JP5119874B2 - Cationic copolymer and cosmetic for hair - Google Patents

Description

  The present invention relates to a cationic copolymer and a cosmetic for hair containing the polymer as an active ingredient.

Phosphorylcholine group-containing polymers are excellent in biocompatibility such as blood compatibility, complement inactivation, and non-adsorption of biological substances due to the phospholipid-like structure derived from biological membranes. It is known to have excellent properties such as properties. Research and development on the synthesis and use of polymers for the purpose of developing bio-related materials that make use of such functions are being actively conducted.
Among these, in the cosmetics field, 2- (meth) acryloyloxyethyl-2 '-(trimethylammonio) ethyl phosphate homopolymer, 2- (meth) acryloyloxyethyl-2'-(trimethylammonio) ethyl phosphate And a hydrophilic monomer and / or a hydrophobic monomer such as butyl methacrylate are based on a moisturizing effect and an improvement effect on the skin, and a film-forming effect on the hair It is known to show a protective effect. For example, Patent Documents 1 to 4 disclose that cosmetics containing these polymers can be provided.
Patent Document 1 describes a polymer of 2-methacryloyloxyethyl phosphorylcholine and a hydrophobic monomer. However, this binary polymer has insufficient adsorptivity to the hair, and it is difficult to leave a sufficient amount of polymer on the hair surface to express its function. These phosphorylcholine group-containing polymers known as cosmetics are water-soluble because they need to be dissolved or dispersed in water. Therefore, such a polymer exhibits an effect by forming a hydrous gel film on the skin and hair.
In particular, with regard to hair cosmetics used for the purpose of healthy growth and maintenance of hair, it has been proposed that the surface of the hair becomes smooth and glossy due to a polymer film formed on the surface. However, in this case, the intensity of reflected light on the hair surface increases, and the psychological glossiness resulting therefrom is only improved. For this reason, the reflected light inside the hair is not sufficient, and the glittering and glittering feeling caused by the reflected light is not improved. Therefore, it cannot be said that the effect is sufficient as a polymer for polishing.

Patent Document 5 proposes application of a polymer containing isobornyl (meth) acrylate units to hair. However, this polymer also has an insufficient adsorptivity to hair, and it is difficult to leave a sufficient amount of polymer on the hair surface to express its function.
Further, Patent Document 6 discloses a copolymer of 2-((meth) acryloyloxy) ethyl-2- (trimethylammonio) ethyl phosphate and 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride. A hair film-forming agent has been proposed. However, even in this copolymer, the effect of improving the intensity of reflected light on the hair surface and inside the hair is poor, and there is room for improvement as a polymer for polishing.
Japanese Patent Laid-Open No. 5-70321 JP-A-6-157269 JP-A-6-157270 JP-A-6-157271 Japanese National Patent Publication No. 11-506133 JP 2004-189678 A

The object of the present invention is to provide a novel cationic property that combines the ability to adsorb to hair based on a cationic monomer and optical properties based on isobornyl (meth) acrylate, in addition to excellent skin affinity based on a phosphorylcholine-like group. An object of the present invention is to provide a copolymer and a hair gloss polymer using the copolymer.
Another object of the present invention is to provide a hair cosmetic that adsorbs to the hair surface with high efficiency, imparts gloss, exhibits high water-washing resistance, and maintains the gloss and shine of the hair even after washing. There is.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a novel copolymer by polymerizing a specific phosphorylcholine-like group monomer, isobornyl (meth) acrylate and a cationic monomer. The copolymer has good adsorptivity to hair and can improve optical properties such as gloss of hair by amplifying not only hair surface reflection but also internal reflection. The present inventors have found that this can be done and have completed the present invention.

(式(１)中、Ｒ¹は水素原子又はメチル基を示し、Ｘは炭素数１〜６のアルキレン基又はアルキレンオキシ基を示す。ｐは０又は１、ｑは１〜４の整数である。)

(式(２)中、Ｒ²は水素原子又はメチル基を示す。)

(式(３)中、Ｒ³は水素原子又はメチル基を示し、Ｌは−(CH₂)p¹−Ｌ¹、−(C＝O)O−(CH₂)p¹−Ｌ¹、−(C＝O)O−((CH₂)p²−O)p¹−Ｌ¹又は−CH₂CH(OH)CH₂−Ｌ¹である。p¹は０〜２４、p²は２〜５の整数を示し、Ｌ¹はアミノ基、アンモニウム塩基、ピリジル基又はピリジニウム塩基を示す。)
また本発明によれば、上記カチオン性共重合体からなる毛髪つや出し用ポリマーが提供される。
更に本発明によれば、上記毛髪つや出し用ポリマーを０．００１〜５０質量％含有する毛髪用化粧料が提供される。 According to the present invention, the constituent unit U ¹ of the formula (1), and the structural unit U ² of formula (2), and a constituent unit U ³ of the formula (3), and U ¹ A cationic copolymer having a molar ratio of U ² to U ³ of 1 to 16: 1 to 12: 1 to 16 and a weight average molecular weight of 5,000 to 2,000,000 is provided.

(In the formula (1), R ¹ represents a hydrogen atom or a methyl group, X represents an alkylene group or alkyleneoxy group having 1 to 6 carbon atoms, p is 0 or 1, and q is an integer of 1 to 4. .)

(In formula (2), R ² represents a hydrogen atom or a methyl group.)

(In Formula (3), R ³ represents a hydrogen atom or a methyl group, L represents — (CH ₂ ) p ¹ -L ¹ , — (C═O) O— (CH ₂ ) p ¹ -L ¹ , − (C = O) O - ( (CH 2) p 2 -O) p 1 -L 1 or _{-CH 2 CH (OH) CH 2} -L 1 a is .p ¹ is 0-24, p ² is 2 5 represents an integer of 5 and L ¹ represents an amino group, an ammonium base, a pyridyl group or a pyridinium base.)
Moreover, according to this invention, the polymer for hair gloss which consists of the said cationic copolymer is provided.
Furthermore, according to this invention, the cosmetics for hair which contain 0.001-50 mass% of said hair polish polymers are provided.

  The cationic copolymer of the present invention is a novel polymer. In addition to excellent skin affinity based on a phosphorylcholine-like group, the cationic copolymer has adsorptivity to hair and isobornyl (meth) acrylate. It is a material that combines optical properties based on it. Therefore, when the cationic copolymer of the present invention is used as an active ingredient in hair cosmetics, it adsorbs to the hair surface with high efficiency, imparts gloss, and is hydrophobic based on isobornyl (meth) acrylate. In addition, it exhibits high water-washing resistance and maintains the gloss and shine of the hair after washing.

Hereinafter, the present invention will be described in more detail.
The cationic copolymer of the present invention includes a structural unit U ^{1 represented} by the above formula (1) based on a specific phosphorylcholine-like group-containing monomer (hereinafter sometimes abbreviated as monomer M ¹ ), etc. A structural unit U ^{2 represented} by the above formula (2) based on isobornyl (meth) acrylate (hereinafter sometimes abbreviated as monomer M ² ) and the like, and a cationic group-containing monomer (hereinafter referred to as monomer M ^3). A copolymer having a specific weight average molecular weight and containing the structural unit U ^{3 represented} by the above formula (3) in a specific ratio.

