JP2002069184A - Polymer and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer having excellent biodegradability and hygienic safety and satisfying various requirements in a broad range of use, to provide a method of producing the polymer, and further to provide a polymeric drug of surface effecting type having biodegradability with less stimulus to a living body. SOLUTION: The polymer comprises a repeating unit expressed by general formulae (1a) and/or (1b) and a repeating unit expressed by general formulae (2a) and/or (2b) (where R1 represents a pendant group having an acidic group such as a carboxylic group, R2 represents an alkyl and the like, X1 and X2 each represents NH, N(R') and the like, n1 and n2 are 1 or 2). The method of producing the polymer comprises a reaction to introduce the pendant group. The polymeric drug of surface effecting type comprises the polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a biodegradable composition,
It relates to a polymer with excellent safety. Specifically, the present invention relates to a polymer containing a copolymer component having a specific hydrophilic substituent and a copolymer component having a specific hydrophobic substituent in at least a part of a monomer unit, and a method for producing the same. further,
The present invention relates to a surface-active polymer drug having both hydrophilicity and hydrophobicity, which is excellent in biodegradability, does not cause irritation to a living body, and is excellent in safety even after decomposition.

[0002]

2. Description of the Related Art [Technical Background of Degradable Resin] An ordinary resin having no biodegradability has a problem of disposal after use. At the time of disposal, such a resin is incinerated and landfilled. It has been pointed out that the method of treating incinerators causes damage to furnace materials due to heat generated during incineration, as well as global warming and acid rain. In addition, in the method of landfill, plastic has a problem that the volume is bulky and the ground is not stable because it does not rot. In addition, there is no longer a place suitable for landfill.

That is, these resins are poor in biodegradability and exist semipermanently in water and soil, which is a very serious problem in view of environmental conservation in waste treatment. For example, in the case of disposable resins represented by sanitary materials such as disposable diapers and sanitary articles, recycling the resin requires a great deal of cost, and the amount of incineration is large, so that the burden on the global environment is great. It is also reported that when an aqueous solution of sodium polyacrylate is sprayed on soil, it forms a complex with polyvalent ions such as Ca ^{2+ in} the soil to form an insoluble layer (Matsumoto et al., Polymer, Vol. 42 , August, 1993). However, although such layers are said to have low toxicity per se, they are completely absent in nature, and the effects on ecosystems of long-term accumulation of these resins in soil are unknown. , Need to be thoroughly examined and its use requires a careful attitude. Similarly, in the case of a nonionic resin, a complex is not formed, but the nondecomposable resin may accumulate in soil due to its nondegradability, and its effect on the natural world is doubtful.

Further, these polymerization resins use monomers which are highly toxic to human skin and the like, and many studies have been made to remove them from products after polymerization. Is difficult to remove. In particular, it is expected to be more difficult in production on an industrial scale.

[0005] Further, a resin which is not disposed of but is released into the environment has a similar problem. For example, industrial applications such as pharmaceutical carriers, cosmetics, cosmetics, surfactants, and food additives (thickeners, stabilizers, humectants, noodle improvers, cohesive agents, pH adjusters, antibacterial agents, etc.) Most of the resins used are those that are excellent in safety, but at present the release and accumulation in the environment have not been considered at all.

On the other hand, in recent years, biodegradable polymers have attracted attention as "earth-friendly materials" and have been actively studied. As such a biodegradable hydrophilic resin, for example, polyethylene oxide resin, polyvinyl alcohol resin, cellulose resin, starch resin, chitosan resin, alginic acid resin, polyamino acid resin and the like are known. ing. Among them, polyethylene oxide resins and polyvinyl alcohol resins can be biodegraded only by special bacteria, so that biodegradability is slow or not decomposed under general conditions. When the molecular weight is further increased, the decomposability extremely decreases.

[0007] Polysaccharides such as cellulose resin, starch resin, chitosan resin, and alginic acid resin require complicated steps to increase their purity, and the performance characteristics used in various applications are not sufficient. In many cases, it is difficult to improve the performance characteristics. In addition, since a chitosan-based resin, an alginic acid-based resin, and the like are obtained by collecting a natural product and processing the natural product to obtain the resin, there is a concern that a large amount of the resin may cause a loss of natural balance. On the other hand, polyamino acids are biodegradable, so they are friendly to the global environment.Even if they are absorbed into the living body, they are digested and absorbed by enzymatic action, yet they do not show antigenicity in the living body and decomposition products have no toxicity. It is a material that is kind to humans, as it has been clarified. However, polyamino acids themselves did not always have sufficient performance characteristics for use in various applications.

Accordingly, the present inventors have conducted intensive studies from the viewpoint of using compounds that are safe for living bodies and the environment, with the aim of improving performance characteristics while maintaining safety. Ring opening of polysuccinimide using α-amino acid ester, which is an amine having extremely high compatibility and safety to a living body, can substantially cause irritation to a living body (for example, eyes, skin, etc.). Thus, a resin having extremely high safety for living bodies was obtained (Japanese Patent Application Laid-Open No. 8-48766). Although these resins are excellent in safety, they do not always satisfy the required properties when used for applications requiring surface activity, and further improvements have been desired. In addition, since the amino acid used is used as an ester, the raw material used is expensive, and the production thereof requires a large number of steps.

Conventionally, a technique for opening a polysuccinimide using α-amino acids, which are amines having extremely high biocompatibility and safety to living bodies, for opening the polysuccinimide is not described above. Is not known at all. Despite the fact that α-amino acids are known to have extremely high biocompatibility and safety to living organisms, the technique of opening a polysuccinimide using α-amino acids is completely different from the above-mentioned techniques. The reason that it was not known was probably because the technical problem that the α-amino acid was hardly soluble in organic solvents and the reactivity of the α-amino group was extremely low was not solved. Can be

[0010] In addition, α-
A technique for opening a ring of polysuccinimide using an amino acid other than an amino acid is almost unknown other than the above-described technique. Again, amino acids other than α-amino acids,
This is considered to be caused by a technical problem that there is a problem in solubility in an organic solvent and low reactivity. Slightly above-mentioned technology and Die Angewandte Makromolekulare Chemy
mie -Applied Macromolecular Chemistry and Physic
s) (Machado et al.), 195, 35-56 (199).
(2 years), only a technique of opening the ring of polysuccinimide with γ-amino acid γ-aminobutyric acid (piperidic acid) and oligopeptide (dipeptide) glycylglycine is disclosed. However, this Mach
In the technique of ado et al., in the presence of a strong base catalyst, glycylglycine is charged and reacted four times as much as the equivalent of the monomer unit of polysuccinimide. Had only about 0.5 equivalents of glycylglycine involved in the reaction, and the low reactivity was still not solved.

Also, a surfactant (DE-A-2) produced by reacting polyaspartimides with long-chain amines.
No. 253190), a polyaspartic acid derivative having a pendant group containing a mercapto group or a sulfonic acid group in some repeating units (US Pat. No. 4,363,797).
) And a polyaspartic acid derivative having an aromatic sulfonic acid residue as a pendant group (JP-A-8-67752). However, the performance was not satisfactory in any of the inventions, and the manufacturing method was not efficient.

Further, in order to improve the required characteristics in the application to be used, studies have been made to improve the performance characteristics while maintaining safety, and at least some of the repeating units have a pendant group containing a betaine structure. A polyaspartic acid derivative has been reported (JP-A-10-2534).
No. 4). Further, a polymer containing a glycino group as a pendant group (JP-A-2000-44679),
Acidic polyamino acid derivative having a pendant group containing a hydrophilic group and a pendant group containing a hydrophobic group
000-44680). These resins are excellent in safety and exhibit excellent properties for hair treatment agents, cosmetic applications, and the like.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to improve the above-mentioned resin so as to have more suitable properties according to the intended use and the method of use in these application fields requiring hydrophilicity. Is what you do. That is, an object of the present invention is to provide a polymer having excellent biodegradability, excellent safety, and satisfying various required characteristics in a wide range of applications, and an effective production method thereof.

[0014]

Means for Solving the Problems The present inventors have conducted intensive studies from the viewpoint of using compounds that are safe for living organisms and the environment. When a pendant group containing a specific hydrophilic substituent having high safety to the liposome and (2) a pendant group having a specific hydrophobic substituent having high biocompatibility and high safety to the living body are introduced, it becomes very They have found that excellent results can be obtained, and have completed the present invention.

That is, the polymer of the present invention contains
A repeating unit represented by the following general formula (1a) and / or a repeating unit represented by the following general formula (1b):

[0016]

Embedded image

[In the formulas (1a) and (1b), R ¹ represents a carboxyl group, a thiocarboxylic acid group, a dithiocarboxylic acid group, a thiocarbonate group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group,
A pendant group having at least one acidic group selected from the group consisting of a sulfuric acid group, a sulfurous acid group, a sulfinic acid group, an amidosulfuric acid group, a flufamic acid group and a boric acid group, and salts thereof, and X ¹ is NH, NR ′ (R ′ is an alkyl group, an aryl group or an aralkyl group), O or S,
n ¹ is 1 or 2. ].

In the molecule, a repeating unit represented by the following general formula (2a) and / or a repeating unit represented by the following general formula (2b):

[0019]

Embedded image

[In the formulas (2a) and (2b), R ² is an alkyl group, an aryl group or an aralkyl group, and X ² is NH,
N (R ″) (R ″ is an alkyl group, an aryl group or an aralkyl group) or S, and n ² is 1 or 2. ] It is a polymer which has.

