% or less is preferable, More preferably, it is 40 mass% or less, More preferably, it is preferable that it is 30 mass% or less. By making it 50% by mass or less, water solubility can be maintained and the foam quality is improved.

  Moreover, it is preferable that a hydrophilic monomer (B) contains 50 mass% or more as a structural unit of a copolymer. More preferably, it is 70 mass% or more, More preferably, it is 75 mass% or more. Water solubility can be improved by setting it as 50 mass% or more. Moreover, 99 mass% or less is preferable, More preferably, it is 95 mass% or less, More preferably, it is preferable that it is 90 mass% or less, More preferably, it is 85 mass% or less. By setting it to 99% by mass or less, the amphiphilic monomer (A) of the copolymerization component is 1% by mass or more, and the foam quality can be sufficiently improved, which is preferable.

  Moreover, the weight average molecular weight of the foam-modifying copolymer of the present invention is preferably 200,000 or less. By setting it to 200,000 or less, foaming is accelerated, which is preferable. More preferably, it is 100,000 or less, More preferably, it is 50,000 or less.

  About the suitable range other than description here, it is the same as that of what was mentioned as a suitable range of the copolymer of this invention as stated above.

1-2. When used with a nonionic surfactant Another preferred form of use of the copolymer of the present invention is a copolymer composition used with a nonionic surfactant. Nonionic surfactants are generally preferred because they are less irritating to the human body, such as the skin and eyes, and can be used in combination with the copolymer of the present invention to suppress irritation. In the foam-modifying copolymer composition containing the nonionic surfactant, a more preferable form of the copolymer of the present invention is as follows.

  The amphiphilic monomer (A) is preferably contained in an amount of 1% by mass or more as a constituent unit of the copolymer. More preferably, it is 5 mass% or more, More preferably, it is 10 mass% or more, Furthermore, it is preferable that it is 15 mass% or more. By setting it as 1 mass% or more, interaction with the micelle which a surfactant forms increases and foam quality improves. Moreover, 50 mass% or less is preferable, More preferably, it is 40 mass% or less, More preferably, it is preferable that it is 30 mass% or less. By making it 50% by mass or less, water solubility can be maintained and the foam quality is improved.

  Moreover, it is preferable that a hydrophilic monomer (B) contains 50 mass% or more as a structural unit of a copolymer. More preferably, it is 70 mass% or more, More preferably, it is 75 mass% or more. Water solubility can be improved by setting it as 50 mass% or more. Moreover, 99 mass% or less is preferable, More preferably, it is 95 mass% or less, More preferably, it is preferable that it is 90 mass% or less, More preferably, it is 85 mass% or less. By setting it to 99% by mass or less, the amphiphilic monomer (A) of the copolymerization component is 1% by mass or more, and the foam quality can be sufficiently improved, which is preferable.

  The copolymer may further contain structural units derived from other vinyl monomers, but among the above-mentioned as a preferable range of the copolymer of the present invention, particularly preferable ones are as follows. , Anionic monomers such as acrylic acid, methacrylic acid and maleic anhydride, amphoteric monomers such as betaine group-containing (meth) acrylic ester and betaine group-containing (meth) acrylamide, and amine oxide group-containing (meth) And semipolar monomers such as acrylic ester and amine oxide group-containing (meth) acrylamide. More preferred are anionic monomers such as acrylic acid, methacrylic acid and maleic anhydride. This is because when the micelle formed by the nonionic surfactant interacts with the foam-modifying copolymer of the present invention, it has an effect of imparting electrostatic repulsion instead of the anionic surfactant. , Foam quality is improved.

  The weight average molecular weight of the copolymer of the present invention is preferably 8,000 or more. By setting it as 8,000 or more, moderate viscosity can be given and foaming improves. More preferably, it is 20,000 or more, More preferably, it is 50,000 or more.

  The preferred ranges other than those described here are the same as those mentioned as the preferred ranges of the copolymer of the present invention described above.

2. Utilization of Conditioning Effect The copolymer of the present invention has an excellent conditioning effect when used in, for example, a cleaning agent or a cosmetic. In addition, it consists of the copolymer of the present invention, and when blended as a component of the copolymer composition, the evaluation method shown in the examples of the present invention improves the feeling when rinsing and the feeling after drying. May be referred to as a conditioning copolymer.

2-1. When used with amphoteric surfactants The most effective conditioning effect is that the conditioning copolymer is uniformly dissolved or dispersed in the copolymer composition and is not diluted in water such as in the rinsing process. It is a composition that causes homogenization or formation of precipitates. This is because the cationic conditioning polymer forms a complex called “coacervate” with the anionic surfactant and exhibits the conditioning effect, and the copolymer of the present invention and the amphoteric surfactant form a complex. (In this specification, it may be referred to as a “coacervate-like complex”) and exerts a conditioning effect.

  Therefore, a preferred form of the conditioning copolymer of the present invention is a copolymer composition containing an amphoteric surfactant. By containing the amphoteric surfactant, the conditioning copolymer of the present invention can easily form a coacervate-like complex, and the fingering during rinsing is improved. The reason why the amphoteric surfactant is preferable is not clear, but it can be considered that the balance between hydrophilicity and hydrophobicity is related. In this amphoteric surfactant-containing copolymer composition, the more preferred form of the conditioning copolymer is as follows.

  The amphiphilic monomer (A) that is a constituent unit of the conditioning copolymer preferably has a structure represented by the general formula (2).

  In the general formula (2), m is preferably 4 or more, more preferably 9 or more, still more preferably 15 or more, and particularly preferably 20 or more. Further, m is preferably 60 or less, more preferably 40 or less, and still more preferably 30 or less. An appropriate chain length is suitable for forming a coacervate-like complex.

In the general formula (2), R ⁶ preferably has 12 or more carbon atoms. More preferably, it is 14 or more, More preferably, it is 16 or more, Most preferably, it is 18 or more. A large number of carbons increases the hydrophobicity and is suitable for forming a coacervate-like complex.

  Specific examples of the amphiphilic monomer (A) represented by the general formula (2) are the same as those described as preferable examples in the copolymer of the present invention described above. Among them, particularly preferred specific examples are lauroxy polyethylene glycol (20)-(meth) acrylate, stearoxy polyethylene glycol (30)-(meth) acrylate, and the like.

  The amphiphilic monomer (A) is preferably contained in an amount of 10% by mass or more as a constituent unit of the copolymer. More preferably, it is 20 mass% or more, More preferably, it is 30 mass% or more, Furthermore, it is preferable that it is 40 mass% or more. By setting it as 10 mass% or more, interaction with the micelle which a surfactant forms increases, formation of a coacervate-like complex is promoted, and a conditioning effect improves. Moreover, 80 mass% or less is preferable, More preferably, it is 70 mass% or less, More preferably, it is preferable that it is 60 mass% or less. By making it 80% by mass or less, water solubility can be maintained and the conditioning effect is improved.

  Moreover, it is preferable that a hydrophilic monomer (B) contains 20 mass% or more as a structural unit of a copolymer. More preferably, it is 30 mass% or more, More preferably, it is 40 mass% or more. Water solubility can be improved by setting it as 20 mass% or more. Moreover, 90 mass% or less is preferable, More preferably, it is 80 mass% or less, More preferably, it is preferable that it is 70 mass% or less, More preferably, it is 60 mass% or less. By making it into 90 mass% or less, the amphiphilic monomer (A) of a copolymerization component will be 10 mass% or more, and it can improve a conditioning effect fully, and is preferable.

