JP2001354768A - Polymer and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer excellent in biodegradability and safety, improved in moisture retention and the like, and satisfying characteristics required in wide applications, and its manufacturing method. SOLUTION: The polymer has a pendant group containing a betaine group of general formula (1) (wherein R1, R2 and R3 are each alkyl or the like) or its salt. The method of manufacturing the polymer comprises reacting a polysuccinimide or a polymer having acidic groups with a compound of general formula (3) [wherein Y is NH2, NH(R') or the like; and Z is an organic residue] to convert amino groups into quaternary ammonium groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer having a specific substituent on at least a part of a monomer unit and a method for producing the polymer. More specifically, the present invention relates to a polymer which is excellent in biodegradability, does not cause irritation to a living body, and has excellent safety even after being decomposed, and a method for producing the same.

[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, these resins are incinerated and landfilled.However, in the incinerator method, in addition to damage to furnace materials due to heat generated during incineration, global warming and It is pointed out that it causes 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 has also been 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. Molecule, Vol. 42, August, 19
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. Furthermore, these polymerization resins use monomers that are highly toxic to human skin, etc., and many studies have been made to remove them from products after polymerization. It is difficult. 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] On the other hand, polyamino acids are biodegradable and thus are friendly to the global environment. Even when absorbed into the body, they are digested and absorbed by enzymatic action, and do not show antigenicity in the body. It has been shown to be non-toxic, making it a gentle material for humans. But,
Polyamino acids themselves did not necessarily have sufficient performance characteristics for use in various applications.

[0008]

SUMMARY OF THE INVENTION Accordingly, the present inventors
For the purpose of improving performance characteristics while maintaining safety, from the viewpoint of using compounds that are safe for living organisms and the environment,
As a result of intensive studies, it has been found that polysuccinimide is ring-opened using an ester of an α-amino acid, which is an amine having extremely high biocompatibility and safety to the living body, to produce a living body (eg, eye, skin) And the like, which have substantially no stimulus-inducing property and extremely high safety for living organisms (JP-A-8-48766).

It is an object of the present invention to further improve the above-mentioned resin, to be excellent in biodegradability, excellent in safety, and further improved in terms of moisturizing properties, etc., and to satisfy various required properties in a wide range of applications. And a method for producing the same.

[0010]

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. It has been found that when a betaine group having high safety and high hydrophilicity is introduced, very excellent results can be obtained, and the present invention has been completed.

That is, the polymer of the present invention is a polymer in which at least a part of the repeating units constituting the molecule has a betaine group represented by the following general formula (1) or a pendant group containing a salt thereof. is there.

[0012]

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[In the formula (1), R ¹ , R ² and R ³ represent hydrogen, an alkyl group, an aryl group or an aralkyl group. ].

Further, the production method of the present invention is a method for producing the above polymer, wherein a compound represented by the following general formula (3) is reacted with polysuccinimide or a polymer having an acidic group. And a method for producing a polymer, which further comprises quaternizing an amino group.

[0015]

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[In the formula (3), Y is NH ₂ , NH (R ′)
(R ′ is an alkyl group, an aryl group or an aralkyl group),
OH or SH, and Z is an organic residue. ]

[0017]

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) Basic polymer skeleton of polymer The basic polymer skeleton of the polymer of the present invention is not particularly limited. However, the polymer basic skeleton excluding the pendant groups is preferably one composed of an acidic polymer having an acidic group such as a carboxyl group or a sulfonic acid group. For example, polyacrylic acid, a copolymer of acrylic acid and vinyl acetate, a partial hydrolyzate of a copolymer of acrylic acid and vinyl acetate, a copolymer of acrylic acid and vinylacetamide, and a partial hydrolysis of a starch-acrylonitrile copolymer Product, starch-acrylic acid graft copolymer, hydrolyzate of vinyl acetate-acrylic ester copolymer, poly 2-acrylamido-methylpropanesulfonic acid, copolymer of 2-acrylamido-methylpropanesulfonic acid and acrylic acid Copolymer of 2-acrylamide-methylpropanesulfonic acid and vinyl acetate, hydrolyzate of isobutylene-maleic anhydride copolymer, poly (2-hydroxyacrylic acid), copolymer of acrylic acid and 2-hydroxyacrylic acid Coalescence, carboxymethylcellulose, carboxymethylated starch, alginic acid,
Polysaccharides including glucuronic acid, polyaspartic acid, polyglutamic acid, and the like are included.