The production method of the present invention is a method for producing the above-mentioned polymer, which comprises at least a pendant group introduction reaction. Further, the present invention is a surface-acting high-molecular-weight drug and a film-forming agent composition containing the above polymer.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION (1) Structure of Polymer The polymer of the present invention comprises a polymer basic skeleton and a side chain portion. Hereinafter, these will be described in two parts.

(1-1) Polymer Basic Skeleton of Polymer Since the polymer basic skeleton of the polymer of the present invention is an acidic polyamino acid such as polyglutamic acid or polyaspartic acid, the main chain is composed of glutamic acid or aspartic acid as a repeating unit. To form The following description focuses on polyaspartic acid-based resins that are more useful for industrial production.

These may contain another amino acid as a repeating unit. Specific examples of other amino acid components include, for example, 20 kinds of protein constituent amino acids, L-ornithine, a series of α-amino acids, β-alanine, γ-aminobutyric acid, neutral amino acids, acidic amino acids, and ω- of acidic amino acids. Examples include esters, basic amino acids, N-substituted basic amino acids, amino acids and amino acid derivatives such as aspartic acid-L-phenylalanine dimer (aspartame), and aminosulfonic acids such as L-cysteic acid. The α-amino acid is an optically active form (L
, D-form) or a racemic form. Further, the polymer may be a copolymer containing a repeating unit other than an amino acid.

Examples of the repeating unit of the copolymer include dehydration condensates such as aminocarboxylic acid, aminosulfonic acid, aminophosphonic acid, hydroxycarboxylic acid, mercaptocarboxylic acid, mercaptosulfonic acid, and mercaptophosphonic acid.

In addition, polyamines, polyhydric alcohols, polythiols, polycarboxylic acids, polysulfonic acids, polyphosphonic acids, polyhydrazine compounds, polycarbamoyl compounds, polysulfonamide compounds, Phosphonamide compounds, polyepoxy compounds, polyvalent isocyanate compounds, polyvalent isothiocyanate compounds, polyvalent aziridine compounds, polyvalent carbamate compounds, polyvalent carbamic acid compounds, polyvalent oxazoline compounds, polyvalent unsaturated bonds Examples include compounds, dehydration condensates of polyvalent metals, adducts, and substituted products.

When it is a copolymer, it may be a block copolymer or a random copolymer. Further, it may be a graft copolymer. Among them, polyaspartic acid and polyglutamic acid having a high degree of polymerization and excellent biodegradability are preferably used as a basic skeleton, and a homopolymer of polyaspartic acid suitable for industrial production is particularly preferable.

As the polymer basic skeleton of the polymer of the present invention, in the case of polyaspartic acid, the amide bond in the main chain may be an α bond or a β bond. In the case of polyglutamic acid, the amide bond in the main chain may be an α bond or a γ bond.

That is, in the case of polyaspartic acid and a copolymer thereof, an α-bond is formed when the amino group of aspartic acid or a copolymer monomer is bonded to a carboxyl group at the α-position of aspartic acid. The case where the amino acid is bonded to the β-carboxyl group of aspartic acid is a β bond.
In the case of polyglutamic acid and its copolymer, an amino group of glutamic acid or a copolymer monomer and an α-carboxyl group bonded to the α-position carboxyl group of glutamic acid are α-bonds, and a γ-position carboxyl group of glutamic acid. Bonding is γ-bonding. Α-bond and β-bond in the case of polyaspartic acid, α-bond and γ in the case of polyglutamic acid
The bonding mode of the bonding is not particularly limited.

The side chain group of the present invention is basically a carboxylic acid derivative in which a carboxyl group of an acidic polyamino acid is substituted. The details will be described below.

In the present invention, regardless of the mode of bonding,
The monomer part consisting of aspartic acid in the polymer is called `` polyaspartic acid residue '', the monomer part consisting of glutamic acid in the polymer is called `` polyglutamic acid residue '', and both are called `` acid polyamino acid residue '' Call.

The polymer of the present invention is preferably a non-crosslinked product or a slightly crosslinked product. The finely crosslinked product refers to a polymer crosslinked within a range that does not impair the intrinsic physical properties of the polymer, particularly the solubility. However, the degree of crosslinking is preferably low enough to maintain water solubility or oil solubility.

(2) Side chain structure of the polymer The polymer of the present invention comprises a polyamino acid residue or a repeating unit represented by the above general formula (1a) in which a carboxyl group of the polyamino acid residue is further derived. A unit and / or a repeating unit represented by the following general formula (1b), a repeating unit represented by the general formula (2a), and / or a repeating unit represented by the general formula (2b) It is characterized by having both. That is, the side chain of the polymer of the present invention has a specific structure in which a carboxy group of an acidic polyamino acid residue as a polymer main chain is derived.

The general formulas (1a) and (1b) and the general formula (2)
The number of repeating units (a) and (2b) may be appropriately determined according to the intended use of the polymer, and is not particularly limited. In general, the number of repeating units in the general formulas (1a) and (1b) is 0.2 to 99.8% of the total number of all repeating units constituting the molecule, and the general formulas (2a) and (2b) Is 0.2 to 99.8%. In particular, each is preferably 1 to 99%, and 10 to 90%, respectively.
Is more preferable.

In addition, for example, when used as an interface-acting high-molecular-weight drug, an appropriate balance between hydrophilic groups and hydrophobic groups (that is, appropriate ratios to the total number of both) is generally required. It is preferable that the number of repeating units of general formulas (1a) and (1b) is 20 to 80%, and the number of repeating units of general formulas (2a) and (2b) is 20 to 80%. ) Is 30
It is more preferable that the number of repeating units of the general formulas (2a) and (2b) is 30 to 70%.

When used as an internally acting polymer drug, the polymer generally needs to have properties close to hydrophilicity, and the number of repeating units of the general formulas (1a) and (1b) is 30 to 99%. It is preferable that the number of repeating units of the general formulas (2a) and (2b) is 1 to 70%,
a) The number of repeating units of (1b) is more preferably 50 to 99%, and the number of repeating units of general formulas (2a) and (2b) is more preferably 1 to 50%.

When used as a surface-acting type high molecular drug, the polymer generally needs to have properties close to hydrophobicity, and the number of repeating units of the general formulas (1a) and (1b) is 1 to 70%. The number of repeating units of the general formulas (2a) and (2b) is preferably 30 to 99%, and the general formula (1
a) The number of repeating units of (1b) is more preferably 1 to 50%, and the number of repeating units of general formulas (2a) and (2b) is more preferably 50 to 99%.

Of these various types of high molecular drugs, there are, of course, those having different hydrophilicity / hydrophobicity balances, but it is also possible to appropriately deal with them.

The molecular weight of the polymer of the present invention is not particularly limited, and may be appropriately determined depending on the use. For example, when a film-forming ability or the like is required, a higher molecular weight is better, and when a higher decomposability is required, a lower molecular weight is preferable. In general, the weight average molecular weight of the raw material polymer before introducing a pendant group is about 1,000 to 1,000,000, preferably about 5000 to 1,000,000, and more preferably about 10,000 to 200,000.

Next, the hydrophilic side chain structures of the general formulas (1a) and (1b) and the hydrophobic side chain structures of the general formulas (2a) and (2b) will be described separately.

(2-1) Hydrophilic Polymer Side Chain Structure In the general formulas (1a) and (1b), the side chain structure is represented by X ¹ bonded to the polymer main chain and a pendant group having a specific acidic group ( R ¹ ). The pendant group (R ¹ ) includes a carboxyl group, a thiocarboxylic acid group, a dithiocarboxylic acid group, a thiocarbonate group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfurous acid group, a sulfinic acid group, and an amide sulfate group , A form having at least one acidic group selected from the group consisting of a fluamic acid group and a boric acid group, and salts thereof. In particular, it is preferably a group having at least one acidic group selected from the group consisting of a carboxyl group and a salt thereof, a phosphate group and a salt thereof, a phosphonic acid group and a salt thereof, a sulfate group and a salt thereof.

In the general formulas (1a) and (1b), X ¹ is a bond selected from —NH—, —N (R ′) —, —O—, and —S—. Alternatively, a plurality of mixtures may be used. Here, R ′ is, for example, an optionally branched alkyl group, aralkyl group, or aryl group having 1 to 16 carbon atoms.

In the case of an aspartic acid residue, the side chain group of the polymer of the present invention is an amide bond of the polymer main chain.
It may be substituted at the α-position or at the β-position, and in the case of a glutamic acid residue, it may be substituted at the α-position or substituted at the γ-position.

In the general formulas (1a) and (1b), the pendant group (R ¹ ) has the above-mentioned acidic group, but the portion other than the acidic group is mainly composed of carbon and hydrogen. It is called a hydrocarbon group for convenience.

The hydrocarbon group is not particularly restricted but includes alkylene, aralkylene, phenylene, naphthylene and the like. These may be linear, branched, or cyclic.

This hydrocarbon group may have a part of its carbon atoms substituted by a substituent containing O, N, S, P, B, Si or the like. That is, in the case of a ring structure, a part of carbon atoms may be substituted with O, N, S, P, B, Si, or the like, and O, N, S, P, B, Si, or the like may be introduced. Ether group, ester group, carbonyl group, urea group, thioester group, thiocarbonyl group, sulfone group,
It may be substituted with a substituent such as a sulfonyl group, a sulfonamide group, a secondary amino group, a tertiary amino group, an amide group, a phosphon group, and a phosphonamide group.

The substitution position of the specific functional group with respect to the hydrocarbon group is not particularly limited. Specific examples of the hydrocarbon group are shown below. In addition, the following example illustrates the part of the hydrocarbon group of a pendant group for convenience. The actual pendant group in the present invention has a structure in which hydrogen of these hydrocarbon groups is substituted with a specific functional group.