  The copolymer may further contain structural units derived from other vinyl monomers, but among the above-mentioned as a preferable range of the copolymer of the present invention, particularly preferable ones are as follows. , Anionic monomers such as acrylic acid, methacrylic acid and maleic anhydride, amphoteric monomers such as betaine group-containing (meth) acrylic ester and betaine group-containing (meth) acrylamide, and amine oxide group-containing (meth) And semipolar monomers such as acrylic ester and amine oxide group-containing (meth) acrylamide. More preferably, amphoteric monomers such as betaine group-containing (meth) acrylic esters and betaine group-containing (meth) acrylamides, and semipolar polarities such as amine oxide group-containing (meth) acrylic esters and amine oxide group-containing (meth) acrylamides It is a monomer. This is because, when the proportion of the amphiphilic monomer (A) is increased in order to enhance the conditioning effect, the hydrophilicity of the copolymer is lowered. This is because the water-solubility of the coalescence is improved.

  Moreover, the weight average molecular weight of the conditioning copolymer of the present invention is preferably 10,000 or more. By adjusting the viscosity to 10,000 or more, an appropriate viscosity can be imparted and a coacervate-like complex can be easily formed, so that the conditioning effect is improved. More preferably, it is 30,000 or more, More preferably, it is 50,000 or more.

  About the suitable range other than description here, it is the same as that of what was mentioned as a suitable range of the copolymer of this invention as stated above.

3. Utilization of Thickening Effect The copolymer of the present invention can also be suitably used for thickening a copolymer composition. This is because the copolymer of the present invention interacts with the micelle formed by the surfactant. It is thought that the apparent molecular weight increases by linking each of the copolymer of the present invention while interacting with the micelle formed with the surfactant.

  In the present specification, “thickening” means a copolymer composition containing the copolymer of the present invention and a surfactant, and the viscosity of the composition is a comparative standard sample by containing the copolymer of the present invention. Means more rising effect. Further, the viscoelasticity of the composition is changed by the increase in viscosity, and thixotropic properties can be imparted. Thereby, the feeling of use, such as a feeling of application, can be improved when a copolymer composition using the copolymer of the present invention together with a surfactant is used as a cleaning composition or a cosmetic composition. Incidentally, a copolymer comprising the copolymer of the present invention, which is accompanied by an increase in viscosity when blended as a component of the copolymer composition, may be referred to as a thickening copolymer.

<Copolymer composition>
As will be described below, the copolymer of the present invention can be combined with a hydrophilic solvent, various surfactants, a cationic conditioning agent, an additive and the like to form a composition. Hereinafter, the composition containing the copolymer of the present invention is referred to as “copolymer composition of the present invention” and will be described in detail below.

  The hydrophilic solvent as used herein refers to a solvent having a solubility in water (dissolution mass in 100.0 g of water) of 1.0 g or more at 25 ° C., as defined above. Although it is used in the concept including infinite and water, specifically, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n-propanol, i-propanol, n -Alcohol solvents, such as butanol, i-butanol, sec-butanol, water, etc. are mentioned. These may be used alone or in combination of two or more. It is preferable to use an alcohol solvent or water. More preferred are ethanol, i-propanol and water.

  The copolymer composition of the present invention can be usefully used in a detergent composition or a cosmetic composition. For example, by blending various surfactants and the copolymer of the present invention, a copolymer composition excellent in foam quality, rinsing feel, feel after drying and the like can be obtained. The copolymer composition of the present invention can be produced by simply mixing with the composition described in detail below. For example, the copolymer of the present invention is mixed with a hydrophilic solvent such as water or alcohol. It is possible to mix the dissolved or dispersed material with various raw materials that can be used for the copolymer composition, and stir as appropriate.

  Specifically, the cleaning composition includes industrial cleaning agents such as automotive cleaning agents and information electronic component substrate cleaning agents, hair cleaning agents such as shampoos and conditioners, facial cleansing cosmetics, and body cleaning agents. Suitable for cosmetic cleaning agents such as cosmetics (body soap). Among the detergent compositions, it is particularly suitable for cosmetics, and particularly suitable for hair cleansing agents.

  Cosmetic compositions include hair cosmetics such as shampoos and conditioners, facial cleansing cosmetics, body cleansing cosmetics (body soap), and makeup such as lipsticks, mascaras, eye shadows, and foundations. It is suitable for cosmetics, skin care cosmetics such as emulsions, facial packs and wrinkle prevention creams, and hair cosmetics such as wax, aerosol sprays, pump sprays and foams. Among the cosmetic compositions, it is particularly suitable for a detergent and a hair cosmetic, and particularly suitable for a hair cosmetic of a detergent.

  In the following (1) to (3), preferred usage forms of the copolymer composition of the present invention will be described more specifically.

(1) Anionic surfactant-containing copolymer composition In general, anionic surfactants have excellent detergency with respect to other surfactants, and therefore there are many anionic surfactants in detergents and cosmetics. It is used. By using the anionic surfactant and the copolymer of the present invention in combination, a copolymer composition with dramatically improved foam quality can be obtained without affecting other properties.

  When the copolymer of the present invention is blended with an anionic surfactant to obtain a copolymer composition having an excellent foam-modifying effect, 0.01% of the copolymer of the present invention is added to the copolymer composition. It is preferable to contain -40 mass% and 1-40 mass% of anionic surfactant, and the copolymer composition of the said composition shall be called "anionic surfactant containing copolymer" in this specification. There is.

The anionic surfactant-containing copolymer composition can be suitably used as a cleaning composition and a cosmetic composition, but is particularly useful as a hair cleaning composition and a hair cosmetic composition.
In this anionic surfactant-containing copolymer composition, a preferred blending composition is as follows with the entire copolymer composition being 100% by mass.

Copolymer of the present invention 0.01 to 10% by mass
Anionic surfactant 1-40% by mass
10-99% by mass of water
Amphoteric surfactant 0-40% by mass
Cationic conditioning agent 0-10% by mass
Additive 0-80% by mass

  When the copolymer composition of the present invention is used together with an anionic surfactant to obtain a copolymer composition having an excellent foam-modifying effect, the copolymer of the present invention is used with respect to the copolymer composition. It is preferable to contain 0.1-10 mass%. That is, the copolymer content is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.3% by mass or more in order to obtain sufficient foam characteristics. is there. From the viewpoint of moderate viscosity and easy handling and cost, the foam-modifying copolymer content is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass. It is as follows.

  The amount of water effective to dissolve the copolymer is preferably in the range of 10 to 99% by mass with respect to the copolymer composition. In order to obtain sufficient foam properties, the water content is preferably 99% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less, and particularly preferably 70% by mass. It is as follows. From the viewpoint of moderate viscosity and easy handling and cost, the content is preferably 10% by mass or more, more preferably 40% by mass or more, and still more preferably 60% by mass or more.

  The amount of anionic surfactant for imparting detergency is usually in the range of 1 to 40% by mass relative to the copolymer composition. In order to make the detergency sufficient, the content of the anionic surfactant is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and particularly preferably. Is 15% by mass or more. 40 mass% or less is preferable from the point of the viscosity being moderate and easy to handle and the point of cost, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less.

  Examples of the anionic surfactant include α-olefin sulfonate, higher alcohol sulfate, polyoxyethylene alkyl ether sulfate, paraffin sulfonate, polyoxyethylene alkyl ether carboxylate, alkyl sulfosuccinic acid. Those commonly used in detergents and cosmetics such as salts, N-acyl-β-alanine salts, N-acyl glutamate salts, and acylmethyl taurate salts can be used. Examples of counter ions of these anionic surfactants include sodium, potassium, ammonium, triethanolamine, diethanolamine and the like. Of these, polyoxyethylene alkyl ether sulfates are preferably used. An anionic surfactant may be used individually by 1 type, and may use 2 or more types together.