式(４)中、Ｒ¹は水素原子又はメチル基を示し、Ｘは炭素数１〜６のアルキレン基又はアルキレンオキシ基を示す。ｐは０又は１、ｑは１〜４の整数である。 In the structural unit U ^{1 represented} by the above formula (1), R ¹ represents a hydrogen atom or a methyl group, and X represents an alkylene group or alkyleneoxy group having 1 to 6 carbon atoms. p is 0 or 1, and q is an integer of 1 to 4.
Constituent unit U ¹ is a unit derived from monomer M ^1, the monomer M ¹ is a specific phosphorylcholine-like group-containing monomer represented by the formula (4).

In formula (4), R ¹ represents a hydrogen atom or a methyl group, and X represents an alkylene group having 1 to 6 carbon atoms or an alkyleneoxy group. p is 0 or 1, and q is an integer of 1 to 4.

Examples of the monomer M ¹ include 2-((meth) acryloyloxy) ethyl-2 ′-(trimethylammonio) ethyl phosphate, 3-((meth) acryloyloxy) propyl-2 ′-(trimethyl). Ammonio) ethyl phosphate, 4-((meth) acryloyloxy) butyl-2 '-(trimethylammonio) ethyl phosphate, 5-((meth) acryloyloxy) pentyl-2'-(trimethylammonio) ethyl Phosphate, 6-((meth) acryloyloxy) hexyl-2 '-(trimethylammonio) ethyl phosphate, 2-((meth) acryloyloxy) propyl-2'-(trimethylammonio) ethyl phosphate, 2- ((Meth) acryloyloxy) butyl-2 ′-(trimethylammonio) ethyl phosphate, 2-((meth) acryloyloxy) pentyl-2 ′-(trimethylammonio) ethyl Examples include ruphosphate and 2-((meth) acryloyloxy) hexyl-2 ′-(trimethylammonio) ethyl phosphate. Here, (meth) acryloyl means acryloyl and methacryloyl. These monomers M ¹ can be used singly or in combination of two or more when producing the copolymer of the present invention.
Among the above examples, 2-((meth) acryloyloxy) ethyl-2 ′-(trimethylammonio) ethyl phosphate is preferable, and 2- (methacryloyloxy) ethyl-2 ′-(trimethylammonio) ethyl phosphate (MPC and (Omitted) is more preferable from the viewpoint of availability.

The monomer M ¹ can be produced by a known method. For example, a method of reacting a compound obtained by reacting a hydroxyl group-containing polymerizable monomer and 2-bromoethyl phosphoryl dichloride in the presence of a tertiary base with a tertiary amine as disclosed in JP-A-54-63025. Can be produced by a method in which a cyclic compound is obtained by the reaction of a hydroxyl group-containing polymerizable monomer and a cyclic phosphorus compound, and then a ring-opening reaction with a tertiary amine, as disclosed in JP-A-58-154591. .

式(５)中、Ｒ²は水素原子又はメチル基を示す。
In the structural unit U ² represented by the above formula (2), R ² represents a hydrogen atom or a methyl group.
Constituent unit U ² is a unit derived from monomer M ^2, the monomer M ² is a mono-acrylic acid esters and / or monomethacrylate of isoborneol of formula (5).

In the formula (5), R ² represents a hydrogen atom or a methyl group.

式(６)中、Ｒ³は水素原子又はメチル基を示し、Ｌは−(CH₂)p¹−Ｌ¹、−(C＝O)O−(CH₂)p¹−Ｌ¹、−(C＝O)O−((CH₂)p²−O)p¹−Ｌ¹又は−CH₂CH(OH)CH₂−Ｌ¹である。p¹は０〜２４、p²は２〜５の整数を示し、Ｌ¹はアミノ基、アンモニウム塩基、ピリジル基又はピリジニウム塩基を示す。 In the structural unit U ³ represented by the above formula (3), R ³ represents a hydrogen atom or a methyl group, L represents — (CH ₂ ) p ¹ -L ¹ , — (C═O) O— (CH ₂ ) p ¹ -L ^1, - a _{- (((CH 2 C =} O) O) p 2 -O) p 1 -L 1 or _{-CH 2 CH (OH) CH 2} -L 1. p ¹ represents an integer of 0 to 24, p ² represents an integer of ² to 5, and L ¹ represents an amino group, an ammonium base, a pyridyl group or a pyridinium base.
Constituent units U ³ is a unit derived from monomer M ^3, the monomer M ³ represents a cationic group-containing monomer represented by the formula (6).

In the formula (6), R ³ represents a hydrogen atom or a methyl group, L represents — (CH ₂ ) p ¹ -L ¹ , — (C═O) O— (CH ₂ ) p ¹ -L ¹ , — ( C = O) O - is a ^{_{((CH 2) p 2 -O}} ) p 1 -L 1 or _{-CH 2 CH (OH) CH 2} -L 1. p ¹ represents an integer of 0 to 24, p ² represents an integer of ² to 5, and L ¹ represents an amino group, an ammonium base, a pyridyl group or a pyridinium base.

Examples of the monomer M ³ include allylamine, aminoethyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylamide, and 2- (N, N-dimethylamino) ethyl (meth) acrylate. , Monomers having an amino group such as 2- (N, N-diethylamino) ethyl (meth) acrylate and 3- (N, N-dimethylamino) propyl (meth) acrylamide; N, N, N-trimethyl-N -(3- (meth) acrylamidopropyl) ammonium chloride, N- (3- (meth) acrylamide) propyl-N, N-dimethyl-N- (2-hydroxypropyl) ammonium acetate, N- (3- (meth) Acrylamide) propyl-N, N, N-trimethylammonium sulfate, N, N, N-trimethyl-N- (2- (meth) acryloxyethyl) ammonium Chloride, N, N-dimethyl-N-benzyl-N- (2- (meth) acryloxyethyl) ammonium chloride, N, N, N-trimethyl-N- (2-hydroxy-3- (meth) acryloxypropyl) ) Ammonium chloride, N- (2- (meth) acryloyloxy) ethyl-N, N, N-trimethylammonium methyl sulfate, N- (2- (meth) acryloyloxy) ethyl-N, N-dimethyl-N- Ethylammonium ethyl sulfate, N- (2- (meth) acryloyloxy) ethyl-N, N, N-trimethylammonium p-toluenesulfonate, N- (3- (meth) acryloyloxy-2-hydroxy) ethyl-N , N, N-trimethylammonium acetate, N, N-dimethyl-N, N-diallylammonium chloride, etc. Monomer having a monium base; Monomer having a pyridyl group such as 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 3- (2- (meth) acryloxy) ethoxycarbonylpyridine; N-methyl- And monomers having a pyridinium base such as 2-vinylpyridinium chloride. These monomers M ³ are, when producing the copolymer of the present invention may be used alone or in combination of two or more.
Among the above examples, (meth) acrylic acid esters are more preferable, and specific examples include aminoethyl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, and N, N-dimethyl. -N-benzyl-N- (2- (meth) acryloxyethyl) ammonium chloride, N, N, N-trimethyl-N- (2-hydroxy-3- (meth) acryloxypropyl) ammonium chloride.