For example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,
Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, alkyl groups such as octadecyl, cyclopropyl, cyclobutyl,
Cycloalkyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tujanyl, calanyl, bornanyl, norbornanyl, pinanyl, decalinyl, etc. , Cyclohexadienyl group, cycloheptenyl group, cyclooctatetraenyl group, cyclopolyenyl group such as fulbenyl group, benzyl group, phenylethyl group, phenylpropyl group, aralkyl group such as phenylbutyl group, ethoxyethyl group,
Propoxyethyl group, butoxyethyl group, pentyloxyethyl group, hexyloxyethyl group, heptyloxyethyl group, octyloxyethyl group, decyloxyethyl group, undecyloxyethyl group, dodecyloxyethyl group, tridecyloxyethyl group, An alkoxyalkyl group such as a tetradecyloxyethyl group, a pentadecyloxyethyl group, a hexadecyloxyethyl group, a heptyldecyloxyethyl group, an octyldecyloxyethyl group,
Aryloxyalkyl group such as phenoxyethyl group, benzyloxyethyl group, aralkyloxyalkyl group such as tolyloxyethyl group, methylthioethyl group, ethylthioethyl group, propylthioethyl group, butylthioethyl group, pentylthioethyl group, Hexylthioethyl group,
Heptylthioethyl, octylthioethyl, nonylthioethyl, decylthioethyl, undecylthioethyl, dodecylthioethyl, tridecylthioethyl, tetradecylthioethyl, pentadecylthioethyl, hexa Alkylthioalkyl groups such as decylthioethyl group, heptyldecylthioethyl group and octyldecylthioethyl group; arylthioalkyl groups such as phenylthioethyl group and tolylthioethyl group; aralkylthioalkyl groups such as benzylthioethyl group; methyl Aminoethyl group, ethylaminoethyl group, propylaminoethyl group,
Butylaminoethyl group, pentylaminoethyl group, hexylaminoethyl group, heptylaminoethyl group, octylaminoethyl group, nonylaminoethyl group, decylaminoethyl group, undecylaminoethyl group, dodecylaminoethyl group, tridecylaminoethyl Group, tetradecylaminoethyl group, pentadecylaminoethyl group, hexadecylaminoethyl group, heptyldecylaminoethyl group, alkylaminoalkyl group such as octyldecylaminoethyl group, dimethylaminoethyl group, diethylaminoethyl group, dipropylamino Ethyl group, dibutylaminoethyl group, dipentylaminoethyl group, dihexylaminoethyl group, diheptylaminoethyl group, dioctylaminoethyl group, dinonylaminoethyl group, didecylaminoethyl group, diun Silaminoethyl group, didodecylaminoethyl group, ditridecylaminoethyl group, ditetradecylaminoethyl group, dipentadecylaminoethyl group, dihexadecylaminoethyl group, diheptyldecylaminoethyl group, dioctyldecylaminoethyl group , An ethylmethylaminoethyl group, a dialkylaminoalkyl group such as a methylpropylaminoethyl group, a methyloxycarbonylethyl group, an ethyloxycarbonylethyl group,
Propyloxycarbonylethyl group, butyloxycarbonylethyl group, pentyloxycarbonylethyl group,
Hexyloxycarbonylethyl group, heptyloxycarbonylethyl group, octyloxycarbonylethyl group, nonyloxycarbonylethyl group, decyloxycarbonylethyl group, undecyloxycarbonylethyl group, dodecyloxycarbonylethyl group, tridecyloxycarbonylethyl group, Tetradecyloxycarbonylethyl group, pentadecyloxycarbonylethyl group,
Alkyloxycarbonylalkyl groups such as hexadecyloxycarbonylethyl group, heptyldecyloxycarbonylethyl group, octyldecyloxycarbonylethyl group, methylcarbonyloxyethyl group, ethylcarbonyloxyethyl group, propylcarbonyloxyethyl group, butylcarbonyloxyethyl Group, pentylcarbonyloxyethyl group, hexylcarbonyloxyethyl group, heptylcarbonyloxyethyl group, octylcarbonyloxyethyl group, nonylcarbonyloxyethyl group, decylcarbonyloxyethyl group, undecylcarbonyloxyethyl group, dodecylcarbonyloxyethyl group , Tridecylcarbonyloxyethyl group, tetradecylcarbonyloxyethyl group, pentadecylcarbonyloxyethyl group Hexadecyl carbonyloxy ethyl group, a heptyl decyl carbonyloxy ethyl group, an alkylcarbonyloxy alkyl group such as octyl decyl carbonyloxy ethyl group, a phenyl group, a biphenyl group, an indenyl group, indanyl group, a naphthyl group, 1,
4-dihydronaphthyl group, tetralinyl group, binaphthyl group, azulenyl group, biphenylenyl group, acenaphthyl group, acenaphthenyl group, fluorenyl group, phenanthrenyl group, anthracenyl group, fluorantenenyl group, aceanthrenyl group, triphenyl group, pyrenyl group , A chrysenyl group, a naphthacenyl group, a picenyl group, a perylenyl group, a rubicenyl, a coronel group, an aryl group such as an opalenyl group, an oxetanyl group, a thietanyl group, an azetidine group,
Furanyl group, tetrahydrofuranyl group, dioxolanyl group, thiophenyl group, thiolanyl group, pyrrole group, pyrroline group, pyrrolidine group, pyrazole group, pyrazoline group,
Pyrazolidine group, imidazole group, imidazoline group, imidazolidine group, triazole group, tetrazole group, isoxazole group, oxazole group, furazane group, isothiazole group, thiazole group, pyranyl group, oxanyl group, dioxanyl group, thianyl group, dithianyl group , Pyridinyl, piperidinyl, pyridazinyl, pyrimidinyl, pyrazinyl, piperazinyl, triazinyl, tetrazinyl, oxazinyl, morpholininyl, thiazinyl, thienothiophenyl, benzofuranyl, dihydrobenzofuranyl, benzothio Phenyl group, indole group, indoline group, isoindole group, isoindoline group, indolizine group, indazole group, benzimidazole group, benzotriazole group, benzoxazole group Benzothiazole group, benzothiazoline group, purine group, chromene group, chroman group, isochromene group, icycloman group, quinoline group, isoquinoline group, quinolidine group, cinnoline group, quinazoline group, quinoxaline group, phthalazine group, naphthyridine group, pteridine group, Complexes such as dibenzofuran, carbazole, xanthene, dibenzothiopyran, acridine, thianthrene, phenazine, phenoxazine, phenoxazine, phenothiazine, phenanthridine, phenanthroline, benzocinnoline, and quinuclidine groups Ring, benzoquinone group, tropolone group, benzophenone group, benzidine group, naphthoquinone, phenanthrenequinone group, anthrone group, anthraquinone group, benzanthrone group, pyrone group, pyrazolone group, Ntoin group, barbituric acid, phthalide group, coumarin group, isocoumarin group, chromone group, flavones group, xanthine group, Nyosanmoto,
And a cyclic group such as a tropone group.

Next, specific examples of the acidic group contained in the pendant group (R ¹ ) will be described. Pendant group (R ¹ )
Acidic groups contained in carboxyl group, thiocarboxylic acid group, dithiocarboxylic acid group, thiocarbonate group, phosphoric acid group, phosphonic acid group, phosphinic acid group, sulfate group, sulfite group, sulfinic acid group, amide sulfate group, flufamin An acid group or a boric acid group. These acidic groups may be in the form of a salt.
Among these, a carboxyl group, a phosphonic acid group, a sulfamic acid group, a thiocarboxylic acid group, a dithiocarboxylic acid group, a phosphoric acid group, and a sulfate group are preferred, and a carboxyl group, a phosphonic acid group, a phosphate group, and a sulfate group are particularly preferred. .

The counter ion of the acidic group is not particularly restricted but includes alkali metal salts such as sodium, potassium and lithium, ammonium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium and tetrahexyl. Ammonium, ethyltrimethylammonium, trimethylpropylammonium, butyltrimethylammonium, pentyltrimethylammonium, hexyltrimethylammonium, cyclohexyltrimethylammonium, benzyltrimethylammonium, triethylpropylammonium, triethylbutylammonium, triethylpentylammonium, triethylhexylammonium, cyclohexyltriethylammonium Um, ammonium salts such as benzyltriethylammonium, trimethylamine, triethylamine, tripropylamine, tributylamine,
Tripentylamine, trihexylamine, triethanolamine, tripropanolamine, tributanolamine, tripentanolamine, trihexanolamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dicyclohexylamine, Dibenzylamine,
Ethyl methylamine, methylpropylamine, butylmethylamine, methylpentylamine, methylhexylamine, methylamine, ethylamine, propylamine,
Examples thereof include amine salts such as butylamine, pentylamine, hexylamine, octylamine, decylamine, dodecylamine, and hexadecylamine.

Among these, in order to exhibit high hydrophilicity, it is preferable that the molecular weight of the counter ion is small. Also,
When there is a possibility of touching human skin or the like, it is better that the irritation is low, and alkali metal salts such as sodium, potassium and lithium, and ammonium are preferable. Further, the above-described hydrocarbon group may contain a substituent other than the acidic group as long as the properties of the polymer of the present invention are not impaired. Examples of the substituent include an optionally branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aralkyl group, an optionally substituted phenyl group, and an optionally substituted naphthyl. Group, an optionally branched alkoxy group having 1 to 18 carbon atoms, an aralkyloxy group, a phenylthio group, an optionally branched alkylthio group having 1 to 18 carbon atoms, and an optionally branched alkylthio group having 1 to 18 carbon atoms Good alkylamino group, C1-18 optionally branched dialkylamino group, C1-18 optionally branched trialkylammonio group, sulfonic acid group, hydroxyl group, amino group, mercapto group , An alkoxycarbonyl group, an alkylcarbonyloxy group and the like.