  By blending the amphoteric surfactant, the viscosity of the copolymer composition may be improved and foaming may also be improved. Therefore, it is usually blended in the range of 0 to 40% by mass with respect to the copolymer composition. The content of the amphoteric surfactant is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. 40 mass% or less is preferable from the point of the viscosity being moderate and easy to handle and the point of cost, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less.

  Examples of the amphoteric surfactant include an amide amino acid type surfactant, an amide betaine type amphoteric surfactant, an amide sulfobetaine type amphoteric surfactant, a betaine type amphoteric surfactant, and a sulfobetaine type amphoteric interface. Active agent, phosphobetaine type amphoteric surfactant, carbobetaine type amphoteric surfactant, amino acid type amphoteric surfactant, phosphate ester type amphoteric surfactant, imidazolinium type amphoteric surfactant, etc. Can be mentioned. Such amphoteric surfactants are generally commercially available and can be used as they are. Of these, long-chain alkylamidopropylbetaines are preferably used in terms of foaming and detergency. These may be used alone or in combination of two or more.

  Since the smoothness at the time of washing and rinsing is improved by blending the cationic conditioning agent, it is usually preferably blended in the range of 0 to 10% by mass with respect to the copolymer composition. The content of the cationic conditioning agent is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. From the viewpoint of moderate viscosity and easy handling and cost, it is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less.

  Cationic conditioning agents include cation-modified cellulose ether derivatives, cationic starch, cationized guar gum derivatives, homopolymers of diallyl quaternary ammonium salts, quaternized polyvinylpyrrolidone derivatives, polyglycol polyamine condensates, vinyl imidazolium trichloride / Vinylpyrrolidone copolymer, hydroxyethylcellulose / dimethyldiallylammonium chloride copolymer, polydimethyldiallylammonium halide, vinylpyrrolidone / quaternized dimethylaminoethyl methacrylate copolymer, polyvinylpyrrolidone / alkylaminoacrylate copolymer, polyvinylpyrrolidone / Alkylaminoacrylate / vinylcaprolactam copolymer, vinylpyrrolidone / methacrylamidopropyltrimethyl chloride Monium copolymer, alkylacrylamide / acrylate / alkylaminoalkylacrylamide / polyethylene glycol netacrylate copolymer, adipic acid / dimethylaminohydroxypropylethylenetriamine copolymer, dimethyldiallylammonium halide / acrylamide copolymer, dimethylacrylamide / Acrylamidopropyltrimethylammonium chloride copolymer, dimethylacrylamide / methacryloyloxyethyltrimethylammonium chloride copolymer, dimethylacrylamide / methacryloyloxyethyltrimethylammonium chloride / acrylamidopropyltrimethylammonium chloride copolymer, hydroxyethylacrylamide / methacryloyloxyethyltrimethyl Ammonium black Examples thereof include cationic polymers such as Lido copolymer and hydroxyethylacrylamide / acrylamidopropyltrimonium chloride copolymer. Among them, cation-modified cellulose ether derivatives, cationized guar gum derivatives, polydimethyldiallylammonium halide, dimethyldiallylammonium halide / acrylamide copolymer, dimethylacrylamide / methacryloyloxyethyltrimethylammonium chloride copolymer, dimethylacrylamide / methacryloyloxyethyltrimethylammonium chloride. / Acrylamidopropyltrimethylammonium chloride copolymer, hydroxyethylacrylamide / methacryloyloxyethyltrimethylammonium chloride copolymer, hydroxyethylacrylamide / acrylamidopropyltrimonium chloride copolymer and the like are preferably used because of their high conditioning effect. Particularly preferably, dimethylacrylamide / methacryloyloxyethyltrimethylammonium chloride copolymer, dimethylacrylamide / methacryloyloxyethyltrimethylammonium chloride / acrylamidopropyltrimethylammonium chloride copolymer, hydroxyethylacrylamide / methacryloyloxyethyltrimethylammonium chloride copolymer, Hydroxyethylacrylamide / acrylamidopropyltrimonium chloride copolymer and the like.

  When preparing the copolymer composition of the present invention so as to be excellent in the foam modifying effect as an anionic surfactant-containing copolymer composition, an additive is blended within a range that does not significantly impair the performance. The content is preferably 0 to 80% by mass with respect to the copolymer composition. In order to impart the performance of the active ingredient and not hinder the performance, the content of other additives is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 5% by mass. That's it. Moreover, it is preferably 50% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less.

  Specific examples include a semipolar surfactant, a nonionic surfactant, a cationic surfactant, an anionic polymer, a nonionic polymer, an amphoteric polymer, an oil component, and a pearling agent. Other optional components that can be blended in the anionic surfactant-containing copolymer composition are exemplified below.

  Examples of the semipolar surfactant include lauramine oxide (lauryl dimethylamine oxide), which can be suitably used. Such surfactants are generally commercially available and can be used as they are. These may be used alone or in combination of two or more.

  Since the semipolar surfactant has an effect of improving the smoothness at the time of rinsing, it is preferably used in combination with the anionic surfactant and the amphoteric surfactant. At this time, the content of the semipolar surfactant in the anionic surfactant-containing copolymer composition is preferably 0.1 to 5% by mass, more preferably 0, based on the copolymer composition. It is 0.5-5 mass%, More preferably, it is 0.5-3 mass%, Most preferably, it is 0.5-2 mass%.

  Examples of the nonionic surfactant include polyoxyalkylene ether, polyoxyalkylene alkyl ether or polyoxyalkylene alkenyl ether, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polyoxyalkylene alkyl ether, sorbitan fatty acid ester, polyoxyalkylene. Sorbitan fatty acid ester, polyoxyalkylene sorbite fatty acid ester, fatty acid glycerin ester, fatty acid glycol ester, alkylene glycol fatty acid ester, polyalkylene glycol fatty acid ester, polyglycerin fatty acid ester, polyoxyalkylene glycerin fatty acid ester, alkyl saccharide surfactant, fatty acid Monoethanolamide or diethanolamide or ethoxylates thereof , Monoglyceride ethoxylate, fatty acid sucrose ester, polyoxyalkylene lanolin or lanolin alcohol or beeswax derivative, polyoxyethylene sterol or hydrogenated sterol, polyoxyalkylene alkyl ether phosphoric acid or phosphate, polyoxyalkylene alkyl allyl ether, Examples include polyoxyalkylene glyceryl monofatty acid ester, polyoxyalkylene fatty acid ester, polyoxyalkylene fatty acid amide, polyoxyalkylene alkylamide, polyalkyleneimine derivative and the like. Such nonionic surfactants are generally commercially available and can be used as they are. Among them, polyoxyalkylene ether, polyoxyalkylene alkyl ether or polyoxyalkylene alkenyl ether, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polyoxyalkylene alkyl ether and the like are preferable from the viewpoint of versatility and low irritation. Used.

  A nonionic surfactant may be used individually by 1 type, and may use 2 or more types together. Nonionic surfactants can be suitably used because they have a thickening effect.

  As the cationic surfactant, for example, a long-chain alkyl group-containing quaternary ammonium salt is preferable. The long chain alkyl group is preferably one having 6 to 24 carbon atoms. Among them, the carbon number of the long chain alkyl group is preferably 10 or more, more preferably 16 or more. Long chain alkyl group-containing quaternary ammonium salts include, for example, long chains such as cetyl trimethyl ammonium salt, stearyl trimethyl ammonium salt, behenyl trimethyl ammonium salt, cetyl dimethyl benzyl ammonium salt, stearyl dimethyl benzyl ammonium salt, and behenyl dimethyl benzyl ammonium salt. Two long chains such as one, dicetyldimethylammonium salt, distearyltrimethylammonium salt, dibehenyltrimethylammonium salt, dicetylmethylbenzylammonium salt, distearylmethylbenzylammonium salt, dibehenylmethylbenzylammonium salt And three long chains such as tricetylmethylammonium salt, tristearylmethylammonium salt, and tribehenylmethylammonium salt. And the like of it. Among them, one having one or two long chains is preferable, and one having one long chain is more preferable. These may be used alone or in combination of two or more. Cationic surfactants have the effect of improving the feel after drying and can be suitably used.