The copolymer of the present invention contains the structural units U ^{1 to} U ³ in a specific ratio.
The molar ratio of the structural units U ¹ , U ² and U ³ in the copolymer is usually in the range of 1 to 16: 1 to 12: 1 to 16, preferably 2 to 10: 2 to 10: 2 to 12. is there. If the proportion of the structural unit U ¹ is less than the above range, the compatibility with the skin is impaired, and if the proportion of the structural unit U ² is less than the above range, the effect of improving hair brightness cannot be sufficiently exerted, and the proportion of the structural unit U ³ If it is less than the said range, the adsorptivity to hair is inadequate and the desired effect cannot fully be exhibited.
The copolymer of the present invention may contain other structural units in addition to the structural units U ^{1 to} U ^{3 as long} as the desired effects of the present invention are not impaired. The proportion of other structural units can be appropriately determined according to the function and effect of the structure, but is usually preferably 30 mol% or less of the total amount of the copolymer.

In the present invention, the weight average molecular weight of the copolymer is in the range of 5,000 to 2,000,000, preferably 10,000 to 2,000,000. When the molecular weight is less than 5,000, the cohesive strength of the copolymer to the hair is insufficient, and the water-washing resistance may be inferior. On the other hand, when the molecular weight exceeds 2,000,000, the viscosity of the copolymer becomes extremely high, handling properties are poor, and blending into a cosmetic may be difficult.
In the copolymer of the present invention, the number of each structural unit can be selected so as to be in the range of the molar ratio of the structural units and the weight average molecular weight. Usually, the number (n1) of the structural units U ¹ is 1 to 3, 000, the number of constituent units U ² (n2) is preferably 3 to 10,000, the number of constituent units U ³ (n3) can be appropriately determined from the range of 3 to 10,000.

The copolymer of the present invention includes, for example, the monomer M ¹ , the monomer M ² and the monomer M ³ , and can be polymerized as long as necessary without impairing the desired effect of the present application. A monomer composition containing the polymerizable monomer can be easily obtained by radical polymerization in the presence of a polymerization initiator in an inert gas atmosphere such as nitrogen, carbon dioxide, and helium.
Examples of radical polymerization include known methods such as bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. From the viewpoint of purification, solution polymerization is preferred.
In the monomer composition, the proportion of the monomer M ¹ is usually 5 to 80 mol%, preferably 10 to 50 mol%, the proportion of the monomer M ² is usually 5 to 60 mol%, preferably from 10 to 50 mol%, the proportion of the monomer M ³ are usually 5 to 80 mol%, preferably 10 to 60 mol%. If the monomer M ¹ is less than 5 mol%, the compatibility of the resulting copolymer with the skin may be impaired, and if the monomer M ² is less than 5 mol%, the hair brightness improvement effect is sufficient. If the monomer M ³ is less than 5 mol%, the adsorptivity to the hair is insufficient and the desired effect may not be obtained.

As a more specific method for producing the copolymer of the present invention, for example, the following method may be mentioned, but is not limited thereto.
For example, first, a solvent in which a monomer composition such as an ethanol / water (= 8/2, wt / wt) mixture is dissolved is used, and the monomer composition is usually dissolved in an amount of 5 to 30% by mass. Let As a polymerization initiator, for example, azobisisobutyronitrile (AIBN) is usually added in an amount of 2 to 7 parts by mass with respect to 100 parts by mass of the monomer composition, and is usually 40 in an inert gas atmosphere such as nitrogen. The method of superposing | polymerizing at -100 degreeC, preferably 60-80 degreeC for 3 to 15 hours is mentioned.

Further, in preparing the copolymer was changed amount of the structural unit U ¹ ~U ³ can be carried out by changing the charging ratio of monomers M ¹ ~M ³ in the monomer composition . For example, when the molar ratio of U ¹ : U ² : U ³ is desired to be 5: 3: 2, the charging ratio of the corresponding monomer M ¹ : M ² : M ³ is set to a molar ratio of 5: 3: 2. , U ¹ : U ² : U ³ molar ratio is 1: 1: 1, the corresponding monomer M ¹ : M ² : M ³ charge ratio is 1: 1: 1. Thus, a desired copolymer can be obtained.
The molecular weight can be adjusted by, for example, a method of changing the concentration of the polymerization initiator or the polymerization temperature. For example, when the molecular weight is increased, the amount of the polymerization initiator is decreased, or the polymerization temperature is decreased, and when the molecular weight is decreased, the amount of the polymerization initiator is increased or the cation having the desired molecular weight is increased by increasing the polymerization temperature. Sex copolymer can be obtained.
The obtained copolymer can be purified by a general purification method such as a reprecipitation method, a dialysis method, or an ultrafiltration method.

Since the cationic copolymer of the present invention has the above-mentioned properties, it can be used as the hair polish polymer of the present invention.
There are two types of hair gloss: psychological gloss and gloss due to internal reflection of hair.
Psychological gloss is obtained by reflecting light on the surface of the hair. Damaged hair loses the hydrophobic layer on the surface of the hair, lifts the cuticle, reduces the reflected light intensity on the hair surface, and lowers the psychological gloss.
Therefore, by forming a polymer film on the hair surface, the reflected light intensity on the hair surface can be improved and the psychological gloss can be improved.
On the other hand, the gloss caused by the internal reflection of the hair is obtained by reflecting the light incident on the inside of the hair. Damaged hair causes cavities inside the hair due to leakage of intercellular lipids. For this reason, the light incident on the inside of the hair causes irregular reflection, and the gloss is lowered.
Therefore, by reducing the cavities generated in the hair, irregular reflection of the incident light is suppressed, the reflected light intensity is improved, and gloss due to internal reflection of the hair can be improved.

The hair polish polymer of the present invention not only covers the hair surface, but also penetrates into the hair and can reduce the cavities generated in the hair, thereby improving the gloss by internal reflection of the hair. In addition, since the hair polishing polymer that has entered the inside has its hair surface covered with the polymer, it is difficult to leak to the outside of the hair and a highly durable gloss can be obtained.
Hair gloss can be measured using a goniophotometer. For example, 11 hairs are arranged in parallel on a sample stage, and the gloss of hair is measured in a constant temperature and humidity chamber at 25 ° C. and 60% RH using a goniophotometer GP-5 (manufactured by Murakami Color Research Laboratory). It can be performed.
Specifically, it can be measured by calculating with the formulas (A) and (B) shown in the examples described later.

The cosmetic for hair of the present invention contains the above-described hair polish polymer of the present invention.
In the cosmetic of the present invention, the concentration of the hair polish polymer is usually preferably 0.001 to 50% by mass, particularly preferably 0.01 to 30% by mass based on the total amount of the cosmetic. When the concentration is less than 0.001% by mass, the improvement of hair glossiness may be insufficient. On the other hand, when the concentration exceeds 50% by mass, the viscosity of the cosmetic is increased, and the handling property may be deteriorated.