The polymer of the present invention may contain, in addition to the repeating unit containing a pendant group (R ¹ ) having an acidic group, a repeating unit having another side chain group in the molecule. For example, a repeating unit having a side chain group having a group having a carboxyl group, a pendant group having a sulfonic acid group, a pendant group having no substituent and the like in a structure in which an imide ring is simply opened may be mentioned. In the case of other side-chain groups, there are those containing the same substituents as in the case of the hydrocarbon group described above.

Further, the polymer of the present invention further comprises
It may contain acidic polyamino acid residues. For example, a simple acidic polyaspartic acid residue is a polyaspartic acid residue or a polyglutamic acid residue and has a carboxyl group. In addition to the carboxyl group, a formyl group, a carboxylic acid alkylamide group, a carboxylic acid dialkylamide group, and a thiocarboxylic acid group are exemplified. The carboxyl group is bonded to hydrogen or has a salt structure with a counter ion. The counter ion for the carboxyl group of the acidic amino acid residue is not particularly limited, and examples thereof include those described above for the acidic group.

(2-2) Hydrophobic polymer side chain structure In the general formulas (2a) and (2b), the side chain structure is represented by X
² and R ² also constitute a hydrophobic amide structure or a hydrophobic thioester structure of the acidic polyamino acid. In the present invention, these are conveniently referred to as "hydrophobic side chain groups". This hydrophobic side chain group is formed, for example, by a dehydration condensation reaction between a carboxyl group of the polymer main chain and an amino group or thiol group of the reaction reagent.

In the case of an aspartic acid residue, the hydrophobic side chain group may be substituted at the α-position or β-position with respect to the amide bond or thioester bond of the polymer main chain. In the case of a glutamic acid residue, it may be substituted at the α-position or at the γ-position.

In the general formulas (2a) and (2b), X ² is a bond selected from —NH—, —N (R ″) —, —O—, and —S—. Or a plurality of mixtures. Here, R ″ is, for example, carbon number 1
And 16 to 16 optionally branched alkyl groups, aralkyl groups and aryl groups.

In the general formulas (2a) and (2b), R
² is an alkyl group, an aralkyl group or an aryl group. For example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,
Alkyl groups such as tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, tujanyl group, calanyl group, bornanyl Cycloalkyl groups such as a cycloalkyl group such as a group, norbornanyl group, pinanyl group and decalinyl group, cyclopentenyl group, cyclopentadienyl group, cyclohexenyl group, cyclohexadienyl group, cycloheptenyl group, cyclooctatetraenyl group, and fulbenyl group. Aralkyl groups such as enyl group, benzyl group, phenylethyl group, phenylpropyl group and phenylbutyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, pentyloxyethyl group, hexyloxy Ethyl group, heptyloxy ethyl group, an octyloxy ethyl, decyl oxyethyl group,
Undecyloxyethyl group, dodecyloxyethyl group,
Alkoxyalkyl groups such as tridecyloxyethyl group, tetradecyloxyethyl group, pentadecyloxyethyl group, hexadecyloxyethyl group, heptyldecyloxyethyl group, octyldecyloxyethyl group, and aryloxyalkyl groups such as phenoxyethyl group , Benzyloxyethyl group, aralkyloxyalkyl group such as tolyloxyethyl group, methylthioethyl group, ethylthioethyl group, propylthioethyl group, butylthioethyl group,
Pentylthioethyl group, hexylthioethyl group, heptylthioethyl group, octylthioethyl group, nonylthioethyl group, decylthioethyl group, undecylthioethyl group, dodecylthioethyl group, tridecylthioethyl group,
Alkylthioalkyl groups such as tetradecylthioethyl group, pentadecylthioethyl group, hexadecylthioethyl group, heptyldecylthioethyl group, octyldecylthioethyl group, and arylthioalkyl groups such as phenylthioethyl group and tolylthioethyl group An aralkylthioalkyl group such as a benzylthioethyl group, a methylaminoethyl group, an ethylaminoethyl group, a propylaminoethyl group,
Butylaminoethyl group, pentylaminoethyl group, hexylaminoethyl group, heptylaminoethyl group, octylaminoethyl group, nonylaminoethyl group, decylaminoethyl group, undecylaminoethyl group, dodecylaminoethyl group, tridecylaminoethyl Group, tetradecylaminoethyl group, pentadecylaminoethyl group, hexadecylaminoethyl group, heptyldecylaminoethyl group, alkylaminoalkyl group such as octyldecylaminoethyl group, dimethylaminoethyl group, diethylaminoethyl group, dipropylamino Ethyl group, dibutylaminoethyl group, dipentylaminoethyl group, dihexylaminoethyl group, diheptylaminoethyl group, dioctylaminoethyl group, dinonylaminoethyl group, didecylaminoethyl group, diun Silaminoethyl group, didodecylaminoethyl group, ditridecylaminoethyl group, ditetradecylaminoethyl group, dipentadecylaminoethyl group, dihexadecylaminoethyl group, diheptyldecylaminoethyl group, dioctyldecylaminoethyl group , An ethylmethylaminoethyl group, a dialkylaminoalkyl group such as a methylpropylaminoethyl group, a methyloxycarbonylethyl group, an ethyloxycarbonylethyl group,
Propyloxycarbonylethyl group, butyloxycarbonylethyl group, pentyloxycarbonylethyl group,
Hexyloxycarbonylethyl group, heptyloxycarbonylethyl group, octyloxycarbonylethyl group, nonyloxycarbonylethyl group, decyloxycarbonylethyl group, undecyloxycarbonylethyl group, dodecyloxycarbonylethyl group, tridecyloxycarbonylethyl group, Tetradecyloxycarbonylethyl group, pentadecyloxycarbonylethyl group,
Alkyloxycarbonylalkyl groups such as hexadecyloxycarbonylethyl group, heptyldecyloxycarbonylethyl group, octyldecyloxycarbonylethyl group, methylcarbonyloxyethyl group, ethylcarbonyloxyethyl group, propylcarbonyloxyethyl group, butylcarbonyloxyethyl Group, pentylcarbonyloxyethyl group, hexylcarbonyloxyethyl group, heptylcarbonyloxyethyl group, octylcarbonyloxyethyl group, nonylcarbonyloxyethyl group, decylcarbonyloxyethyl group, undecylcarbonyloxyethyl group, dodecylcarbonyloxyethyl group , Tridecylcarbonyloxyethyl group, tetradecylcarbonyloxyethyl group, pentadecylcarbonyloxyethyl group Hexadecyl carbonyloxy ethyl group, a heptyl decyl carbonyloxy ethyl group, an alkylcarbonyloxy alkyl group such as octyl decyl carbonyloxy ethyl group, a phenyl group, a biphenyl group, an indenyl group, indanyl group, a naphthyl group, 1,
4-dihydronaphthyl group, tetralinyl group, binaphthyl group, azulenyl group, biphenylenyl group, acenaphthyl group, acenaphthenyl group, fluorenyl group, phenanthrenyl group, anthracenyl group, fluorantenenyl group, aceanthrenyl group, triphenyl group, pyrenyl group , A chrysenyl group, a naphthacenyl group, a picenyl group, a perylenyl group, a rubicenyl, a coronel group, an aryl group such as an opalenyl group, an oxetanyl group, a thietanyl group, an azetidine group,
Furanyl group, tetrahydrofuranyl group, dioxolanyl group, thiophenyl group, thiolanyl group, pyrrole group, pyrroline group, pyrrolidine group, pyrazole group, pyrazoline group,
Pyrazolidine group, imidazole group, imidazoline group, imidazolidine group, triazole group, tetrazole group, isoxazole group, oxazole group, furazane group, isothiazole group, thiazole group, pyranyl group, oxanyl group, dioxanyl group, thianyl group, dithianyl group , Pyridinyl, piperidinyl, pyridazinyl, pyrimidinyl, pyrazinyl, piperazinyl, triazinyl, tetrazinyl, oxazinyl, morpholininyl, thiazinyl, thienothiophenyl, benzofuranyl, dihydrobenzofuranyl, benzothio Phenyl group, indole group, indoline group, isoindole group, isoindoline group, indolizine group, indazole group, benzimidazole group, benzotriazole group, benzoxazole group Benzothiazole group, benzothiazoline group, purine group, chromene group, chroman group, isochromene group, icycloman group, quinoline group, isoquinoline group, quinolidine group, cinnoline group, quinazoline group, quinoxaline group, phthalazine group, naphthyridine group, pteridine group, Complexes such as dibenzofuran, carbazole, xanthene, dibenzothiopyran, acridine, thianthrene, phenazine, phenoxazine, phenoxazine, phenothiazine, phenanthridine, phenanthroline, benzocinnoline, and quinuclidine groups Ring, benzoquinone group, tropolone group, benzophenone group, benzidine group, naphthoquinone, phenanthrenequinone group, anthrone group, anthraquinone group, benzanthrone group, pyrone group, pyrazolone group, Ntoin group, barbituric acid, phthalide group, coumarin group, isocoumarin group, chromone group, flavones group, xanthine group, Nyosanmoto,
And a cyclic group such as a tropone group.