Of these, carboxymethyl cellulose, carboxymethylated starch, poly (2-hydroxyacrylic acid), polysaccharides including alginic acid and glucuronic acid, polyaspartic acid, and polyglutamic acid, which are biodegradable, are preferred. Polyaspartic acid and polyglutamic acid are preferred.

(1-2) Acidic polyamino acid-based resin as the basic skeleton of the polymer As the basic skeleton of the polymer of the present invention, an acidic polyamino acid-based resin is particularly useful. As acidic polyamino acids,
Polyglutamic acid and polyaspartic acid can be mentioned. Hereinafter, description will be made mainly of a polyaspartic acid-based resin more suitable for industrial production.

The acidic polyamino acid particularly preferred as the basic skeleton of the polymer of the present invention may be a homopolymer of glutamic acid or aspartic acid, a copolymer thereof, or a copolymer with another amino acid. Specific examples of the amino acid component in the copolymer 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-
Amino acids and amino acid derivatives such as esters, basic amino acids, N-substituted basic amino acids, aspartic acid-L-phenylalanine dimer (aspartame);
Examples thereof include aminosulfonic acids such as cysteic acid. The α-amino acid may be an optically active form (L-form, D-form) or a racemic form. Further, the copolymer may be a block copolymer or a random copolymer.

Further, a copolymer with another polymer having a basic skeleton or a graft copolymer may be used. Examples of the polymer having another basic skeleton include synthetic polymers such as polyacrylic acid, polyvinyl alcohol, and polyoxyalkylene, and polysaccharides such as starch, cellulose, chitin, and chitosan.

Among these, polyaspartic acid, a copolymer of aspartic acid and glutamic acid, a copolymer of aspartic acid and / or glutamic acid and lysine, which are suitable for industrial production, are preferred, and polyaspartic acid is particularly preferred.

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.

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 film forming ability is required, the higher the molecular weight, the better,
When it is necessary to increase the decomposability, the lower the molecular weight, the better. Generally, the weight average molecular weight of the raw material polymer before introducing the pendant group is about 1,000 to 10,000,000, preferably about 5000 to 1,000,000, and more preferably about 10,000 to 200,000.

(3) Side Chain Structure of Polymer In the polymer of the present invention, at least a part of the repeating units constituting the molecule contains a betaine group represented by the above formula (1) or a salt thereof. It has a pendant group. That is, the side chain structure of the polymer is composed of a substituent binding to the polymer main chain and an organic residue (pendant group) containing at least one betaine group or a salt thereof.

The betaine group contained in the pendant group of the polymer of the present invention is a group containing a carboxyl group and an ammonium group at the terminal. Specifically, it is represented as a betaine group which is a tautomer represented by the following general formula (4), or a salt thereof.

[0028]

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[0029] In the formula ^{(4), R 1, R} 2, R 3 is hydrogen, an alkyl group, an aryl group or an aralkyl group, R ^1,
Any ^{two of} R ² and R ³ may combine to form a ring,
X is an anion. ].

That is, the carboxyl group in betaine becomes a free carboxylic acid group which has not been dissociated in the presence of a strong acid, and functions as a cation instead of betaine. There is no problem if the polymer of the present invention is used as a cation in the presence of a strong acid.

The form of the carboxyl group of the betaine group in the polymer of the present invention is not particularly limited. Specifically, it may be an ammonium group in the betaine group and a counter ion (betaine), a free carboxyl group, or a carboxylic acid salt. In this,
An amino group in the betaine group and a counter ion (betaine) or a free carboxyl group are preferred.