  In the hair cosmetic composition of the present invention, additives commonly used in cosmetics can be appropriately blended as necessary. The additive is not particularly limited as long as the desired effect of the present invention is not hindered. For example, oils, surfactants, moisturizers, thickeners, colorants, alcohols, UV protection agents, amino acids, vitamins, whitening agents, organic acids, inorganic salts, enzymes, antioxidants, stabilizers, antiseptics Agents, fungicides, anti-inflammatory agents, skin activators, blood circulation promoters, anti-seborrheic agents, anti-inflammatory agents, etc., sequestering agents, pH adjusters, astringents, refreshing agents, fragrances, pigments, water It is done.

The kind of the cosmetic for hair of the present invention is not particularly limited, and examples thereof include shampoo, rinse, hair mist, hair cream, and hair foam.
In addition to the above-mentioned hair cosmetics, the cationic copolymer of the present invention can be used, for example, in skin care cosmetics such as lotions, emulsions, creams, cosmetics, foundations, makeup cosmetics, massage cosmetics, and pack cosmetics. It can also be used. Furthermore, it can be used as a bath preparation, and can also be used in body care cosmetics such as body shampoos and hand soaps.

Next, the contents of the present invention will be described in more detail with reference to synthesis examples, examples and comparative examples, but the present invention is not limited thereto. Various analyzes in the examples were carried out according to the following methods.
1. A method for analyzing the molecular weight of the polymer;
(Molecular weight measurement)
The molecular weight of the copolymer was measured for the test solution under the following GPC (gel permeation chromatography) conditions. The test solution was prepared by first dissolving the sample polymer in a chloroform / methanol (= 6/4, v / v) mixed solvent containing 0.5% by mass of lithium bromide. Next, a 0.5 mass% polymer solution was prepared, and this solution was filtered by a 0.45 μm membrane filter.
[Conditions for GPC analysis]
Column: PLgel 5 μm MIXED-C, 2 in series (manufactured by Polymer Laboratories), elution solvent: chloroform / methanol (= 6/4, v / v) mixed solvent containing 0.5% by mass of lithium bromide, detection; parallax Refractometer, standard substance for weight average molecular weight (Mw) measurement: PMMA (manufactured by Polymer Laboratories), flow rate: 1.0 mL / min, amount of sample solution used: 20 μL, column temperature: 40 ° C., integrator manufactured by Tosoh Corporation A built-in molecular weight calculation program (GPC program for SC-8020) was used.
2. Organic elemental analysis;
A polymer sample was analyzed by elemental analysis using a model Perkin Elmer 2400II-CHNS / i analyzer.
3. MPC component determination method;
Polymer samples were quantified by measuring phosphorus content by vanadomolybdic acid spectrophotometry.
4). Calculation of the composition ratio in the polymer;
(a) The ratio of MPC in the polymer was calculated from the phosphorus content. (b) The ratio of the cationic monomer in the polymer was determined by (actual value of nitrogen by elemental analysis) − (calculated value of nitrogen content from the ratio of MPC determined in (a)). (c) The proportion of isobornyl methacrylate in the polymer is (actual value of carbon by elemental analysis)-(calculated value of carbon content from the proportion of each monomer determined in (a) and (b)) Determined by

Example 1 (Polymer 1; MPC5-IbMA3-QAMA2)
MPC 11.3 g, isobornyl methacrylate (IbMA) 5.1 g and N, N, N-trimethyl-N- (2-hydroxy-3-methacryloxypropyl) ammonium chloride (QAMA) 3.6 g were added to ethanol / water ( = 8/2, wt / wt) The mixture was dissolved in 180 g of the mixed solution, and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, the deposited precipitate was filtered, and vacuum dried at room temperature for 48 hours to obtain 15.8 g of powder. The weight average molecular weight of the obtained copolymer was 279,000. This is polymer 1. The IR, NMR, phosphorus quantitative analysis, and elemental analysis data are shown below.
IR: 3413 cm ⁻¹ (−OH), 2954 cm ⁻¹ (−CH), 1732 cm ⁻¹ (C═O), 1489 cm ⁻¹ (−CH), 1246 cm ⁻¹ (P═O), 1161 cm ⁻¹ (C− O-C), 1088 cm < ^-1 > (P-O-C).
_{NMR: 0.8-1.2ppm (CH 3 -C -} ), 1.4-2.2ppm (-CH 2 CH 2 -, - CHCH -), 3.3ppm (-N (CH 3) 3), 3.5-5.0ppm (-CH _{2 CH 2 O -, - C} -CH-O -, - CH 2 CH (OH) -).
Phosphorus content: 59126ppm (theoretical value: 59373ppm)
Elemental analysis data: Actual measurement value: C; 53.83%, H; 8.17%, N; 3.80% (theoretical value: C; 53.67%, H; 8.26%, N; 3.74%)
Kjeldahl nitrogen content 3.75% (theoretical value 3.74%)
The chemical structure of the polymer 1 obtained from the above results has the following random structure.
― [― (MPC) ₅₃₂ ― (IbMA) ₃₀₉ ― (QAMA) ₂₂₅ ―] ―

Example 2 (Polymer 2; MPC1-IbMA1-QAMA1)
MPC 7.8g, IbMA 5.9g, and QAMA 3.6g were melt | dissolved in 180g of ethanol / water (= 8/2, wt / wt) liquid mixture, and the inside of reaction container was fully substituted with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, the deposited precipitate was filtered, and vacuum dried at room temperature for 48 hours to obtain 16.1 g of powder. The weight average molecular weight of the obtained copolymer was 326,000. This is polymer 2. The IR, NMR, phosphorus quantitative analysis, and elemental analysis data are shown below.
IR: 3413 cm ⁻¹ (−OH), 2954 cm ⁻¹ (−CH), 1732 cm ⁻¹ (C═O), 1489 cm ⁻¹ (−CH), 1246 cm ⁻¹ (P═O), 1161 cm ⁻¹ (C− O-C), 1088 cm < ^-1 > (P-O-C).
_{NMR: 0.8-1.2ppm (CH 3 -C -} ), 1.4-2.2ppm (-CH 2 CH 2 -, - CHCH -), 3.3ppm (-N (CH 3) 3), 3.5-5.0ppm (-CH _{2 CH 2 O -, - C} -CH-O -, - CH 2 CH (OH) -).
Phosphorus content: 40547ppm (theoretical value: 40983ppm)
Elemental analysis data: Actual measurement values: C; 55.43%, H; 8.51%, N; 3.81% (theoretical values: C; 55.69%, H; 8.48%, N; 3.71%)
Kjeldahl nitrogen content 3.73% (theoretical value 3.71%)
The chemical structure of the polymer 2 obtained from the above results had the following random structure.
― [― (MPC) ₄₂₆ ― (IbMA) ₄₀₉ ― (QAMA) ₄₆₁ ―] ―