Further, the above-mentioned hydrophobic group may contain a substituent as long as the properties of the polymer are not impaired.
Examples of the substituent include an optionally branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aralkyl group, an optionally substituted phenyl group, and an optionally substituted naphthyl. Group, an optionally branched alkoxy group having 1 to 18 carbon atoms, an aralkyloxy group, a phenylthio group, an optionally branched alkylthio group having 1 to 18 carbon atoms, and an optionally branched alkylthio group having 1 to 18 carbon atoms Good alkylamino group, C1-18 optionally branched dialkylamino group, C1-18 optionally branched trialkylammonio group, sulfonic acid group, hydroxyl group, amino group, mercapto group , An alkoxycarbonyl group, an alkylcarbonyloxy group and the like.

As the hydrophobic group, in addition to the above substituents,
As long as the properties of the polymer are not impaired, the amino acid may contain a carboxyl group which is esterified, amidated or thioesterified to make the amino acid hydrophobic. Examples thereof include esters, amides and thioesters of the above-mentioned hydrophobic amino acids, asparagine, aspartic acid, alanine, arginine, allothreonine, ergothioneine,
Ornithine, canavanine, carboxymethylcysteine, kynurenine, glycine, glutamine, glutamic acid, cysteine, cysteic acid, citrulline, 3,4-
Dihydroxyphenylalanine, serine, threonine,
Esters such as histidine, hydroxylysine, homoserine, 1-methylhistidine, lysine and the like, amides, thioesters and the like can be mentioned. Further examples include half esters such as cystathionine, cystine and lanthionine, amides and thioesters. In addition, examples of amino acid derivatives include hydrophobic amino acid dimers, trimers, multimers, and peptides. These can be used in any of L-form, D-form and DL-form.

(3) Method for Producing Polymer The method for producing the polymer of the present invention is not particularly limited. Here, a more useful polyaspartic acid-based resin will be mainly described.

The method for producing the polyaspartic acid-based resin of the present invention is not particularly limited, and a method for introducing a pendant group containing a specific acidic group (hereinafter simply referred to as an acidic group) into polyaspartic acid, There is a method of polymerizing a monomer into which a pendant group containing a is introduced. Further, there is a method using a polysuccinimide having a structure in which one molecule of water is further dehydrated from a polyaspartic acid unit. Furthermore, a method of introducing a pendant group containing a precursor which can be an acidic group by the above method and converting the pendant group into an acidic group can also be mentioned.

In the method of introducing a pendant group containing an acidic group into polysuccinimide, the reaction proceeds under mild conditions,
It is particularly preferred because there are no by-products.

Since the production method using polysuccinimide or using polyaspartic acid obtained by hydrolyzing polysuccinimide is suitable for industrial production, these methods will be described.

The method of introducing the hydrophilic copolymer component and the hydrophobic copolymer component may be a method of introducing the monomer units and then polymerizing them. However, in the present invention, the method of introducing acidic polyamino acids, polysuccinimides and the like may be used. The method of inducing hydrophilicity and hydrophobicity using the above polymer is preferable, and this will be described. Here, the method for deriving the hydrophilic copolymer component and the hydrophobic copolymer component are not strictly under the same production conditions, but the reaction is basically performed on the same principle. As the reaction conditions, in the case of hydrophilicity and hydrophobicity, the polarity of the reaction reagent that can be used as a pendant group,
The reaction solvent, reaction temperature, reaction time, and the like differ because the reactivity, the polarity of the polymer undergoing the reaction, the reactivity, the process of undergoing the reaction, and the polarity of the polymer after the reaction differ.
The order of introduction of the hydrophilic group and introduction of the hydrophobic group is not particularly limited. It may be performed at the same time, or a method may be adopted in which one is introduced and then the other is introduced. These may be appropriately selected depending on the reactivity of the reaction reagent used, the polarity of the reaction solvent used, and the like.

(4) Method for Producing Polysuccinimide The method for producing polysuccinimide is not particularly limited.
Journal of the American Chemical Society (J. Amer. Chem. Soc.), 80, 336
It can be easily produced by the method described on pages 1 to (1958) and the like. When producing the polysuccinimide for use in the present invention, an amino acid other than aspartic acid and a monomer component other than the amino acid can be added to produce a copolymer.

In the case of producing a copolymer, another copolymerizable monomer is added to aspartic acid during the production of polysuccinimide and polymerized.

Specific examples of amino acid components other than aspartic acid and glutamic acid include, for example, 20 kinds of protein constituent amino acids, L-ornithine, a series of α-amino acids, β-alanine, γ-aminobutyric acid, neutral amino acids Acidic amino acids, ω-esters of acidic amino acids, basic amino acids, N-substituted basic amino acids, amino acids and amino acid derivatives such as aspartic acid-L-phenylalanine dimer (aspartame), and aminosulfones such as L-cysteic acid Acids and the like can be mentioned. The α-amino acid may be an optically active form (L-form, D-form) or a racemic form. Further, the polymer may be a copolymer containing a repeating unit other than an amino acid.

Examples of other copolymers include dehydration condensates such as aminocarboxylic acid, aminosulfonic acid, aminophosphonic acid, hydroxycarboxylic acid, mercaptocarboxylic acid, mercaptosulfonic acid, and mercaptophosphonic acid.

Further, polyamines, polyhydric alcohols, polythiols, polycarboxylic acids, polysulfonic acids, polyphosphonic acids, polyhydrazine compounds, polycarbamoyl compounds, polysulfonamide compounds, polyvalent sulfonamide compounds, Phosphonamide compounds, polyepoxy compounds, polyvalent isocyanate compounds, polyvalent isothiocyanate compounds, polyvalent aziridine compounds, polyvalent carbamate compounds, polyvalent carbamic acid compounds, polyvalent oxazoline compounds, polyvalent unsaturated bonds Examples include compounds, dehydration condensates of polyvalent metals, adducts, and substituted products.

However, when these polyvalent compounds are used as a copolymer component, if they are used in an excessively large amount, they become in a cross-linked state, become insoluble in water or an organic solvent, and do not meet the original object of the present invention. It is not preferable. The cross-linking used in the present invention preferably shows a fine cross-linking state in which the original properties of the resin are not lost.

(5) Pendant Group Introduction Reaction Although the polymer of the present invention has a hydrophilic copolymer component and a hydrophobic copolymer component, it is introduced here as a pendant group regardless of hydrophilicity or hydrophobicity. Things will be described. The method for deriving an acidic polyamino acid residue will be described in section (6).

The method for introducing a pendant group into the polymer of the present invention is not particularly limited, and the method is described below. The introduction reaction of a pendant group containing a precursor that can be an acidic group is based on the same principle, and therefore, both are collectively described here. In the present invention, for convenience, a substituent that can be an anionic group is referred to as a precursor.

For example, a method of reacting at least one compound selected from the group consisting of amines, alcohols and thiols having at least one specific functional group with polysuccinimide; dehydrating the above compound with an acidic polyamino acid A method of performing a condensation reaction; a method of performing an ester / amide exchange reaction of the above compound with an acidic polyamino acid ester, and the like.

Regarding the reaction reagent which can be a pendant group to be introduced, both those having a hydrophilic substituent and those having a hydrophobic substituent can react by the same introduction method. However,
When introducing an amino acid, a special method is used, which will be described later.

The molecular weight of the polysuccinimide used is
It is not particularly limited, and varies depending on the intended use. For example, when a film forming ability or the like is required, the higher the better, the better the molecular weight is. Generally, it is 1000 or more and 1,000,000 or less. The appropriate molecular weight depends on the application used.

Examples including such a method are listed below. (5-1) a method of reacting polysuccinimide with an amine or the like having an acidic group, (5-2) a method of reacting an acidic polyamino acid or a derivative thereof with an amine or the like having an acidic group by a dehydration condensation reaction, 3) a method of ester / amide exchange between an acidic polyamino acid ester and an amine having an acidic group or the like; (5-4) polysuccinimide:
A method in which a pendant group having a precursor of an acidic group is introduced and further substituted with an acidic group.

Among these, a method that can efficiently react under mild conditions is preferable. In particular, a method of reacting polysuccinimide or a derivative thereof with an amine containing an acidic group, or a pendant group containing a precursor Is preferable.

In (5-2) and (5-3), when an amine containing an acidic group is reacted, the acidic group itself may react with the amine or the like. That is,
Elongation of side groups occurs, but may result in less hydrophilic groups.

The method of introducing a pendant group containing an acidic group into polysuccinimide and the method of introducing a pendant group containing a precursor of an acidic group have a lot in common, and are described together.

The reaction reagent used for the pendant group introduction reaction may contain an acidic group or may contain a precursor which can be an acidic group. Representative examples of the reaction reagent include amines, thiols, and alcohols having at least one acidic group. Examples of the basic skeleton other than the reactive groups include those corresponding to R ¹ described in the description of the structure of the polymer.

When a carboxyl group is introduced as an acidic group, 20 kinds of protein constituent amino acids, L-ornithine, a series of α-amino acids, β-alanine, γ-aminobutyric acid, neutral amino acids, acidic amino acids, acidic amino acids Ω-ester, basic amino acid, basic amino acid N
Amino acids such as a substituted product and an aspartic acid-L-phenylalanine dimer (aspartame) can also be used as a usable reaction reagent. The α-amino acid may be in an optically active form (L-form, D-form) or a racemic form.
These may be used alone or as a mixture of two or more.

The reaction product after the pendant group introduction reaction may be taken out of the system or, if necessary, may be continuously subjected to a substitution reaction with an acidic group, a cationization reaction or a betaine reaction as it is. Here, when the reaction product is taken out of the system, the reaction product may be dried before use.

The reaction product after the pendant group introduction reaction is:
In some cases, a part of the imide ring may be hydrolyzed.