The form of the ammonium group of the betaine group is not particularly limited as long as it is other than a primary amine, but quaternary ammonium is preferred. Specifically, an alkyl group, an aryl group,
Ammonium to which three of the aralkyl groups are bonded. In these, two substituents may combine to form a ring. For example, an ethylene imine ring, a piperidine ring,
And a morpholine ring.

In the polymer of the present invention, the number of repeating units having a pendant group containing a betaine group or a salt thereof varies depending on the intended use. In the case of a water-soluble polymer, it is preferably 1 to 99.8%, more preferably 10 to 99.8%, based on the total number of repeating units constituting the molecule. The type of the other repeating unit is not particularly limited, but is preferably a unit containing a hydrophilic substituent.

In the case of a polymer having surface activity, it is preferably 10 to 90%, more preferably 30 to 70%, and more preferably 40 to 60%, based on the total number of repeating units constituting the molecule.
Is particularly preferred. The type of the other repeating unit is not particularly limited, but is preferably a long chain alkyl group, an aryl group, an aralkyl group or the like having hydrophobicity.

In the case of an oil-soluble polymer, it is preferably from 1 to 30% with respect to the total number of repeating units constituting the molecule,
-20% is more preferable, and 1-10% is particularly preferable.
The type of the other repeating unit is not particularly limited, but is preferably a long chain alkyl group, an aryl group, an aralkyl group or the like having hydrophobicity.

The polymer of the present invention is preferably one of water-soluble, water-swellable, oil-soluble, and oil-swellable. These properties are determined by the balance between the repeating unit containing the zwitterion and the hydrophobic moiety contained elsewhere. The ratio is
Although it cannot be unambiguously determined, generally, when the number of repeating units is large, the tendency of water solubility is high, and when the number of hydrophobic parts is large, the tendency of oil solubility is high. In addition, there is a portion between these, where water swelling and oil swelling can be exhibited. The water swellability also changes depending on the pH, temperature, etc. of the aqueous solution, and may become water-soluble at high temperatures.

When the polymer of the present invention comprises an acidic polyamino acid, typically, a repeating unit represented by the following general formula (2a) and a repeating unit represented by the following general formula (2b) are exemplified. Can be

[0038]

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In the formulas (2a) and (2b), R is an organic residue, X ¹ is NH, N (R ′) (R ′ is an alkyl group, an aryl group or an aralkyl group), O or S , R ¹ ,
R ² and R ³ are hydrogen, an alkyl group, an aryl group or an aralkyl group, and any ^{two of} R ¹ , R ² and R ³ may combine to form a ring, and n is 1 or 2 . ].

In the general formulas (2a) and (2b), the side chain structure includes X ¹ bonded to the polymer main chain, and a pendant group having at least one betaine group [general formula (1)] or a salt thereof. (R + betaine group).

The pendant group (R + betaine group)
In the case of polyaspartic acid, it may be substituted at the α-position or at the β-position with respect to the amide bond of the polymer main chain. In the case of polyglutamic acid, even when substituted at the α-position to the amide bond of the polymer main chain, γ
It may be substituted at the position.

X ¹ is -NH-, -NR'-, -O-, -S-
And a single bond or a mixture of a plurality of these bonds. Here, R ′ is, for example, an optionally branched alkyl group, aralkyl group, or aryl group having 1 to 16 carbon atoms.

In the general formulas (2a) and (2b), R
And X ¹ may be a polymer having only the same repeating unit, or R and X ¹ may be a polymer having different repeating units at the same time. R ′ in X ¹
Is preferably an aralkyl, phenyl or naphthyl group, and in the case of an alkyl group, is preferably an alkyl group having 1 to 20 carbon atoms which may be branched.

The organic residue portion (R) other than the betaine group or a salt thereof constituting the pendant group is not particularly limited, and examples thereof include an alkylene, aralkylene, phenylene, and naphthylene group. These may be linear or branched. Further, the substitution position of the betaine group with respect to the organic residue is not particularly limited. Among these organic residues, an alkylene group is preferable in view of biodegradability and the like, and those derived from lysine or ornithine are particularly preferable.