Example 3 (Polymer 3; MPC2-IbMA1-DMAEMA2)
10.5 g of MPC, 3.9 g of IbMA and 5.6 g of 2- (N, N-dimethylamino) ethyl methacrylate (DMAEMA) are dissolved in 180 g of an ethanol / water (= 8/2, wt / wt) mixed solution, and nitrogen gas is added. The inside of the reaction vessel was sufficiently replaced with. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 17.3 g of powder. The weight average molecular weight of the obtained copolymer was 258,000. This is polymer 3. The IR, NMR, phosphorus quantitative analysis, and elemental analysis data are shown below.
IR: 2954cm ^-1 (-CH), 1732cm ^-1 (C = O), 1489cm ^-1 (-CH), 1246cm ^-1 (P = O), 1161cm ^-1 (C-O-C), 1088cm ^-1 (P-O-C).
_{NMR: 0.8-1.2ppm (CH 3 -C -} ), 1.4-2.2ppm (-CH 2 CH 2 -, - CHCH -), 3.3ppm (-N (CH 3) 2), 3.5-5.0ppm (-CH _{2 CH 2 O -, - C} -CH-O-,).
Phosphorus content: 55021ppm (theoretical value: 55169ppm)
Elemental analysis data: Actual measurement: C; 55.51%, H; 8.38%, N; 5.04% (theoretical value: C; 55.37%, H; 8.52%, N; 4.99%)
Kjeldahl nitrogen content 4.85% (theoretical value 4.99%)
The chemical structure of the polymer 3 obtained from the above results has the following random structure.
― [― (MPC) ₄₅₈ ― (IbMA) ₂₂₁ ― (DMAEMA) ₄₇₁ ―] ―

Example 4 (Polymer 4; MPC5-IbMA3-AEMA2)
MPC12.3g, IbMA5.5g and aminoethyl methacrylate (AEMA) 2.2g are dissolved in 180g of ethanol / water (= 8/2, wt / wt) mixed solution, and the inside of the reaction vessel is sufficiently replaced with nitrogen gas. did. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 16.5 g of powder. The weight average molecular weight of the obtained copolymer was 355,000. This is polymer 4. The IR, NMR, phosphorus quantitative analysis, and elemental analysis data are shown below.
IR: 2954cm ^-1 (-CH), 1732cm ^-1 (C = O), 1489cm ^-1 (-CH), 1246cm ^-1 (P = O), 1161cm ^-1 (C-O-C), 1088cm ^-1 (P-O-C).
_{NMR: 0.8-1.2ppm (CH 3 -C -} ), 1.4-2.2ppm (-CH 2 CH 2 -, - CHCH -), 3.5-5.0ppm (-CH 2 CH 2 O -, - C-CH-O −,).
Phosphorus content: 64434ppm (theoretical value: 64627ppm)
Elemental analysis data: Actual measurement: C; 54.63%, H; 8.01%, N; 4.23% (theoretical value: C; 54.47%, H; 8.25%, N; 4.11%)
Kjeldahl nitrogen content 4.08% (theoretical value 4.11%)
The chemical structure of the polymer 4 obtained from the above results has the following random structure.
― [― (MPC) ₇₃₈ ― (IbMA) ₄₂₄ ― (AEMA) ₃₃₅ ―] ―

Example 5 (Polymer 5; MPC12-IbMA1-AEMA7)
15.2 g of MPC, 1.0 g of IbMA and 3.8 g of AEMA were dissolved in 180 g of an ethanol / water (= 8/2, wt / wt) mixed solution, and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, the deposited precipitate was filtered, and vacuum dried at room temperature for 48 hours to obtain 16.2 g of powder. The weight average molecular weight of the obtained copolymer was 286,000. This is designated as Polymer 5. The IR, NMR, phosphorus quantitative analysis, and elemental analysis data are shown below.
IR: 2954cm ^-1 (-CH), 1732cm ^-1 (C = O), 1489cm ^-1 (-CH), 1246cm ^-1 (P = O), 1161cm ^-1 (C-O-C), 1088cm ^-1 (P-O-C).
_{NMR: 0.8-1.2ppm (CH 3 -C -} ), 1.4-2.2ppm (-CH 2 CH 2 -, - CHCH -), 3.5-5.0ppm (-CH 2 CH 2 O -, - C-CH-O −,).
Phosphorus content: 79513ppm (theoretical value: 79864ppm)
Elemental analysis data: Actual measurement value: C; 48.73%, H; 7.48%, N: 5.54% (theoretical value: C; 48.40%, H; 7.78%, N; 5.67%)
Kjeldahl nitrogen content 5.41% (theoretical value 5.67%)
The chemical structure of the polymer 5 obtained from the above results has the following random structure.
― [― (MPC) ₇₃₄ ― (IbMA) ₈₂ ― (AEMA) ₃₉₈ ―] ―

Example 6 (Polymer 6; MPC1-IbMA12-QAMA16)
MPC 0.9g, IbMA 7.9g, and QAMA 11.2g were melt | dissolved in ethanol / water (= 8/2, wt / wt) liquid mixture 180g, and the inside of reaction container was fully substituted by nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, the deposited precipitate was filtered, and vacuum dried at room temperature for 48 hours to obtain 16.2 g of powder. The weight average molecular weight of the obtained copolymer was 298,000. This is designated as Polymer 6. The IR, NMR, phosphorus quantitative analysis, and elemental analysis data are shown below.
IR: 3413 cm ⁻¹ (−OH), 2954 cm ⁻¹ (−CH), 1732 cm ⁻¹ (C═O), 1489 cm ⁻¹ (−CH), 1246 cm ⁻¹ (P═O), 1161 cm ⁻¹ (C− O-C), 1088 cm < ^-1 > (P-O-C).
_{NMR: 0.8-1.2ppm (CH 3 -C -} ), 1.4-2.2ppm (-CH 2 CH 2 -, - CHCH -), 3.3ppm (-N (CH 3) 3), 3.5-5.0ppm (-CH _{2 CH 2 O -, - C} -CH-O -, - CH 2 CH (OH) -).
Phosphorus content: 4617ppm (theoretical value: 4729ppm)
Elemental analysis data: Actual measurement: C; 59.80%, H; 9.04%, N; 3.53% (theoretical value: C; 60.20%, H; 8.97%, N; 3.51%)
Kjeldahl nitrogen content 3.54% (theoretical value 3.51%)
The chemical structure of the polymer 6 obtained from the above results has the following random structure.
― [― (MPC) ₄₄ ― (IbMA) ₅₂₇ ― (QAMA) ₇₀₇ ―] ―

Example 7 (Polymer 7; MPC16-IbMA1-QAMA16)
0.9 g of MPC, 7.9 g of IbMA and 11.2 g of QAMA were dissolved in 180 g of a mixed solution of ethanol / water (= 8/2, wt / wt), and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 16.6 g of powder. The weight average molecular weight of the obtained copolymer was 302,000. This is designated as Polymer 7. The IR, NMR, phosphorus quantitative analysis, and elemental analysis data are shown below.
IR: 3413 cm ⁻¹ (−OH), 2954 cm ⁻¹ (−CH), 1732 cm ⁻¹ (C═O), 1489 cm ⁻¹ (−CH), 1246 cm ⁻¹ (P═O), 1161 cm ⁻¹ (C− O-C), 1088 cm < ^-1 > (P-O-C).
_{NMR: 0.8-1.2ppm (CH 3 -C -} ), 1.4-2.2ppm (-CH 2 CH 2 -, - CHCH -), 3.3ppm (-N (CH 3) 3), 3.5-5.0ppm (-CH _{2 CH 2 O -, - C} -CH-O -, - CH 2 CH (OH) -).
Phosphorus content: 4617ppm (theoretical value: 4729ppm)
Elemental analysis data: Actual measurement value: C; 48.21%, H; 7.84%, N; 5.11% (theoretical value: C; 48.03%, H; 7.94%, N; 5.13%)
Kjeldahl nitrogen content 5.14% (theoretical value 5.13%)
The chemical structure of the polymer 7 obtained from the above results has the following random structure.
― [― (MPC) ₅₅₀ ― (IbMA) ₃₉ ― (QAMA) ₅₅₂ ―] ―