In the pendant group introduction reaction, even if a pendant group is introduced in one step, a substituent is first introduced, and then another substituent is reacted with the substituent to form a pendant group. It does not matter.

(5-1) Method of reacting polysuccinimide with an amine having an acidic group The solvent used for the reaction of introducing a pendant group into polysuccinimide is not particularly limited, and polysuccinimide or polysuccinimide is used. Capable of dissolving derivatives,
Alternatively, any solvent can be used as long as it can dissolve the reaction reagent that can be a pendant group, and any common solvent used for chemical reactions can be used.

The above-mentioned solvents can be used as the reaction solvent. Particularly, since the reaction reagent containing an acidic group has a high polarity,
Polar solvents are preferred. Among them, water, methanol, ethanol, propanol, isopropanol, acetone and the like are preferable, and water is particularly preferable. These solvents may be used alone or in combination of two or more.

The concentration of the polysuccinimide at the time of the reaction for introducing a pendant group into the polysuccinimide is not particularly limited, but is preferably 0.1 to 50% by mass, particularly preferably 1 to 40% by mass. In the pendant group introduction reaction, a catalyst may be used if necessary. As the catalyst, a base catalyst or an acid catalyst is generally used.

Examples of the base catalyst include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate and lithium carbonate, sodium hydrogen carbonate and hydrogen carbonate. Inorganic base reagents such as alkali metal bicarbonates such as potassium, alkali metal acetates such as sodium acetate and potassium acetate, alkali metal salts such as sodium oxalate, and ammonia; trimethylamine, triethylamine, tripropylamine, tributylamine, tributylamine Pentylamine, trihexylamine, triethanolamine, tripropanolamine, tributanolamine, tripentanolamine, trihexanolamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentyne Amine, dihexyl amine, dicyclohexylamine, dibenzylamine, ethylmethylamine, methylpropylamine, butyl methylamine, methyl pentyl amine, methyl hexyl amine, pyridine, picoline, include organic bases agents such as amines quinoline.

Specific examples of the acid catalyst include, for example, hydrochloric acid,
Inorganic acids such as hydrobromic acid, hydroiodic acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, carbonic acid and phosphoric acid; carboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid and benzoic acid; methanesulfonic acid; Sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid; and phosphonic acids such as benzenephosphonic acid. The catalyst can be used alone or in combination of two or more.

The reaction temperature in the pendant group introduction reaction is not particularly limited, but is preferably from 0 to 120 ° C., particularly preferably from 10 to 60 ° C.

(5-2) Method of reacting an acidic polyamino acid with an amine having an acidic group As a method for introducing a pendant group into an acidic polyamino acid, a method of dehydrating and condensing an acidic polyamino acid with the above-mentioned reaction reagent is generally used. It is. In the case of an acidic group, in the method of dehydrating and condensing an acidic polyamino acid and an amine containing an acidic group,
Depending on the reaction conditions, the acidic group itself may react with an amine or the like. That is, although the extension of the side chain group occurs,
As a result, the number of hydrophilic groups may decrease. Therefore, in some cases, a method of protecting an acidic group may be adopted. The dehydration condensation may be any of a method of removing generated water by azeotropic distillation with a solvent, a method of adding molecular sieve as a dehydrating agent, a method of reacting using a dehydrating condensing agent, and a method of using an enzyme. Alternatively, aspartic acid and the crosslinking agent can be uniformly mixed, and the reaction can be performed in a solid phase state in which the solvent is removed.

Examples of the condensing agent include carbodiimides such as dicyclohexylcarbodiimide and N-ethyl-N '-(3-dimethylaminopropyl) carbodiimide;
Acyl imidazolide, 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline, triphenylphosphine / carbon tetrachloride, triphenylphosphine / bromotrichloromethane, phenylphosphonic acid bis (2-nitrophenyl ester), cyanophosphone Phosphorus-containing compounds such as diethyl acid, diphenylphosphoroazide, 2-fluoro-1-ethylpyridium tetrafluoroborate,
Oxidation-reduction condensing agents such as triphenylphosphine / bis (benzothiazole) disulfide and tributylphosphine / bis (benzothiazole) disulfide. Examples of enzymes include lipases such as penicillin acylase and yeast lipase. The reaction temperature at the time of dehydration condensation is preferably 20 to 250 ° C, and 100 to 18 ° C.
0 ° C. is particularly preferred.

Further, a method of esterifying, amidating, or thioesterifying an acidic polyamino acid may be used.

In this case, usual reaction conditions used in organic chemistry can be used. As the method, an acidic polyamino acid may be used as an acidic amino acid residue, and the carboxyl group may be reacted with an ester, amide or thioester forming group. Further, after increasing the reactivity as a derivative, an ester, amide or thioester forming group may be introduced.

For example, a method in which a carboxyl group of an acidic amino acid residue is subjected to a dehydration condensation reaction with an alcohol, an amine, and a thiol,
A method of activating with an acid halide, an acid azide or the like and reacting with an alcohol, an amine or a thiol, a method of reacting a carboxyl group of an acidic amino acid residue with an activated alcohol such as an ester of an alcohol, a sulfonate or a sulfate); A method of reacting an activated amine (eg, a silicon derivative of an amine), a method of reacting a carboxyl group of an acidic amino acid residue with an epoxy compound, an isocyanate compound, an aziridine compound, an alkyl metal, or the like; As a salt, a method of reacting with a halide or the like, a method of reacting a carboxyl group of an acidic amino acid residue as an active ester group by transesterification or transamidation, or the like can be used.

(5-3) Method of reacting polyaspartic acid ester with an amine having an acidic group The method of reacting the acidic polyamino acid ester is not particularly limited, and the reaction reagent and the acidic polyamino acid ester are reacted in an organic solvent. Is generally used. Examples of the ester used include a small alcohol component such as methyl and ethyl, an alcohol component having an electron withdrawing group such as chloromethyl and dichloromethyl, and an alcohol such as N-hydroxysuccinimide.

In some cases, a catalyst such as an acid catalyst or a base catalyst may be used. When the reaction system becomes heterogeneous or when the raw materials used are insoluble, a phase transfer catalyst may be used.

(5-4) Method Using Acidic Group Precursor The polymer of the present invention can be replaced with an acidic group after introducing a substituent which is a precursor of the acidic group by the above method. . In particular, it is preferable to perform this method because the functional groups themselves are unstable for a sulfuric acid group, a phosphoric acid group, and the like and can be converted more easily than a hydroxyl group.

(6) Post-treatment after the reaction The treatment after completion of the pendant group introduction reaction and the conversion reaction of the precursor into an acidic group is not particularly limited, and a general method used in the production of the compound may be used. Can be. The method for isolating the produced polymer from the reaction solution after completion of the reaction employed in the method for producing a polymer of the present invention is not particularly limited as long as the reaction product can be substantially isolated with a desired purity. Not done. The above-mentioned isolation method may be any of publicly known and public methods. Generally, known and publicly used isolation procedures such as concentration, recrystallization, and reprecipitation are employed.

Specific examples of the above isolation method include, for example,
After completion of the reaction, an excess poor solvent (eg, methyl alcohol, ethyl alcohol, isopropyl alcohol, etc.) is added to the reaction solution in which the reaction product is dissolved at an appropriate temperature, and the precipitated reaction product is decanted. , Filtration or suction filtration, washing with a poor solvent that does not dissolve the precipitate, and drying. As another specific example, for example, after completion of the reaction, at an appropriate temperature, the reaction solution in which the reaction product is dissolved,
In addition to the same excess of the poor solvent as described above, a method of isolating, washing, and drying a precipitate of a precipitated reaction product in the same manner as described above may be used.

The drying temperature of the resin is not particularly limited.
Generally, the temperature is preferably from 20 to 150 ° C, particularly from 40 to 100 ° C.
C is preferred.

The method for drying these resins is not particularly limited, but may be hot air drying, drying with specific steam, microwave drying, reduced pressure drying, drum dryer drying, azeotropic drying in a hydrophobic organic solvent. Drying can be performed by a known method such as drying by dehydration. Drying temperature is 20 ~ 200 ℃
Is preferable, and 50 to 120 ° C. is more preferable.

(7) Uses of Polymer The use of the polymer of the present invention is not particularly limited, but conventional surface-acting polymer drugs, interface-acting polymer drugs, internal-acting polymer drugs, and binding-acting polymer drugs can be used. It can be used in any of the applications where polymeric drugs can be used.

For example, as an interface-acting type high molecular drug,
The main purpose of dispersion is pigment dispersant, pesticide granule dispersant, pulverized coal dispersant, cement dispersant, scale inhibitor, lubricating oil cleaning dispersant, pour point depressant, plastic coloring aid , Compatibilizers, and those mainly used for aggregation include polymer flocculants, drainage / retention improvers, etc., and those mainly used for adhesion include binders for printing inks, Polymer, non-woven fabric binder, plastic reinforcing fiber binder, electrophotographic toner binder, magnetic tape binder, resin concrete binder, foundry sand binder, fine ceramic binder, sealant, adhesive, etc. As the object, a foam stabilizer, an antifoaming agent, an emulsion breaker, a lubricant and the like can be mentioned.

The surface-acting high-molecular-weight agents mainly used for surface protection include hair conditioning agents, humectants, coating polymers, floor polish polymers, tablet coating agents, masking agents, and optical fiber coating agents. Agents, plastic / hard coat agents, polymers for photoresists, moisture-proof coating agents for printed wiring boards, etc. The main purpose of surface modification is as a paper sizing agent, paper strength enhancer, polishing coating agent And dye-proofing agents for textiles, antistatic agents / conductive agents, coating agents for electromagnetic wave shielding, waterproofing agents for concrete, primers and the like.