  Examples of nonionic polymers include methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, and the like. Of these, hydroxypropylmethylcellulose is preferably used in terms of compoundability.

  Examples of the anionic polymer include polyacrylic acid and salts thereof, acrylic acid derivatives such as acrylic acid / acrylamide / ethyl acrylate copolymers and salts thereof, methacrylic acid derivatives, and crotonic acid derivatives. Examples of nonionic polymers include hydroxyethyl acrylate / methoxyethyl acrylate copolymers, acrylic acid derivatives such as polyacrylamide, and vinyl pyrrolidone derivatives such as polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers.

  Examples of amphoteric polymers include those obtained by copolymerizing a cationic monomer and an anionic monomer such as acrylamide / acrylic acid / dimethyldiallylammonium chloride copolymer, acrylic acid / dimethyldiallylammonium chloride copolymer, etc. And those obtained by polymerizing amphoteric monomers such as a methacryloyloxyethylcarboxybetaine / alkyl methacrylate copolymer. These polymers are preferably contained in an amount of 0.1 to 5% by mass with respect to the copolymer composition.

  Oils include lauryl alcohol, myristyl alcohol, cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, 2-octyldodecanol, alcohols having 8 or more carbon atoms such as cetostearyl alcohol, dimethylpolysiloxane, amino-modified silicone , Polyether-modified silicone, methylphenylpolysiloxane, fatty acid-modified silicone, alcohol-modified silicone, alkoxy-modified silicone, epoxy-modified silicone, fluorine-modified silicone, cyclic silicone, alkyl-modified silicone and other silicone oils, perfluoropolyether and other fluorine oils , Hydrocarbons such as squalane, squalene, liquid paraffin, liquid isoparaffin, cycloparaffin, polyhydric alcohol fat Esters, fatty acid esters, fatty acid alkyl esters, polybasic acid esters, alkyl glyceryl ethers and their fatty acid ester oils, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, coconut oil fatty acid Higher fatty acids having 8 or more carbon atoms such as isostearyl acid and isopalmitic acid, glycerides such as jojoba oil and olive oil, waxes such as beeswax, lanolin and carnauba wax, isopropyl palmitate, isopropyl myristate, octyldodecyl myristate, Esters such as hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, tridodecyl isononanoate, isostear Glyceryl ether, polyoxypropylene butyl ether, and the like. The oil content is preferably 0.1 to 3% by mass with respect to the copolymer composition.

  Among these, alcohols having 8 or more carbon atoms can have a suitable viscosity when blended to obtain a copolymer composition that produces fine bubbles. Among alcohols having 8 or more carbon atoms, alcohols having 8 to 22 carbon atoms are preferably used, and alcohols having 14 to 22 carbon atoms are more preferable. The carbon chain of an alcohol having 8 or more carbon atoms may have any of a straight chain structure, a branched structure, and a cyclic structure. Preferred is a straight chain structure or a branched structure. Is composed only of a straight chain structure. The carbon chain of the alcohol having 8 or more carbon atoms is preferably one having no double bond and one having no double bond. Specific examples include lauryl alcohol, myristyl alcohol, cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, 2-octyldodecanol, cetostearyl alcohol and the like. Of these, myristyl alcohol, cetyl alcohol and stearyl alcohol are preferable, and cetyl alcohol and stearyl alcohol are more preferable. Of these, myristyl alcohol, cetyl alcohol, and stearyl alcohol are preferable, and cetyl alcohol is more preferable. The content of the alcohol having 8 or more carbon atoms is usually 0 to 3% by mass, more preferably 0.1 to 2% by mass, and further preferably 0.3 to 1% by mass with respect to the copolymer composition. . When blended in an amount of 3% by mass or more, the viscosity cannot be maintained properly, and the transparency and low-temperature storage stability of the copolymer composition are deteriorated. Moreover, Preferably it is 2 mass% or less, More preferably, it is 1 mass% or less.

  Moreover, the silicone oil improves the smoothness after drying by blending. Among these, it is more preferable to use dimethylpolysiloxane and amino-modified silicone. Content of silicone oil is 0-4 mass% normally with respect to a copolymer composition, More preferably, it is 0.1-3 mass%, More preferably, it is 0.3-2 mass%. When it is blended in an amount of 4% by mass or more, it is excessively adsorbed on the hair, and after drying, the oil-specific stickiness is produced. Preferably it is 3 mass% or less, More preferably, it is 2 mass% or less.

  Other ingredients include solubilizers such as ethylene glycol and propylene glycol, moisturizers such as glycerin, sorbitol, maltitol, dipropylene glycol, 1,3-butylene glycol, and hyaluronic acid, foam enhancers, and natural extracts of animals and plants. And derivatives thereof, proteins obtained from shells, pearls, silk, etc. and hydrolysates thereof, organic acids such as citric acid and lactic acid, inorganic acids such as phosphoric acid, hydrochloric acid and sulfuric acid, and pH adjusters such as citric acid and sodium hydroxide , Inorganic salts such as sodium chloride, sodium sulfate, ammonium chloride, sodium citrate, thickeners, fragrances, preservatives, chelating agents, UV absorbers, antioxidants, higher fatty acids, antidandruff agents, vitamins, bactericides , Anti-inflammatory agents, colorants such as dyes and pigments, suspensions such as polystyrene emulsions, functional capsules and beads It can be blended within a range that does not impair the light effect.

(2) Nonionic surfactant-containing copolymer composition Generally, anionic surfactants have excellent detergency with respect to other surfactants, and therefore, anionic surfactants are often used in detergents. However, there is also a problem that the skin irritation is high because the cleaning power is too strong. For this reason, although there are compositions mainly composed of nonionic surfactants and amphoteric surfactants, they are not sufficient in terms of foaming and foam quality.

  By using the copolymer of the present invention and a nonionic surfactant in combination, the foam quality can be improved without increasing skin irritation without using a large amount of anionic surfactant. In general, unlike low molecular weight surfactants, high molecular weight compounds are low irritation because of low skin permeability. Since the skin is anionic, amphoteric, anionic and nonionic polymers are considered to be less irritating to the skin than cationic ones. Of these, nonionic polymers are preferred.

  In the case of using the copolymer of the present invention for foam modification and blending with a nonionic surfactant to obtain a copolymer composition without increasing skin irritation, the copolymer composition is: It is preferable to contain 0.01-40 mass% of the copolymer of this invention with respect to a copolymer composition, and 1-40 mass% of nonionic surfactant, The copolymer composition of the said composition Is sometimes referred to herein as “nonionic surfactant-containing copolymer composition”.

  This nonionic surfactant-containing copolymer composition can be suitably used as a cleaning composition or a cosmetic composition, but is particularly useful as a hair cleaning composition or hair cosmetic composition. In the nonionic surfactant-containing copolymer composition, preferred blending compositions are as follows.