Example 8 (Polymer 8; MPC16-IbMA12-QAMA1)
12.4 g of MPC, 7.0 g of IbMA and 0.6 g of QAMA were dissolved in 180 g of an ethanol / water (= 8/2, wt / wt) mixed solution, and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 15.9 g of powder. The weight average molecular weight of the obtained copolymer was 286,000. This is designated as Polymer 8. The IR, NMR, phosphorus quantitative analysis, and elemental analysis data are shown below.
IR: 3413 cm ⁻¹ (−OH), 2954 cm ⁻¹ (−CH), 1732 cm ⁻¹ (C═O), 1489 cm ⁻¹ (−CH), 1246 cm ⁻¹ (P═O), 1161 cm ⁻¹ (C− O-C), 1088 cm < ^-1 > (P-O-C).
_{NMR: 0.8-1.2ppm (CH 3 -C -} ), 1.4-2.2ppm (-CH 2 CH 2 -, - CHCH -), 3.3ppm (-N (CH 3) 3), 3.5-5.0ppm (-CH _{2 CH 2 O -, - C} -CH-O -, - CH 2 CH (OH) -).
Phosphorus content: 65021ppm (theoretical value: 65153ppm)
Elemental analysis data: Actual measurement value: C; 55.34%, H; 8.39%, N; 3.18% (theoretical value: C; 55.74%, H; 8.34%, N; 3.12%)
Kjeldahl nitrogen content 3.17% (theoretical value 3.12%)
The chemical structure of the polymer 8 obtained from the above results has the following random structure.
― [― (MPC) ₆₀₀ ― (IbMA) ₄₃₈ ― (QAMA) ₅₀ ―] ―

Example 9 (Polymer 9; MPC1-IbMA1-QAMA16)
MPC1.4g, IbMA1.0g and QAMA17.6g were melt | dissolved in 180g of ethanol / water (= 8/2, wt / wt) liquid mixture, and the inside of reaction container was fully substituted by nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, the deposited precipitate was filtered, and vacuum dried at room temperature for 48 hours to obtain 16.1 g of powder. The weight average molecular weight of the obtained copolymer was 291,000. This is designated as Polymer 9. The IR, NMR, phosphorus quantitative analysis, and elemental analysis data are shown below.
IR: 3413 cm ⁻¹ (−OH), 2954 cm ⁻¹ (−CH), 1732 cm ⁻¹ (C═O), 1489 cm ⁻¹ (−CH), 1246 cm ⁻¹ (P═O), 1161 cm ⁻¹ (C− O-C), 1088 cm < ^-1 > (P-O-C).
_{NMR: 0.8-1.2ppm (CH 3 -C -} ), 1.4-2.2ppm (-CH 2 CH 2 -, - CHCH -), 3.3ppm (-N (CH 3) 3), 3.5-5.0ppm (-CH _{2 CH 2 O -, - C} -CH-O -, - CH 2 CH (OH) -).
Phosphorus content: 7331ppm (theoretical value: 7356ppm)
Elemental analysis data: Actual measurement value: C; 51.42%, H; 8.51%, N; 5.48% (theoretical value: C; 51.38%, H; 8.43%, N; 5.52%)
Kjeldahl nitrogen content 5.55% (theoretical value 5.52%)
The chemical structure of the polymer 9 obtained from the above results has the following random structure.
― [― (MPC) ₆₉ ― (IbMA) ₅₄ ― (QAMA) ₁₀₈₉ ―] ―

Example 10 (Polymer 10; MPC1-IbMA12-QAMA1)
1.9 g of MPC, 16.7 g of IbMA and 1.5 g of QAMA were dissolved in 180 g of ethanol / water (= 8/2, wt / wt) mixed solution, and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 16.5 g of powder. The weight average molecular weight of the obtained copolymer was 286,000. This is polymer 10. The IR, NMR, phosphorus quantitative analysis, and elemental analysis data are shown below.
IR: 3413 cm ⁻¹ (−OH), 2954 cm ⁻¹ (−CH), 1732 cm ⁻¹ (C═O), 1489 cm ⁻¹ (−CH), 1246 cm ⁻¹ (P═O), 1161 cm ⁻¹ (C− O-C), 1088 cm < ^-1 > (P-O-C).
_{NMR: 0.8-1.2ppm (CH 3 -C -} ), 1.4-2.2ppm (-CH 2 CH 2 -, - CHCH -), 3.3ppm (-N (CH 3) 3), 3.5-5.0ppm (-CH _{2 CH 2 O -, - C} -CH-O -, - CH 2 CH (OH) -).
Phosphorus content: 9423ppm (theoretical value: 9958ppm)
Elemental analysis data: Actual measurement: C; 70.56%, H; 9.64%, N; 0.88% (theoretical value: C; 71.01%, H; 9.58%, N; 0.87%)
Kjeldahl nitrogen content 0.88% (theoretical value 0.87%)
The chemical structure of the polymer 10 obtained from the above results has the following random structure.
― [― (MPC) ₈₇ ― (IbMA) ₁₀₇₃ ― (QAMA) ₉₃ ―] ―

Example 11 (Polymer 11; MPC16-IbMA1-QAMA1)
MPC18.2g, IbMA0.9g and QAMA0.9g were melt | dissolved in 180g of ethanol / water (= 8/2, wt / wt) liquid mixture, and the inside of reaction container was fully substituted with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 17.2 g of powder. The weight average molecular weight of the obtained copolymer was 286,000. This is designated as Polymer 11. The IR, NMR, phosphorus quantitative analysis, and elemental analysis data are shown below.
IR: 3413 cm ⁻¹ (−OH), 2954 cm ⁻¹ (−CH), 1732 cm ⁻¹ (C═O), 1489 cm ⁻¹ (−CH), 1246 cm ⁻¹ (P═O), 1161 cm ⁻¹ (C− O-C), 1088 cm < ^-1 > (P-O-C).
_{NMR: 0.8-1.2ppm (CH 3 -C -} ), 1.4-2.2ppm (-CH 2 CH 2 -, - CHCH -), 3.3ppm (-N (CH 3) 3), 3.5-5.0ppm (-CH _{2 CH 2 O -, - C} -CH-O -, - CH 2 CH (OH) -).
Phosphorus content: 94851ppm (theoretical value: 95627ppm)
Elemental analysis data: Actual measurement value: C; 46.12%, H; 7.72%, N; 4.61% (theoretical value: C; 46.40%, H; 7.61%, N; 4.60%)
Kjeldahl nitrogen content 0.88% (theoretical value 4.58%)
The chemical structure of the polymer 11 obtained from the above results has the following random structure.
― [― (MPC) ₉₀₀ ― (IbMA) ₅₆ ― (QAMA) ₆₉ ―] ―

Comparative Reference Example 1 (Polymer 12; MPC7-IbMA3)
15.1 g of MPC and 4.9 g of IbMA were dissolved in 180 g of an ethanol / water (= 8/2, wt / wt) mixed solution, and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 15.6 g of powder. The weight average molecular weight of the obtained copolymer was 288,000. This is designated as Polymer 12.