The organic residue (R) constituting the pendant group may be unsubstituted or substituted. When the organic residue is substituted, specific examples of the substituent include C1 to C18.
An alkyl group which may be branched, a cycloalkyl group having 3 to 8 carbon atoms, an aralkyl group, a phenyl group which may be substituted, a naphthyl group which may be substituted,
8, an optionally branched alkoxy group, an aralkyloxy group, a phenylthio group, an optionally branched alkylthio group having 1 to 18 carbon atoms, an optionally branched alkylamino group having 1 to 18 carbon atoms, A branched dialkylamino group having 1 to 18 carbon atoms, a trialkylammonium group optionally having 1 to 18 carbon atoms, a hydroxyl group, an amino group, a mercapto group, a carboxyl group, a sulfone group,
Phosphon groups and salts thereof, alkoxycarbonyl groups,
And an alkylcarbonyloxy group. Further, a primary amine, a secondary amine, or a tertiary amine which has insufficient quaternary cationization reaction in the production process of the betaine group may be contained.

(3) Method for Producing Polymer The method for producing the polymer of the present invention is not particularly limited, but a method for introducing a pendant group into a polymer after polymerization and a method for introducing a pendant group into a polymerizable monomer. There is a method of performing polymerization later. In addition, there is a method of deriving a betaine group into a polymer containing a pendant group containing a substituent which is a precursor of the betaine group.

Among them, a method of introducing a pendant group into a polymer after polymerization and a method of introducing a betaine group into a polymer containing a pendant group containing a substituent which is a precursor of a betaine group are preferable. At this time, there is also a method of introducing a pendant group containing a substituent serving as a precursor of a betaine group into the polymer after polymerization.

The polymer used in the method for introducing a pendant group into the polymer after polymerization includes polyacrylic acid, a copolymer of polyacrylic acid and vinyl acetate, and a partial hydrolyzate of a copolymer of polyacrylic acid and vinyl acetate. Hydrolyzate, copolymer of polyacrylic acid and vinylacetamide, partial hydrolyzate of starch-acrylonitrile copolymer, starch-acrylic acid graft copolymer, hydrolyzate of vinyl acetate-acrylic ester copolymer, poly 2 -Acrylamide-methylpropanesulfonic acid, copolymer of 2-acrylamide-methylpropanesulfonic acid and acrylic acid, copolymer of 2-acrylamide-methylpropanesulfonic acid and vinyl acetate,
Hydrolyzate of isobutylene-maleic anhydride copolymer,
Poly (2-hydroxyacrylic acid), a copolymer of acrylic acid and poly (2-hydroxyacrylic acid), carboxymethylcellulose, carboxymethylated starch, polyaspartic acid, polyglutamic acid, and the like. Further, polysuccinimide obtained by dehydrating one molecule of water from an acidic polyamino acid may be used.

The method for introducing a pendant group into the polymer after polymerization is basically the same as the method for producing a polymer using an acidic polyamino acid in the method for producing a polyaspartic acid-based resin (4) described later. Therefore, it is described in the column of (4).

In the method of performing polymerization after introducing a pendant group into a polymerizable monomer, of the above-mentioned polymers, those which polymerize using a reactive unsaturated bond and those which polymerize using a dehydration condensation And a copolymer of the above polymer is obtained.

Here, a substituent useful as a betaine group precursor (hereinafter, referred to as a betaine precursor group) is a substituent having a carboxyl group and an amino group.
The amino group can be converted to betaine by quaternary ammonium.

(4) Method for Producing Polyaspartic Acid Resin The method for producing a polyaspartic acid resin which is more useful as the polymer of the present invention will be described.

As a method for producing a polyaspartic acid-based resin having a pendant group containing a betaine group, the polyaspartic acid contains a betaine group or a betaine precursor group as in the method described in the above section (3). There are a method of introducing a pendant group and a method of polymerizing a monomer having a pendant group containing a betaine group or a betaine precursor group.