Copolymer of the present invention 0.01 to 10% by mass
Nonionic surfactant 1-40% by mass
10-99% by mass of water
Amphoteric surfactant 0-40% by mass
Additive 0-80% by mass

  In the nonionic surfactant-containing copolymer composition of the present invention, the copolymer of the present invention is preferably contained in an amount of 0.1 to 10% by mass relative to the copolymer composition. That is, in order to obtain sufficient foam properties, the content of the foam-modifying copolymer is more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and particularly preferably 0.8%. 3% by mass or more. Further, from the viewpoint of moderate viscosity and easy handling and cost, the copolymer content of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less. It is.

  The amount of water effective to dissolve the copolymer is preferably in the range of 10 to 99% by mass with respect to the copolymer composition. In order to obtain sufficient foam properties, the water content is preferably 99% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less, and particularly preferably 70% by mass. It is as follows. From the viewpoint of moderate viscosity and easy handling and cost, the content is preferably 10% by mass or more, more preferably 40% by mass or more, and still more preferably 60% by mass or more.

  The amount of nonionic surfactant for imparting detergency is preferably in the range of 1 to 40% by mass with respect to the copolymer composition. In order to make the detergency sufficient, the content of the nonionic surfactant is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and particularly preferably. Is 15% by mass or more. 40 mass% or less is preferable from the point of the viscosity being moderate and easy to handle and the point of cost, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less.

Examples of the nonionic surfactant are the same as those described as examples that can be used in the above-described anionic surfactant-containing copolymer composition.
A nonionic surfactant may be used individually by 1 type, and may use 2 or more types together.

  By blending the amphoteric surfactant, the viscosity of the copolymer composition may be improved and foaming may be improved. Therefore, it is preferable to blend in the range of 0 to 40% by mass with respect to the copolymer composition. . The content of the amphoteric surfactant is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. 40 mass% or less is preferable from the point of the viscosity being moderate and easy to handle and the point of cost, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less.

Examples of the amphoteric surfactant are the same as those given as examples that can be used in the above-described anionic surfactant-containing copolymer composition.
One amphoteric surfactant may be used alone, or two or more amphoteric surfactants may be used in combination.

  When used as a nonionic surfactant-containing copolymer composition, additives can be blended within a range that does not significantly impair the performance, and the content is 0 to 0 relative to the copolymer composition. 80 mass% is preferable. In order to impart the performance of the active ingredient and not hinder the performance, the content of other additives is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 5% by mass. That's it. Moreover, it is preferably 50% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less.

  Specifically, anionic surfactants, semipolar surfactants, cationic surfactants, cationic polymers, anionic polymers, nonionic polymers, amphoteric polymers, oil components, pearlizing agents, etc. is there. Other optional components that can be blended in the nonionic surfactant-containing copolymer composition are exemplified below.

  Specific examples of what can be used as the anionic surfactant are the same as those described as suitable examples in the above-described anionic surfactant-containing composition. However, from the viewpoint of skin irritation, the amount of the anionic surfactant is preferably 5% by mass or less, more preferably 1% by mass or less, and still more preferably used based on the copolymer composition. Is not to.

  As a semipolar surfactant, it is the same as that of what was mentioned as an example which can be used in the above-mentioned anionic surfactant containing copolymer composition.

  Since the semipolar surfactant has an effect of improving the smoothness at the time of rinsing, it is preferably used in combination with the nonionic surfactant and the amphoteric surfactant. At this time, the content of the semipolar surfactant in the nonionic surfactant-containing copolymer composition is preferably 0.1 to 5% by mass, more preferably 0.5 to 5% by mass. More preferably, it is 0.5-3 mass%, Most preferably, it is 0.5-2 mass%.

Examples of the cationic surfactant are the same as those given as examples that can be used in the aforementioned anionic surfactant-containing copolymer composition.
Cationic surfactants have the effect of improving the feel after drying and can be suitably used. However, from the viewpoint of skin irritation, the blending amount is preferably 5% by mass or less, more preferably 1% by mass or less, based on the copolymer composition.

Examples of the cationic polymer are the same as those described as examples of the cationic conditioning polymer suitable for the anionic surfactant-containing copolymer composition described above.
However, from the viewpoint of skin irritation, the blending amount is preferably 1% by mass or less, more preferably 0.3% by mass or less, based on the copolymer composition.

  Examples of the nonionic polymer, the anionic polymer, and the amphoteric polymer are the same as those described as examples that can be used in the above-described anionic surfactant-containing copolymer composition. These nonionic polymers, anionic polymers and amphoteric polymers are preferably contained in an amount of 0.1 to 5% by mass based on the copolymer composition.

  The oil component is the same as that exemplified as an example that can be used in the above-described anionic surfactant-containing copolymer composition. The oil content is preferably 0.1 to 3% by mass with respect to the copolymer composition.

  Other components are the same as those mentioned as examples that can be used in the above-described anionic surfactant-containing copolymer composition.

(3) Amphoteric surfactant-containing copolymer composition In general, a cationic conditioning polymer is blended in the detergent composition to improve the smoothness during washing and the smoothness after drying. However, the cationic conditioning polymer is a substance that is feared to affect the ecology, and it is not preferable to mix it in a large amount in the composition discharged to the environment.

  The copolymer of the present invention can impart a conditioning effect when used in the form described below as a copolymer composition.

  In the case where the copolymer of the present invention is used and the amphoteric surfactant is used, the detergent composition and the cosmetic composition include 0.01 to 40% by mass of the copolymer of the present invention, and the amphoteric interface. The activator is preferably contained in an amount of 1 to 40% by mass, and the copolymer composition prepared with the composition may be referred to as an “amphoteric surfactant-containing copolymer composition” in the present specification.

This amphoteric surfactant-containing copolymer composition can be suitably used as a cleaning composition or a cosmetic composition. In addition, it is particularly useful as a hair washing agent or hair cosmetic.
In this amphoteric surfactant-containing copolymer composition, preferred blending compositions are as follows.

Copolymer of the present invention 0.01 to 10% by mass
Amphoteric surfactant 1-40% by mass
10-99% by mass of water
Anionic surfactant 1-40% by mass
Additive 0-80% by mass

  In the amphoteric surfactant-containing copolymer composition of the present invention, the copolymer of the present invention is preferably contained in an amount of 0.1 to 10% by mass. That is, in order to make the conditioning property sufficient, the copolymer content is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.3% by mass or more. is there. Further, from the viewpoint of moderate viscosity and easy handling and cost, the copolymer content of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less. It is.

  Since the copolymer of the present invention tends to form a coacervate-like complex with an amphoteric surfactant when used in a preferred embodiment as the amphoteric surfactant-containing copolymer composition described above, the amphoteric surfactant It is preferable to make an agent into the range of 1-40 mass%. In order to make the conditioning property sufficient, the content of the amphoteric surfactant is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and particularly preferably. It is 15 mass% or more. 40 mass% or less is preferable from the point of the viscosity being moderate and easy to handle and the point of cost, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less.

  Examples of the amphoteric surfactant are the same as those given as examples that can be used in the above-described anionic surfactant-containing copolymer composition. One amphoteric surfactant may be used alone, or two or more amphoteric surfactants may be used in combination.

  The amount of water effective to dissolve the copolymer is preferably in the range of 10 to 99% by mass. In order to obtain sufficient foam properties, the water content is preferably 99% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less, and particularly preferably 70% by mass. It is as follows. From the viewpoint of moderate viscosity and easy handling and cost, the content is preferably 10% by mass or more, more preferably 40% by mass or more, and still more preferably 60% by mass or more.

  The amount of anionic surfactant for imparting detergency is preferably in the range of 1 to 40% by mass. In order to make the detergency sufficient, the content of the anionic surfactant is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and particularly preferably. Is 15% by mass or more. 40 mass% or less is preferable from the point of the viscosity being moderate and easy to handle and the point of cost, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less.