Comparative Reference Example 2 (Polymer 13; MPC7-QAMA3)
14.9 g of MPC and 5.1 g of QAMA were dissolved in 180 g of an ethanol / water (= 8/2, wt / wt) mixed solution, and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 15.1 g of powder. The weight average molecular weight of the obtained copolymer was 306,000. This is designated as Polymer 13.

Comparative Reference Example 3 (Polymer 14; IbMA3-QAMA7)
5.7 g of IbMA and 14.3 g of QAMA were dissolved in 180 g of an ethanol / water (= 8/2, wt / wt) mixed solution, and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 16.3 g of powder. The weight average molecular weight of the obtained copolymer was 241,000. This is polymer 14.

Comparative Reference Example 4 (Polymer 15; MPC44-IbMA1-AEMA55)
12.8 g of MPC, 0.2 g of IbMA and 7.0 g of AEMA were dissolved in 180 g of an ethanol / water (= 8/2, wt / wt) mixed solution, and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 17.2 g of powder. The weight average molecular weight of the obtained copolymer was 277,000. This is designated as Polymer 15.

Comparative Reference Example 5 (Polymer 16; MPC74-IbMA25-AEMA1)
15.9 g of MPC, 4.0 g of IbMA and 0.1 g of AEMA were dissolved in 180 g of an ethanol / water (= 8/2, wt / wt) mixed solution, and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, the deposited precipitate was filtered, and vacuum dried at room temperature for 48 hours to obtain 15.4 g of powder. The weight average molecular weight of the obtained copolymer was 292,000. This is designated as Polymer 16.

Comparative Reference Example 6 (Polymer 17; MPC1-IbMA24-QAMA32)
MPC 0.5 g, IbMA 8.0 g, and QAMA 11.5 g were dissolved in 180 g of ethanol / water (= 8/2, wt / wt) mixed solution, and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 16.8 g of powder. The weight average molecular weight of the obtained copolymer was 278,000. This is designated as Polymer 17.

Comparative Reference Example 7 (Polymer 18; MPC32-IbMA1-QAMA32)
MPC 10.9 g, IbMA 0.3 g and QAMA 8.8 g were dissolved in 180 g of ethanol / water (= 8/2, wt / wt) mixed solution, and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 17.6 g of powder. The weight average molecular weight of the obtained copolymer was 295,000. This is designated polymer 18.

Comparative Reference Example 8 (Polymer 19; MPC32-IbMA24-QAMA1)
12.6 g of MPC, 7.1 g of IbMA and 0.3 g of QAMA were dissolved in 180 g of a mixed solution of ethanol / water (= 8/2, wt / wt), and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 16.9 g of powder. The weight average molecular weight of the obtained copolymer was 297,000. This is designated as Polymer 19.

Comparative Reference Example 9 (Polymer 20; MPC1-IbMA1-QAMA16)
MPC 0.7 g, IbMA 0.6 g and QAMA 18.7 g were dissolved in 180 g of ethanol / water (= 8/2, wt / wt) mixed solution, and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 17.5 g of powder. The weight average molecular weight of the obtained copolymer was 301,000. This is designated as Polymer 20.

Comparative Reference Example 10 (Polymer 21; MPC32-IbMA1-QAMA1)
19.0 g of MPC, 0.5 g of IbMA and 0.5 g of QAMA were dissolved in 180 g of an ethanol / water (= 8/2, wt / wt) mixed solution, and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 16.8 g of powder. The weight average molecular weight of the obtained copolymer was 286,000. This is polymer 21.

Comparative Reference Example 11 (Polymer 22; MPC1-IbMA24-QAMA1)
1.0 g of MPC, 18.2 g of IbMA and 0.8 g of QAMA were dissolved in 180 g of ethanol / water (= 8/2, wt / wt) mixed solution, and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, the deposited precipitate was filtered, and vacuum dried at room temperature for 48 hours to obtain 17.1 g of powder. The weight average molecular weight of the obtained copolymer was 279,000. This is designated as Polymer 22.

Comparative Reference Example 12 (Polymer 23; MPC17-IbMA1-QAMA1)
MPC18.3g, IbMA0.8g and QAMA0.9g were melt | dissolved in 180g of ethanol / water (= 8/2, wt / wt) liquid mixture, and the inside of reaction container was fully substituted with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 15.6 g of powder. The weight average molecular weight of the obtained copolymer was 294,000. This is designated as Polymer 23.

Comparative Reference Example 13 (Polymer 24; MPC1-IbMA13-QAMA1)
1.7 g of MPC, 16.9 g of IbMA, and 1.4 g of QAMA were dissolved in 180 g of an ethanol / water (= 8/2, wt / wt) mixed solution, and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 15.1 g of powder. The weight average molecular weight of the obtained copolymer was 287,000. This is designated as Polymer 24.

Comparative Reference Example 14 (Polymer 25; MPC1-IbMA1-QAMA17)
1.3 g of MPC, 1.0 g of IbMA and 17.7 g of QAMA were dissolved in 180 g of an ethanol / water (= 8/2, wt / wt) mixed solution, and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 16.3 g of powder. The weight average molecular weight of the obtained copolymer was 299,000. This is designated as Polymer 25.

Comparative Reference Example 15 (Polymer 26; MPC17-IbMA13-QAMA1)
MPC12.3g, IbMA7.1g and QAMA0.6g were melt | dissolved in ethanol / water (= 8/2, wt / wt) liquid mixture 180g, and the inside of reaction container was fully substituted by nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 17.2 g of powder. The weight average molecular weight of the obtained copolymer was 288,000. This is polymer 26.

Comparative Reference Example 16 (Polymer 27; MPC17-IbMA13-QAMA1)
MPC 0.8g, IbMA 8.0g, and QAMA 11.2g were melt | dissolved in ethanol / water (= 8/2, wt / wt) liquid mixture 180g, and the inside of reaction container was fully substituted by nitrogen gas. To this solution, 0.85 g of AIBN was added, immersed in a 60 ° C. warm bath, and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, the deposited precipitate was filtered, and vacuum dried at room temperature for 48 hours to obtain 15.4 g of powder. The weight average molecular weight of the obtained copolymer was 301,000. This is designated as Polymer 27.