Further, in the case of polyaspartic acid, there is a method using a polysuccinimide having a structure in which one molecule of water is dehydrated from a polyaspartic acid unit. This method of introducing a pendant group into polysuccinimide is particularly preferable because the reaction proceeds under mild conditions and there are no by-products.

Since it is difficult to industrially obtain a reagent containing a betaine group itself, it is preferable to perform betaine (cationization or the like) after the reaction of the reaction reagent containing a betaine precursor group.

[Method for Producing Polymer Using Polysuccinimide] The method for producing a polymer using polysuccinimide utilizes a nucleophilic addition reaction of an amine or the like in a reaction reagent to an imide ring of polysuccinimide. Can be implemented. Specifically, it is a method in which a pendant group is formed by reacting a reaction reagent having an amine or the like capable of reacting with an imide ring. The pendant group contains a betaine group or a substituent that becomes a betaine precursor group thereof. Here, the solubility and reactivity of the reaction reagent may be different due to the inclusion of a substituent that becomes a betaine group or a betaine precursor group, but as a basic reaction, it does not matter whether these substituents are included. Since there is no particular difference, both will be described here.

The method for producing polysuccinimide is not particularly limited, but is described in Journal of American Chemical Society (J. Amer. Chem. Soc.), 8
0, p. 3361-(1958).

The molecular weight of the polysuccinimide used is:
It is not particularly limited, and varies depending on the intended use. For example, when film forming ability is required, the higher the molecular weight, the better,
A low molecular weight is preferred to achieve fast degradability.
Generally, the weight average molecular weight is 1000 or more and 1,000,000 or less. The appropriate molecular weight depends on the application used.

The reaction for introducing the pendant group into the polysuccinimide is not particularly limited, but may be carried out in a good solvent for the polysuccinimide, in a good solvent for the polymer to be produced, or in the reaction for forming the pendant group. Examples of the method include a method in which the reagent is performed in a good solvent and a method in which the reagent is performed in a solid phase.
Among these, a method performed in a good solvent for polysuccinimide and a method performed in a good solvent for a polymer to be formed are preferable.

The solvent used for the pendant group introduction reaction is preferably a solvent capable of dissolving a polysuccinimide or polyaspartic acid-based resin, or a solvent capable of dissolving a reaction agent that can be a pendant group. Any solvent can be used.

As a solvent capable of dissolving the polysuccinimide or polyaspartic resin, for example, N, N
-Dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N, N'-dimethylimidazolidinone, dimethylsulfoxide, sulfolane and the like. Among them, N, N-dimethylformamide and N, N-dimethylacetamide, which have high solubility of polysuccinimide, are particularly preferable.

A highly polar solvent is preferable for a polyaspartic acid-based resin having a pendant group containing a betaine group or a betaine precursor group, and a reaction reagent that can be a pendant group containing a betaine group or a betaine precursor group. . For example, water, methanol, ethanol, propanol, acetone, methyl ethyl ketone and the like can be mentioned. Of these, water, methanol and ethanol are preferred, and water is particularly preferred. These solvents may be used alone or in combination of two or more.

The reactant which can be a pendant group used in the present invention includes amines, alcohols and thiols containing a betaine group or a betaine precursor group.
Examples of the reagent containing a betaine precursor group include amines, alcohols, and thiols containing a glycino group or its precursor. These may be deprotected after the reaction by protecting the carboxyl or amino group of the glycino group. For example, a carboxyl group may be reacted in the form of a salt of a carboxylic acid ester, an amide, or a carboxylic acid, and after a reaction such as hydrolysis or salt exchange, it may be derived into a carboxylic acid. Alternatively, the amino group of the glycino group may be converted to an amide, a salt, or the like, and the amino group may be derived after the reaction.

The amount of the reaction reagent which can be used as a pendant group is not particularly limited, but is preferably 1 to 99.8 mol%, more preferably 10 to 99.8 mol% based on polysuccinimide.
Molar% is preferred.

As a reaction reagent, there are a reaction reagent containing a betaine group and a reaction reagent containing a betaine precursor group, but a reaction reagent containing a betaine precursor group is easily available industrially.