  As an anionic surfactant, it is the same as that of what was mentioned as an example which can be used in the above-mentioned anionic surfactant containing copolymer composition. An anionic surfactant may be used individually by 1 type, and may use 2 or more types together.

  When used as an amphoteric surfactant-containing copolymer composition, additives can be blended within a range that does not significantly impair the performance, and the content thereof is 0 to 80 with respect to the copolymer composition. Mass% is preferred. In order to impart the performance of the active ingredient and not hinder the performance, the content of other additives is more preferably 0.1% by mass or more, still more preferably 1% by mass or more, and particularly preferably 5% by mass. % Or more. More preferably, it is 50 mass% or less, More preferably, it is 20 mass% or less, Most preferably, it is 10 mass% or less.

  Specific additives include semipolar surfactants, nonionic surfactants, cationic surfactants, cationic polymers, anionic polymers, nonionic polymers, amphoteric polymers, oil components, and pearlizing. Agents. Other optional components that can be blended in the amphoteric surfactant-containing copolymer composition are exemplified below.

  The semipolar surfactant, nonionic surfactant, and cationic surfactant are the same as those described as examples that can be used in the above-described anionic surfactant-containing copolymer composition. These surfactants may be used alone or in combination of two or more.

  At this time, the content of the semipolar surfactant, nonionic surfactant, and cationic surfactant in the amphoteric surfactant-containing copolymer composition is preferably 0.1 to 10 with respect to the copolymer composition. It is mass%, More preferably, it is 0.5-5 mass%, More preferably, it is 0.5-3 mass%, Most preferably, it is 0.5-2 mass%.

  Examples of the cationic polymer are the same as those described as examples of the cationic conditioning polymer suitable for the anionic surfactant-containing copolymer composition described above. However, from the concern of giving a load to the environment, the blending amount is preferably 1% by mass or less, more preferably 0.3% by mass or less, based on the copolymer composition.

  As the nonionic polymer, the anionic polymer and the amphoteric polymer are the same as those exemplified as examples that can be used in the above-described anionic surfactant-containing copolymer composition. These nonionic polymers, anionic polymers and amphoteric polymers are preferably contained in an amount of 0.1 to 5% by mass based on the copolymer composition.

  The oil component is the same as that exemplified as an example that can be used in the above-described anionic surfactant-containing copolymer composition. The oil content is preferably 0.1 to 3% by mass with respect to the copolymer composition.

  Other components are the same as those exemplified as examples that can be used in the anionic surfactant copolymer composition described above.

<Conditioner composition>
Moreover, the copolymer of this invention can be used conveniently also for a conditioner composition. This is because the copolymer of the present invention also interacts with a lamellar structure composed of a cationic surfactant and a higher alcohol. This can improve the feel of the conditioner. That is, the conditioner composition containing a cationic surfactant, a higher alcohol, and the copolymer of the present invention is excellent in the conditioning effect. In addition, the cationic surfactant mentioned here is the same as that given as an example that can be used in the above-described anionic surfactant-containing copolymer composition. The higher alcohol referred to here is the same as that exemplified as an example that can be used in the above-described anionic surfactant-containing copolymer composition.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely using an Example, this invention is not limited by a following example, unless the summary is exceeded.

[Example 1]
(Production of copolymer (1))
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas introduction tube and a stirring device was charged with 100 parts by mass of ethanol, and stearoxy polyethylene glycol (30) -methacrylate (Blemmer PSE-1300; NOF) was added to the dropping funnel. A monomer mixture consisting of 30 parts by mass, 70 parts by mass of hydroxyethyl acrylamide, and 50 parts by mass of ethanol was charged, and the reactor was purged with nitrogen, and then heated to 80 ° C. After charging 0.5 parts by mass of dimethyl 2,2-azobis (2-methylpropionate) (V-601; manufactured by Wako Pure Chemical Industries, Ltd.) into the reactor, the monomer mixture was added over 2 hours. And dripped. After reacting for 2 hours after completion of the dropwise addition, 0.3 parts by mass of dimethyl 2,2-azobis (2-methylpropionate) was further added. Thereafter, the mixture was reacted for 3 hours and then cooled to obtain an ethanol solution of the copolymer (1). This was dried under reduced pressure to remove ethanol to obtain a powder of copolymer (1).

  The ratio of the structural unit corresponding to each monomer in all the structural units of the obtained copolymer was PSE1300 / HEAA = 30/70 (mass%), and the weight average molecular weight was 10,000. . The weight average molecular weight was measured as follows. Gel permeation chromatography (apparatus: manufactured by Tosoh Corporation, SC8010, SD8022, RI8020, CO8011, PS8010, column: Wako Pure Chemical Industries, Ltd. Wakopak (Wakobeads G-40, G-50), developing solvent: water / methanol / Using acetic acid / sodium acetate = 6/4 / 0.3 / 0.41), the weight average molecular weight was determined using polyethylene glycol as a standard substance.

[Example 2]
(Production of copolymer (2))
The copolymer (2) was prepared in the same manner as the copolymer (1) except that 5 parts by mass of stearoxypolyethylene glycol (30) -methacrylate (PSE-1300) and 95 parts by mass of hydroxyethylacrylamide (HEAA) were used. ) Was manufactured. Table 1 shows the weight percentages and weight average molecular weights of the structural units corresponding to the monomers in all the structural units of the obtained copolymer.

[Example 3]
(Production of copolymer (3))
The copolymer (3) was the same as the copolymer (1) except that 50 parts by mass of stearoxypolyethylene glycol (30) -methacrylate (PSE-1300) and 50 parts by mass of hydroxyethylacrylamide (HEAA) were used. ) Was manufactured. Table 1 shows the weight percentages and weight average molecular weights of the structural units corresponding to the monomers in all the structural units of the obtained copolymer.

[ Reference Example 1 ]
(Production of copolymer (4))
Copolymer (1) except that 30 parts by mass of stearoxypolyethylene glycol (30) -methacrylate (PSE-1300) and 70 parts by mass of dimethylacrylamide (DMAA) instead of hydroxyethylacrylamide (HEAA) were used. Similarly, copolymer (4) was produced. Table 1 shows the weight percentages and weight average molecular weights of the structural units corresponding to the monomers in all the structural units of the obtained copolymer.

[Example 5]
(Production of copolymer (5))
Except for using 30 parts by mass of stearoxy polyethylene glycol (9) -methacrylate (Blenmer PSE-400; manufactured by NOF Corporation) instead of stearoxy polyethylene glycol (30) -methacrylate (PSE-1300), A copolymer (4) was produced in the same manner as the polymer (1). Table 1 shows the weight percentages and weight average molecular weights of the structural units corresponding to the monomers in all the structural units of the obtained copolymer.

[Example 6]
(Production of copolymer (6))
Except for using 30 parts by mass of Lauroxy polyethylene glycol (4) -acrylate (Blemmer ALE-200; NOF Corporation) instead of stearoxy polyethylene glycol (30) -methacrylate (PSE-1300) A copolymer (4) was produced in the same manner as the polymer (1). Table 1 shows the weight percentages and weight average molecular weights of the structural units corresponding to the monomers in all the structural units of the obtained copolymer.