Comparative Reference Example 17 (Polymer 28; MPC0.9-MAA0.1)
19.4 g of MPC and 0.6 of methacrylic acid (MAA) were dissolved in 180 g of an ethanol / water (= 8/2, wt / wt) mixed solution, and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. To this solution, 3.4 g of AIBN was added and immersed in a warm bath at 70 ° C. and polymerized by heating for 8 hours. After cooling, the polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, the deposited precipitate was filtered, and vacuum dried at room temperature for 48 hours to obtain 15.3 g of powder. The weight average molecular weight of the obtained copolymer was 12,000. This is designated polymer 28.
Tables 1 to 3 collectively show the monomer composition, the charged molar ratio, and the measurement results of the above Examples and Comparative Reference Examples.
In Tables 1 to 3, U ^{1 to} U ³ represent structural units represented by the above-described formulas (1) to (3), and M ^{1 to} M ³ represent the above-described formulas (4) to (6 The monomers M ^{1 to} M ^{3 represented} by N1 to n3 mean the numbers in the copolymer of the structural units U ^{1 to} U ³ , respectively.

Examples 12-15, Comparative Examples 1-4
(1) Adsorption test of polymer on hair According to the following hair preparations 1 and 2, healthy hair and damaged hair were prepared. Subsequently, 1.0 g of each polymer obtained in Examples 1 to 11 was dissolved in 99.0 g of distilled water. 1 g of the prepared damaged hair was immersed in the resulting solution for 1 minute, washed with running water, and dried with a dryer. The hair is subjected to surface analysis using an X-ray photoelectron analyzer (model: ESCA-3300 (manufactured by Shimadzu Corporation)), and the ratio of phosphorus atoms to carbon atoms derived from MPC in the polymer (P / C) This value was used as an index of the amount of polymer adsorbed on the hair. Similarly, for polymers 12 to 28 of Comparative Reference Examples 1 to 17, the amount of polymer adsorbed on the hair was determined. The results are shown in Tables 4 and 5 together with the surface analysis results of untreated damaged hair.

(Hair preparation 1)
One person black hair (purchased from Beaulux Co., Ltd.) was rinsed in a 1% by weight aqueous polyoxyethylene sodium lauryl sulfate solution for 1 minute and then washed with running water. Next, the hair was dried with a towel and dried with a dryer to obtain healthy hair.
(Hair preparation 2)
Healthy hair obtained by hair preparation 1 was immersed in an aqueous solution in which 5% by mass of hydrogen peroxide and 3% by mass of ammonia water were mixed at a weight ratio of 1: 1 at room temperature for 20 minutes, and then washed with running water. Then, it was towel-dried and dried with a dryer. This bleaching treatment was repeated 10 times to obtain damaged hair.

(2) Evaluation of hair gloss 1 g of damaged hair was immersed in a solution of 1.0 g of each polymer obtained in Examples 1 to 11 in 99.0 g of distilled water for 1 minute, washed with running water, and dried with a dryer. I let you. 11 hairs are arranged in parallel on the sample stage, and the gloss of the hair is measured in a constant temperature and humidity chamber at 25 ° C. and 60% RH using a goniophotometer GP-5 (manufactured by Murakami Color Research Laboratory). went. Specifically, the incident angle of light is set to 30 °, the direction of incident light is made to coincide with the direction of the hair shaft, the received light angle is changed, the reflected light distribution is measured, and the following formula (A) The psychological glossiness (Constant Gloss) and the internal reflection (Internal Reflection) were calculated by the formula (B).
Psychological gloss (G) = S _f / d (A)
Internal reflection (T) = (S _r / S _f ) × 10 (B)
Here, d is diffuse reflection in the normal direction of hair, S _f is specular reflection peak intensity of hair, and S _r is maximum peak intensity of internal reflection of hair. Similarly, the gloss of hair was measured for the polymers 12 to 28 of Comparative Reference Examples 1 to 17. The results are shown in Tables 4 and 5 as relative values when the gloss of untreated damaged hair is taken as 100.

(3) Sustainability evaluation of hair gloss
The treated hair subjected to the gloss measurement in (2) was immersed in a 1% by mass polyoxyethylene sodium lauryl sulfate aqueous solution, shaken at 40 ° C. for 1 hour, washed with water and dried. About the hair after this washing process, the gloss of the hair was measured according to the method of (2) description. The persistence of hair gloss was calculated by the following formulas (C) and (D).
Persistence of psychological feeling of gloss = (G ₂ −G ₀ ) / (G ₁ −G ₀ ) × 100 (C)
Persistence of internal reflection = (T ₂ −T ₀ ) / (T ₁ −T ₀ ) × 100 (D)
Here, G ₀ is psychological gloss of untreated damaged hair, G ₁ is psychological gloss of treated hair before washing treatment, G ₂ is psychological gloss of treated hair after washing treatment, and T ₀ is unfinished. The internal reflection of the treated damaged hair, T ₁ is the internal reflection of the treated hair before the washing treatment, and T ₂ is the internal reflection of the treated hair after the washing treatment. The results are shown in Tables 4 and 5.

(4) Skin irritation evaluation 1.0 g of each polymer obtained in Examples 1 to 11 was dissolved in 9.0 g of distilled water to obtain a test solution. After impregnating the test liquid into filter paper, it was set in a fin chamber and attached to the back of five adult males. After 24 hours, the sample was peeled off, and the skin reaction was visually determined after 1 hour and 24 hours.
Skin irritation is a skin irritation index calculated by giving a score after judging the skin irritation reaction induced by the test substance in the patch test criteria table shown in Table 6 and introducing it into the formula (E). It was evaluated from. Moreover, the skin irritation was similarly evaluated about the polymers 12-28 of Comparative Reference Examples 1-17. The results are shown in Tables 4 and 5.
Skin irritation index = sum of total scores / number of subjects × 100 (E)

  From Table 4 and Table 5, the cationic copolymers of the present invention of Examples 12 to 15 are superior in adsorptivity to hair and have a psychological gloss corresponding to surface reflection as compared with Comparative Examples 1 to 4. It can be seen that it has the effect of improving hair gloss by enhancing not only the internal reflection. In addition, since the gloss is maintained in the treated hair after washing with a surfactant, it is resistant to washing with water and has no irritation to the skin or scalp, so it is used for highly safe hair polish. It turns out that it is a polymer.

Claims (3)

A constituent unit U ¹ of the formula (1), and the structural unit U ² of formula (2), and a constituent unit U ³ of the formula (3), and U ¹ and U ² and U ³ A cationic copolymer having a molar ratio of 1 to 16: 1 to 12: 1 to 16 and a weight average molecular weight of 5,000 to 2,000,000.

(In the formula (1), R ¹ represents a hydrogen atom or a methyl group, X represents an alkylene group or alkyleneoxy group having 1 to 6 carbon atoms, p is 0 or 1, and q is an integer of 1 to 4. .)

(In formula (2), R ² represents a hydrogen atom or a methyl group.)

(In Formula (3), R ³ represents a hydrogen atom or a methyl group, L represents — (CH ₂ ) p ¹ -L ¹ , — (C═O) O— (CH ₂ ) p ¹ -L ¹ , − (C = O) O - ( (CH 2) p 2 -O) p 1 -L 1 or _{-CH 2 CH (OH) CH 2} -L 1 a is .p ¹ is 0-24, p ² is 2 5 represents an integer of 5 and L ¹ represents an amino group, an ammonium base, a pyridyl group or a pyridinium base.)   A hair polish polymer comprising the cationic copolymer according to claim 1.   A cosmetic for hair containing 0.001 to 50% by mass of the hair polish polymer according to claim 2.