As the internally acting polymer chemicals, those mainly used for thickening include printing agents, polymers for increasing crude oil, polymers for civil engineering, polymers for quenching oil, polymers for hydraulic fluids. , A viscosity index improver and the like, and those mainly intended for viscosity reduction include plasticizers, and those mainly intended for gelation include water-absorbing polymers and oil-absorbing polymers. . Examples of the binding action type polymer drug include a builder, a chelate polymer, a dye fixing agent, and an epoxy resin curing agent.

The film-forming agent containing the polymer of the present invention can form a film having low skin and mucous membrane irritation.
The content of the polymer of the present invention contained in the film-forming agent is appropriately determined depending on the desired film-forming effect, cost, performance and the like of the film-forming agent. From the viewpoint that a uniform film is obtained, the film forming effect is high, and the cost is high, the polymer content is approximately
A range from 0.1% to 80% by weight is preferred. Since the polymer of the present invention has particularly high affinity for hair, skin and mucous membranes, it is preferably used as a film-forming agent for hair, skin and mucous membranes.

The polymer of the present invention can be prepared by balancing hydrophilicity / hydrophobicity according to the purpose of use and intended use.
Can act as an effective polymer in a wide range.

As used herein, the term “film-forming agent” includes, for example, rinsing, hair treatment, hair conditioner, emulsion, emulsion, cream, cleansing cream, whitening, lipstick, lotion, lotion, nail polish, Pedicure, moisturizer,
Also includes packs, mousses, shaving creams, after shaving lotions, hair tonics, hair liquids, hair sprays, deodorants, hair waxes and gels.

(7) Use of Cosmetics (Food) and Cosmetics (Food) The polymer of the present invention can be usefully used in cosmetics and cosmetics.

As used herein, the terms “cosmetics”, “cosmetics”, “cosmetics”, and “cosmetics” include the following:
For example, "Text of the 26th New Employee Cosmetic Technology Seminar" (co-sponsored by Tokyo Cosmetic Industry Association and Tokyo Cosmetic Engineers Association, co-sponsored by Japan Cosmetic Industry Association, June 1994, Asahi Seimei Hall), p.34 and p.34 Includes types and items described in “Table-Types of cosmetics and range of effects” on page 35. All the descriptions are incorporated as a part of the disclosure of the specification of the present application by explicitly citing the cited documents and the cited range, and by referring to the explicitly cited ranges, the matters or disclosures described in the specification of the present application are all Matters or disclosures that can be directly and uniquely derived by the trader.

As used herein, the concepts of “cosmetics” and “cosmetics” include, for example, emulsions, emulsions, creams, cleansing creams, whitening, lipsticks, lotions, lotions, wet tissues, nail polish, pedicures, moisturizers Ingredients, packs, mousses, shaving creams, after shaving lotions, hair tonics, hair liquids, hair sprays, deodorants, deodorants, deodorants and the like.

As used herein, the terms "cosmetics" and "cosmetics" include, for example, hair styling, perfume, eau de Cologne, eau de toilette, fragrances, bath additives, fragrances and the like.

[0114]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples. In the following Examples and Comparative Examples, “parts” means “parts by mass”. In Comparative Examples, the polymer of the present invention is particularly referred to as "polyamino acid polymer". The evaluation methods (1) to (6) employed in the examples and comparative examples are shown below.

(1) Evaluation of Weight Average Molecular Weight of Raw Material Polysuccinimide Weight average molecular weight of raw material polysuccinimide (hereinafter referred to as Mw)
That. ) Was evaluated by gel permeation chromatography (gel filtration chromatography, hereinafter referred to as GPC) under the following conditions using polystyrene as a standard.

Apparatus: JASCO 880-PU Detector: Shodex RID-300 Column: Shodex KD-804 + KD-80M Solvent: 0.01M LiBr / DMF Concentration: 0.5 wt% Injection volume: 20 μl Flow rate: 1.0 ml / min.

(2) Analysis of Polymer Composition (Analysis of Hydrolyzate) -1 In order to examine the composition of the polymer, the monomer and pendant obtained by hydrolysis were subjected to high performance liquid chromatography (hereinafter abbreviated as HPLC). ). The hydrolysis reaction of the polymer was performed by adding 0.5 part of the polymer to 20 parts of 6N hydrochloric acid at 110 ° C. for 24 hours. The decomposition product thus obtained was evaluated under the following conditions.

Analysis of pendant components containing aspartic acid, basic amino acid or betaine group; Apparatus: JASCO 880-PU Detector: 570 nm Column: Shodex CXpak
P-421 Solvent: Sodium citrate buffer (A) 0.2N Na
+ / 12% C ₂ H ₅ OH (pH 3.32) (B) 0.2N Na + (pH 4.20) (C) 1.0N Na + (pH 6.98) (D) 1.8N Na + (pH 7.50) Gradient: (A) 15 minutes → (B) 13 minutes → (C) 1
3 minutes → (D) 27 minutes, flow rate: 0.5 ml / min. Reaction reagent: ninhydrin (0.4 ml / min.).

(3) Analysis of Polymer Composition (Analysis of Hydrolyzate) -2 The aliphatic amine component obtained by hydrolyzing the produced polymer was analyzed by gas chromatography (hereinafter abbreviated as GC). It was measured. The hydrolysis reaction of the polymer was performed under the same conditions as in (3), and the pH of the solution was adjusted to 9 and evaluated under the following conditions.

Analysis of aliphatic amine; Apparatus: Shimadzu GC-14A Column: Unisole 10T + KOH (20 + 4)%
Uniport C80 / 100 GlassCol.I.
D. 3φ × 3m Column temperature: 60 ° C./15 minutes, 60-180 ° C .: Pro
g. 7.5 ° C./min Mobile phase: N ₂ 20 ml / min. Detector: FID103 × 8 Sample size: 0.4 μL.

(4) Skin irritation According to the Draize method (OECD guideline; No. 404), the test was carried out using three white rabbits for each polymer. The active ingredient concentration was adjusted to 5% by mass and applied to rabbits.
From the appearance of the skin after a lapse of a certain time, the evaluation was made according to the following four grades using a Draise score. ◎: Non-irritant ：: Mild-irritant ：: Moderate-irritant ×: Severe-irritant.

(5) Measurement of biodegradability Biodegradability was measured by a compost method. The composting method is an application of ASTM D-5338.92, an ISO
Performed according to CD 14855. That is, first, the amount of carbon contained in the test sample was measured by elemental analysis. Next, 15 parts of the test sample were added to 800 parts of the innoculum, biodegraded at 58 ° C. for 40 days, the amount of generated carbon dioxide was measured, and the amount of carbon contained in the test sample was converted to carbon dioxide. The amount of carbon dioxide generated with respect to the calculated amount was expressed as a biodegradation rate (%).

(6) Sensory Test The use of the polymer of the present invention is not limited. Here, the effect as a humectant was confirmed by a sensory test.
That is, the following lotion was prepared using a polymer, and 2
The smoothness, moistness and stickiness of the skin when each composition was used by 0 panelists were evaluated on the following three scales, and the average score was obtained.

Composition of lotion: 1.0% by mass of polyamino acid polymer, 2.0% by mass of polyoxyethylene (20 mol addition) sorbitan monolaurate, 1.0% of polyoxyethylene (20 mol addition) sodium lauryl ether sulfate Wt%, ethanol 8.0 wt%, glycerin 5.
0% by mass, propylene glycol 4.0% by mass, citric acid 0.2% by mass, purified water residue Sensory evaluation; 3: Very smooth, 2: Slightly smooth, 1: No smoothness 3: Good moist feeling, 2: Normal moist feeling, 1: No moist feeling 3: No sticky feeling 2: Slightly sticky, 1: Very sticky.

Example 1 Laurylamine (5.73) was dissolved in a solution prepared by dissolving 10 parts of polysuccinimide (hereinafter abbreviated as PSI) having an Mw of 106,000 in 20 parts of N, N-dimethylformamide (hereinafter abbreviated as DMF). And reacted at 60 ° C. for 4 hours. The reaction solution is discharged into 200 parts of distilled water,
The precipitate was collected by suction filtration and washed with 50 parts of distilled water. The obtained wet cake is mixed with 50 parts of water and methanol 2
0 parts, and an aqueous solution obtained by dissolving 6.86 parts of L-aspartic acid and 4.29 parts of sodium hydroxide in 20 parts of distilled water was added thereto, and reacted at 50 ° C. for 4 hours. The obtained reaction product was discharged into 500 parts of acetone, and the precipitate was collected by suction filtration and dried at 60 ° C. to obtain 27.9 parts of a polymer.

The decomposition product of the obtained polymer was analyzed by NMR, HPL
When analyzed by C and GC, the composition of the polymer was aspartic acid: pendant aspartic acid: laurylamine = 100: 46: 47 (mol / mol / mol).
The skin irritation of the obtained polymer was ○ and the biodegradation rate was 9
8% showed good biodegradability. In the sensory test, smoothness was 2.8, moist feeling was 2.9, and sticky feeling was 2.7.

Example 2 The procedure of Example 1 was repeated, except that 7.58 parts of L-glutamic acid was used instead of L-aspartic acid. After drying, 29.9 parts of polymer were obtained. The composition of the obtained polymer is aspartic acid: glutamic acid: laurylamine = 10
0:47:47 (mol / mol / mol). The skin irritation of the obtained polymer is ○, and the biodegradation rate is 100%.
And good biodegradability. The sensory test was 2.7 for smoothness, 2.8 for moist feeling, and 2.6 for sticky feeling.
Good results.