[Example 7]
(Production of copolymer (7))
In a reactor equipped with a reflux condenser, a thermometer, a nitrogen gas inlet tube and a stirrer, 150 parts by mass of ethanol, 10 parts by mass of stearoxypolyethylene glycol (30) -methacrylate (PSE-1300), 90 hydroxyethylacrylamide (HEAA) After charging the mass parts and mixing them uniformly, the reactor was purged with nitrogen. The reactor was set at 35 ° C., and 0.5 parts by mass of dimethyl 2,2-azobis (2-methylpropionate) (V-601; manufactured by Wako Pure Chemical Industries, Ltd.) was added, and 80 hours after 1 hour. The temperature was raised to ° C. After reacting for 2 hours after completion of the temperature increase, 0.3 parts by mass of dimethyl 2,2-azobis (2-methylpropionate) was further added. Thereafter, the mixture was reacted for 3 hours and then cooled to obtain an ethanol solution of the copolymer (7). This was dried under reduced pressure to remove ethanol to obtain a powder of copolymer (7).

[Example 8]
(Production of copolymer (8))
The copolymer (8) was prepared in the same manner as the copolymer (7) except that 50 parts by mass of stearoxypolyethylene glycol (30) -methacrylate (PSE-1300) and 50 parts by mass of hydroxyethylacrylamide (HEAA) were used. ) Was manufactured. Table 1 shows the weight percentages and weight average molecular weights of the structural units corresponding to the monomers in all the structural units of the obtained copolymer.

[Example 9]
(Production of copolymer (9))
In a reactor equipped with a reflux condenser, a thermometer, a nitrogen gas inlet tube and a stirrer, 150 parts by mass of ethanol, 70 parts by mass of stearoxy polyethylene glycol (30) -methacrylate (PSE-1300), 10 hydroxyethylacrylamide (HEAA) After 20 parts by mass of 20 parts by mass of dimethylaminopropylacrylamide (DMAPAA) was charged and mixed uniformly, the reactor was purged with nitrogen. The reactor was set at 35 ° C., and 0.5 parts by mass of dimethyl 2,2-azobis (2-methylpropionate) (V-601; manufactured by Wako Pure Chemical Industries, Ltd.) was added, and 80 hours after 1 hour. The temperature was raised to ° C. After reacting for 2 hours after completion of the temperature increase, 0.3 parts by mass of dimethyl 2,2-azobis (2-methylpropionate) was further added. Thereafter, the reaction was allowed to proceed for 3 hours. Thereafter, 15 parts by mass of sodium monochloroacetate was added and the mixture was stirred with heating for 8 hours and then cooled. The produced salt was removed by a centrifugal separator to obtain an ethanol solution of the copolymer (9). This was dried under reduced pressure to remove ethanol to obtain a powder of copolymer (9).

[Comparative Example 1]
(Production of copolymer (10))
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirrer was charged with 100 parts by mass of ethanol, and the dropping funnel was composed of 100 parts by mass of hydroxyethylacrylamide (HEAA) and 50 parts by mass of ethanol. The monomer mixture was charged, the reactor was purged with nitrogen, and then heated to 80 ° C. After charging 0.5 parts by mass of dimethyl 2,2-azobis (2-methylpropionate) (V-601; manufactured by Wako Pure Chemical Industries, Ltd.) into the reactor, the monomer mixture was added over 2 hours. And dripped. After reacting for 2 hours after completion of the dropwise addition, 0.3 parts by mass of dimethyl 2,2-azobis (2-methylpropionate) was further added. Thereafter, the mixture was reacted for 3 hours and then cooled to obtain an ethanol solution of the copolymer (10). This was dried under reduced pressure to remove ethanol to obtain a powder of copolymer (10).
Table 1 shows the weight percentages and weight average molecular weights of the structural units corresponding to the monomers in all the structural units of the obtained copolymer.

[Comparative Example 2]
(Production of copolymer (11))
A copolymer (11) was produced in the same manner as the copolymer (10) except that 90 parts by mass of hydroxyethyl acrylamide (HEAA) and 10 parts by mass of lauryl methacrylate (LMA) were used.
Table 1 shows the weight percentages and weight average molecular weights of the structural units corresponding to the monomers in all the structural units of the obtained copolymer.

[Comparative Example 3]
(Production of copolymer (12))
Same as copolymer (10) except that 70 parts by mass of hydroxyethylacrylamide (HEAA) and 30 parts by mass of methoxypolyethylene glycol (9) -methacrylate (Blenmer PME-400; manufactured by NOF Corporation) were used. Thus, a copolymer (12) was produced.
Table 1 shows the weight percentages and weight average molecular weights of the structural units corresponding to the monomers in all the structural units of the obtained copolymer.

(Preparation and evaluation of copolymer composition)
(Preparation of copolymer composition)
A copolymer composition was prepared using the copolymer obtained by the above method.
Tables 2 and 3 for the anionic surfactant-containing copolymer composition, Table 4 for the nonionic surfactant-containing copolymer composition, and anionic surfactant and amphoteric surfactant-containing copolymer weight Table 5 shows the blended composition of the combined composition. In addition, all the numerical values in each table | surface are the mass (mass part) of an active ingredient.

  In the adjustment, the surfactant, the copolymer of the present invention, and water were sequentially mixed and heated to 50 ° C. to make uniform. Depending on the formulation, conditioning ingredients were then added and mixed. At this time, the surfactant used is a commercially available one, and the amount of water of the surfactant is described as part of the amount of distilled water in the blend composition.

<Cationic conditioning polymer: Copolymer 13>
The cationic conditioning polymer used in the composition of the copolymer containing the anionic surfactant in Table 2 is a cationic copolymer (copolymer (13)) synthesized by the following method. This cationic copolymer is described in Japanese Patent Application Laid-Open No. 2007-63543 as a copolymer having a high conditioning effect.

  A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirrer was charged with 200 parts by mass of distilled water, and N-acryloylaminopropyl-N, N, N-trimethylammonium chloride ( DMAPAAC) A monomer mixture consisting of 47 parts by mass (59 parts by mass as an 80% by mass aqueous solution), 53 parts by mass of N, N-dimethylacrylamide (DMAA), and 80 parts by mass of distilled water was charged, and the reactor was purged with nitrogen After that, it was heated to 90 ° C. After adding 0.5 part by mass of 2,2'-azobis (2-methyl-N- (2-hydroxyethyl) -propionamide) to the reactor, the monomer mixture was added dropwise over 4 hours. After the completion of the dropwise addition, the mixture was reacted for 20 hours and then cooled to obtain a copolymer (13).

  The ratio of the structural unit corresponding to each monomer in all the structural units of the obtained copolymer is DMAPAAC / DMAA = 30/70 (mole percentage), and the weight average molecular weight is 430,000. The viscosity of the 20% by mass aqueous solution was 1490 mPa · s.

  The weight average molecular weight was measured as follows. Gel permeation chromatography (apparatus: manufactured by Tosoh Corporation, SC8010, SD8022, RI8020, CO8011, PS8010, column: Wakopak (Wakobeads G-50), developing solvent: water / methanol / acetic acid / acetic acid Sodium = 6/4 / 0.3 / 0.41), and the weight average molecular weight was determined using polyethylene glycol as a standard substance. Viscosity was measured using a B-type viscometer. 2 was performed at 30 rpm and 25 ° C.

(Evaluation of copolymer composition)
Using the copolymer composition prepared by the above method, the composition appearance, foam amount, foaming speed, foam texture, rinsing feel, precipitation upon water dilution, and feel after drying were evaluated by the methods described below. . The results are shown in the table in which each copolymer composition is described.

<Evaluation method>
[appearance]
The state after each of the obtained copolymer compositions was left at 25 ° C. for 1 day was visually confirmed. A uniform transparent solution is better, but if it has a certain amount of fog, it is a range that can be used as a cleaning composition without any problem.