[Example 3] In Example 1, glycine 3.87 was used instead of the aqueous solution of sodium L-aspartate.
And a solution of 2.15 parts of sodium hydroxide in 5 parts of distilled water was treated in the same manner as in Example 1. After drying, 23.3 parts of polymer were obtained. The composition of the obtained polymer was aspartic acid: glycine: laurylamine = 1.
00:46:47 (mol / mol / mol). The skin irritation of the obtained polymer was ○, and the biodegradation rate was 102.
% And good biodegradability. In the sensory test, the smoothness was 2.7, the moist feeling was 2.8, and the sticky feeling was 2.6.

Example 4 The procedure of Example 3 was repeated, except that 4.59 parts of β-alanine was used instead of glycine. After drying, 23.7 parts of polymer were obtained. The composition of the obtained polymer is aspartic acid: β-
Alanine: laurylamine = 100: 46: 47 (mol / mol / mol). The skin irritation of the obtained polymer was ○, and the biodegradability was 102%, indicating good biodegradability. In the sensory test, the smoothness was 2.7, the moist feeling was 2.8, and the sticky feeling was 2.5.

Example 5 The procedure of Example 1 was repeated, except that 6.76 parts of 6-aminocaproic acid was used instead of glycine. After drying, the polymer 24.7
Parts were obtained. The composition of the obtained polymer was aspartic acid: aminocaproic acid: laurylamine = 100: 3
6:57 (mol / mol / mol). The skin irritation of the obtained polymer was ○, and the biodegradability was 104%, indicating good biodegradability. In addition, the sensory test showed smoothness of 2.
6, a moist feeling of 2.8 and a sticky feeling of 2.5 were good results.

Example 6 The procedure of Example 1 was repeated except that 11.46 parts of laurylamine, 6.06 parts of L-glutamic acid and 3.44 parts of sodium hydroxide were used. After drying, 28.2 parts of polymer were obtained. The composition of the obtained polymer was aspartic acid: glutamic acid: laurylamine = 100: 37: 57 (mol /
Mol / mol). The skin irritation of the obtained polymer was ○, and the biodegradability was 101%, indicating good biodegradability. The sensory test showed smoothness of 2.8 and moist feeling of 2.
7, a sticky feeling of 2.6, which was a good result.

Example 7 The procedure of Example 1 was repeated except that 7.64 parts of laurylamine, 9.10 parts of L-glutamic acid and 5.16 parts of sodium hydroxide were used. After drying, 28.1 parts of polymer were obtained.
The composition of the obtained polymer was aspartic acid: glutamic acid: laurylamine = 100: 57: 38 (mol / mol / mol). The skin irritation of the obtained polymer was ○, and the biodegradability was 100%, indicating good biodegradability.
The sensory test was smoothness 2.7, moist feeling 2.8,
The sticky feeling was 2.5, which was a good result.

Example 8 The procedure of Example 3 was repeated, except that 6.55 parts of 2-aminoethylphosphoric acid was used instead of glycine.
The treatment was performed in the same manner as in Example 1. After drying, the polymer 27.
7 parts were obtained. The composition of the obtained polymer was aspartic acid: 2-aminoethylphosphoric acid: laurylamine = 10
0:36:57 (mol / mol / mol). The skin irritation of the obtained polymer was ○, and the biodegradability was 97%, indicating good biodegradability. In the sensory test, the smoothness was 2.6, the moist feeling was 2.7, and the sticky feeling was 2.6.

Example 9 The procedure of Example 3 was repeated, except that 9.44 parts of 6-aminoethylphosphonic acid was used instead of glycine. After drying, polymer 2
7.1 parts were obtained. The composition of the obtained polymer was aspartic acid: aminoethylphosphonic acid: laurylamine =
100: 36: 57 (mol / mol / mol). The skin irritation of the obtained polymer was ○, and the biodegradation rate was 96.
% And good biodegradability. In the sensory test, the smoothness was 2.7, the moist feeling was 2.8, and the sticky feeling was 2.6.

Example 10 PSI10 with Mw of 96,000
5.73 parts of laurylamine was added to a solution of 20 parts of DMF in DMF, reacted at 60 ° C. for 4 hours, and 3.15 parts of ethanolamine was further added and reacted for 2 hours.
After cooling to room temperature, another 4.54 parts of sulfur trioxide were added,
The reaction was performed for 24 hours. After the reaction, 8.24 parts of a 25% aqueous sodium hydroxide solution was charged over 3 hours. The reaction product was discharged into 400 parts of acetone, and the precipitate was collected by suction filtration.
Drying at 0 ° C. yielded 26.2 parts of polymer.

The decomposition product of the obtained polymer was analyzed by NMR, HPL
When analyzed by C and GC, the composition of the polymer was aspartic acid: ethanolamine derivative: laurylamine = 1
00:47:47 (mol / mol / mol). The skin irritation of the obtained polymer was ○, and the biodegradation rate was 98%.
And good biodegradability. The organoleptic test showed smoothness of 2.8, moist feeling of 2.9, and sticky feeling of 2.7.

Comparative Example 1 A lotion was prepared and evaluated in the same manner as in Example 1 except that the polyamino acid polymer was not added. As a result of the sensory test, the stickiness was good at 2.8, but the smoothness was 2.1 and the moistness was 1.8, which was not good.

Comparative Example 2 A lotion was prepared and evaluated in the same manner as in Example 1 except that sodium polyaspartate having Mw of 820,000 was used instead of the polyamino acid polymer. The results of the sensory test were smoothness 2.4, moist feeling 2.3, and sticky feeling 2.5.

[0139]

As described above, according to the present invention,
It is possible to provide a polymer which is excellent in biodegradability, does not cause irritation to a living body, is excellent in safety after decomposing, and can satisfy various required properties in a wide range of applications, and a method for producing the same.

That is, a pendant group containing a specific hydrophilic substituent having high biocompatibility and safety to the living body obtained by the present invention and a specific hydrophobic substitution having high biocompatibility and safety to the living body are obtained. Acidic polyamino acid derivatives having a pendant group as a pendant group are useful for living organisms (eg, eyes, skin, etc.)
Does not cause irritation to Therefore, it is not irritating to the living body and has biodegradability. Therefore, for example, cosmetics, cosmetics, surfactants, food additives (thickeners, stabilizers, humectants, noodle improvers, It is very useful in the fields of pharmaceutical carriers, pharmaceuticals, quasi-drugs and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Keisuke Takuma 3-5 Kasumigaseki, Chiyoda-ku, Tokyo Mitsui Chemicals Co., Ltd. (72) Inventor Hosei Masaru Shinoda 580-32 Nagaura, Sodegaura City, Chiba Prefecture Mitsui Chemicals Co., Ltd.F-term (reference) UA761 YB32

Claims (14)

[Claims] 1. A recurring unit represented by the following general formula (1a) and / or a recurring unit represented by the following general formula (1b) in a molecule: [In the formulas (1a) and (1b), R ¹ represents a carboxyl group, a thiocarboxylic acid group, a dithiocarboxylic acid group, a thiocarbonate group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfate group, a sulfite group, a sulfinic acid group. A pendant group having at least one acidic group selected from the group consisting of a group, an amidosulfate group, a fluamic acid group and a boric acid group, and salts thereof, and X ¹ is NH, N (R ′) (R ′ Is an alkyl group, an aryl group or an aralkyl group), O or S, and n ¹ is 1
Or 2. In the molecule, a repeating unit represented by the following general formula (2a) and / or a repeating unit represented by the following general formula (2b): [In the formulas (2a) and (2b), R ² is an alkyl group, an aryl group or an aralkyl group, and X ² is NH, N (R ″)
(R ″ is an alkyl group, an aryl group or an aralkyl group) or S, and n ² is 1 or 2. ] The polymer which has these. 2. n ¹ in the general formulas (1a) and (1b),
And / or n ² in the general formulas (2a) and (2b) is
The polymer according to claim 1, which is 1. 3. X ¹ in the general formulas (1a) and (1b),
And / or X ² in the general formulas (2a) and (2b) is
3. The polymer according to claim 1, which is NH. 4. R in the general formulas (1a) and (1b)
¹ is a carboxyl group or a salt thereof.
The polymer according to any one of the above. 5. The polymer according to claim 1, wherein the acidic group in the general formulas (1a) and (1b) is a phosphate group or a salt thereof. 6. The polymer according to claim 1, wherein the acidic group in the general formulas (1a) and (1b) is a phosphonic acid group or a salt thereof. 7. The polymer according to claim 1, wherein the acidic group in the general formulas (1a) and (1b) is a sulfate group or a salt thereof. 8. The number of the repeating units represented by the general formulas (1a) and (1b) is 0.2 to 99.8% of the total number of all the repeating units constituting the molecule. (2
a) The number of repeating units represented by (2b) is 0.2 to 9
The polymer according to any one of claims 1 to 7, which is 9.8%. 9. The polymer according to any one of claims 1 to 8, which is an acidic polyamino acid-based polymer having a main chain formed by using a repeating unit composed of polyglutamic acid or polyaspartic acid as a basic skeleton. 10. A method for producing a polymer according to claim 1, comprising at least a pendant group introduction reaction. 11. The method for producing a polymer according to claim 10, wherein a carboxylic acid salt of an amino acid is used in the pendant group introduction reaction. 12. The method for producing a polymer according to claim 10, wherein a pendant group is introduced into the polysuccinimide. 13. A surface-acting high-molecular-weight drug comprising the polymer according to any one of claims 1 to 9. 14. A film-forming agent composition comprising the polymer according to any one of claims 1 to 9 in an amount of 0.1 to 80% by weight.