[Amount of foam]
The amount of foam when foamed with a hand mixer was measured. Specifically, 1.5 g of the copolymer composition and 148.5 g of distilled water were weighed into a 500 ml polycup and bubbled for 20 seconds with a hand mixer (National hand mixer MK-H1-X, memory setting 2). The polycup foam and liquid were transferred to a 1 L graduated cylinder. After 5 minutes from the end of foaming, the graduated cylinder was tilted to remove only the waste liquid, and the amount of foam remaining in the graduated cylinder was read to obtain the amount of foam (ml).

[Speed of foaming]
Relative evaluation was performed by sensory evaluation by the half head method. Specifically, after pre-washing the hair of the monitor panel with warm water, the hair is divided symmetrically, and 1.0 g of the copolymer composition to be evaluated and 1.0 g of the comparative standard sample are foamed when foamed. The speed was evaluated in four stages. In addition, the monitor of this evaluation implementation is low-damaged hair that has not been treated with bleach or perm.

In the evaluation of the anionic surfactant-containing copolymer composition shown in Table 2, Comparative Example 4 was used as a comparative standard sample. In the evaluation of the anionic surfactant-containing copolymer composition shown in Table 3 (cationic copolymer-containing composition), Comparative Example 8 was used as a comparative standard sample. In the evaluation of the nonionic surfactant-containing copolymer composition shown in Table 4, Comparative Example 12 was used as a comparative standard sample.
0: Same bubbling speed as the comparison standard sample 1: Bubbling slightly faster than the comparison standard sample 2: Bubbling faster than the comparison standard sample 3: Bubbling significantly faster than the comparison standard sample

[Foam texture]
Relative evaluation was performed by sensory evaluation by the half head method. Specifically, following the evaluation of the foaming speed, the foam texture was evaluated in four stages. The foam texture was evaluated for wateriness and richness based on the elasticity and fineness of the foam. At this time, it was judged that a material having elasticity, fine texture, and rich feel was good.
0: Same foam texture as the comparative standard sample 1: Slightly better foam texture than the comparative standard sample 2: Better foam texture than the comparative standard sample 3: Superior foam texture better than the comparative standard sample

[Rinse feel]
Relative evaluation was performed by sensory evaluation by the half head method. Specifically, following the evaluation of the foaming speed and foam texture, the feel when rinsed in running water at 40 ° C. was evaluated in four stages. In addition, about the thing which has not evaluated the speed of foaming and foam texture, it evaluated after performing the same process. At this time, it was judged that the one with a good touch and smooth feel was good.
In the evaluation of the amphoteric surfactant-containing copolymer composition shown in Table 5, Comparative Example 17 was used as a comparative standard sample.
0: The same rinsing feel as the comparative standard sample 1: Slightly rinsing feel better than the comparative standard sample 2: Better rinsing feel than the comparative standard sample 3: Superior rinsing feel superior to the comparative standard sample

[Feel after drying]
Relative evaluation was performed by sensory evaluation by the half head method. Specifically, following the evaluation of the rinsing feeling, the feeling after towel drying and drying with a dryer was evaluated in four stages. At this time, it was determined that a material with high smoothness and less sway was good.
0: Compared to the standard sample, smoothness and non-stickiness are inferior 1: Compared to the standard sample, smoothness or non-stickiness is inferior 2: Feeling after drying is the same as the comparative standard sample 3: Feeling after drying, compared to the comparative standard sample Is good

[Precipitation when diluted with water]
The appearance when the copolymer composition was diluted with water was visually confirmed. Specifically, after the copolymer composition was diluted with 4 times distilled water and mixed, the appearance of the solution left standing was visually confirmed and evaluated in the following four stages. At this time, the better the non-uniform solution was formed as a coacervate-like complex was formed.
0: Uniform and transparent 1: Slightly fogged 2: Scratched 3: Heterogeneous solution such as phase separation

  As can be seen from the above results, the copolymer according to the present invention is compared with Comparative Examples 1 and 2 and Comparative Example 3 which are copolymers having no amphiphilic monomer (A) as a constituent unit. When used as a copolymer composition, the foaming speed and the foam texture are excellent. In the evaluation results of Table 2, the amount of foam, the speed of foaming, and the foam texture are important. In the evaluation results of Table 3, the amount of foam, the speed of foaming, and the foam texture are not reduced without decreasing the rinsing feel. It is important to improve, and in the evaluation results in Table 4, the amount of foam, the speed of foaming, and the foam texture can be obtained without adding an anionic surfactant. is important. Further, the conditioning effect is excellent in the feeling at the time of rinsing and the feeling after drying without using a cationic conditioning polymer in the evaluation results of Table 5. Therefore, the copolymer composition of the present invention is excellent as a cleaning composition and a cosmetic composition, and is particularly suitable as a hair cleaning composition and a hair cosmetic composition.

  The copolymer of the present invention is excellent in foam modifying effect, conditioning effect, thickening effect and the like when used as a composition, and the copolymer composition of the present invention is a detergent composition, a cosmetic. It is suitable as a composition, and is particularly useful as a hair cleanser and hair cosmetic.

Claims (14)

Radical polymerizable vinyl group, and constituting units corresponding to the amphiphilic monomer (A) from the polyalkylene oxide and carbon 6 with 30 hydrocarbon group, a hydrophilic represented by the following following general formula (1) including co-polymer and a structural unit corresponding to the monomer (B).
^{_{CH 2 = C (R 1)}} -CO-NR 2 R 3 (1)
(In General Formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently represent a hydrogen atom or an alkyl group optionally having a hydroxyl group having 1 to 4 carbon atoms. represents the sum of carbon numbers of R ² and R ³ Ri der 1 to 4, at least either one of R ² and R ³ is an alkyl group having a hydroxyl group.) The copolymer according to claim 1, wherein the amphiphilic monomer (A) is represented by the following general formula (2).
^{_{CH 2 = C (R 4)}} -CO- (O) a (NH) 1-a -X- (CH 2 CH (R 5) O) m -Y-R 6 (2)
(In General Formula (2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom, a methyl group, or an ethyl group, and R ⁶ is a carbon that may contain any of a linear, branched, or cyclic structure. A hydrocarbon group having a number of 6 to 30; X and Y each independently represent any divalent linking group or direct bond; a is 0 or 1, and m is 2 to 100. Total of all structural units constituting the copolymer, the constituting units corresponding to the structural unit and parent aqueous monomer corresponding to both amphiphilic monomer (A) (B) satisfies the following proportions, The copolymer according to claim 1 or 2.
Structural units corresponding to both amphiphilic monomer (A): 0.1 to 90 wt%
Structural units corresponding to the parent aqueous monomer (B): 1-99.9 wt%   The copolymer according to any one of claims 1 to 3, wherein the weight average molecular weight is 3,000 to 1,000,000.   A copolymer composition containing 1 to 40% by mass of an anionic surfactant and 0.01 to 40% by mass of the copolymer according to any one of claims 1 to 4.   The copolymer composition according to claim 5, comprising 0.01 to 40% by mass of a cationic conditioning agent.   A copolymer composition containing 1 to 40% by mass of a nonionic surfactant and 0.01 to 40% by mass of the copolymer according to any one of claims 1 to 4.   A copolymer composition containing 1 to 40% by weight of an amphoteric surfactant and 0.01 to 40% by weight of the copolymer according to any one of claims 1 to 4. The copolymer composition according to claim 8, which contains 1 to 40% by mass of an anionic surfactant. A cleaning composition comprising the copolymer composition according to any one of claims 5 to 9 . A hair cleansing composition comprising the cleaning composition according to claim 10 . A cosmetic composition comprising the copolymer composition according to any one of claims 5 to 9 . A hair cosmetic comprising the cosmetic composition according to claim 12 .   A conditioner composition comprising a cationic surfactant, a higher alcohol, and the copolymer according to any one of claims 1 to 4.