For example, as a reaction reagent containing a betaine precursor group, a compound represented by the following general formula (3) is preferable.

[0067]

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[In the formula (3), Y is NH ₂ , NH (R ′)
(R ′ is an alkyl group, an aryl group or an aralkyl group),
OH or SH, and Z is an organic residue. ].

The compound represented by the general formula (3)
In particular, amine compounds such as lysine and ornithine are preferred.

The amine compound used in the reaction with the polysuccinimide used in the present invention is particularly preferably a primary amine. Further, it is preferable that the carbon at the α-position where the amino group is present is not branched. When Y is OH or SH, it can be reacted as an alcoholate or thiolate to increase the reactivity.

The pendant group introduction reaction may use a catalyst if necessary. Generally, a base catalyst is used as the catalyst.

The reaction product after the pendant group introduction reaction is:
In some cases, a part of the remaining imide ring may be hydrolyzed, or another pendant group may be introduced. These reactions can be performed before the introduction of the pendant group (including a betaine group or a betaine precursor group) of the present invention,
You may go later. Generally, when a highly hydrophilic substituent is introduced, it is preferable to use a polar solvent such as the above-mentioned water. In the case of introducing a pendant group having high hydrophobicity, it is preferable to introduce the pendant group in a good solvent of polysuccinimide. That is, the selection of the solvent at the time of the reaction may be appropriately determined in consideration of the other pendant group introduction reaction and the pendant group introduction reaction according to the present invention. Further, two or more solvents can be used in combination.

When the ring opening reaction of the remaining imide ring is carried out, it is carried out in water or an organic solvent miscible with water. The reagent that can be used for opening the remaining imide ring is not particularly limited, but generally alkaline water is used.

After the pendant group introduction reaction or after the ring opening reaction of the remaining imide ring, the carboxylic acid can be neutralized and used if necessary. The degree of neutralization is not particularly limited, but is preferably from 0 to 50 mol%, particularly preferably from 0 to 30 mol%, as a monomer unit. The method of neutralization is not particularly limited. For example, a method of adjusting the pH by adding an acid after the ring-opening reaction of the remaining imide ring may be used.

After the ring-opening reaction of the remaining imide ring, the carboxylic acid or a salt of the carboxylic acid can be replaced with another salt if necessary. Counter ions used for salt exchange include alkali metal salts, ammonium salts, amine salts and the like.

In this case, when the molecular weight of the counter ion becomes large, the molecular weight per monomer unit becomes relatively large and the amount of water absorption per unit mass becomes small. Therefore, the molecular weight of the counter ion is preferably small. When there is a possibility of touching human skin or the like, the less irritating to the skin or the like is better, and inorganic salts or ammonium salts are preferable. Among them, sodium, potassium, lithium, ammonium and amine salts of triethanolamine are preferable, and sodium and potassium are particularly preferable in view of cost.

The drying temperature of the resin after the alkali ring opening is not particularly limited, but is generally preferably from 20 to 150 ° C.
Particularly, 40 to 100 ° C is preferable.

[Method for Producing Polymer Using Acidic Polyamino Acid] The method for producing a polymer using acidic polyamino acid is as follows.
It can be produced by utilizing a dehydration condensation reaction or an addition reaction of a carboxyl group of an acidic polyamino acid with an amine or the like in a reaction reagent. Specifically, it is a method in which a pendant group is produced by reacting a reaction reagent having an amine or the like capable of reacting with a carboxyl group. This pendant group has
It contains a betaine group or a substituent that becomes a precursor thereof. Here, the solubility and reactivity of the reaction reagent may be different due to the inclusion of a betaine group or a substituent that becomes a precursor thereof, but as a basic reaction, even if these substituents are included, Since there is no particular difference, both will be described here. The method for producing a polymer using an acidic polyamino acid is not particularly limited, but there is no significant difference between polyaspartic acid and polyglutamic acid. Further, the method of the present invention can be applied to a polymer having an acidic group other than the acidic polyamino acid.

The pendant group introduction reaction of polyaspartic acid is not particularly limited, and may be a liquid phase or a solid phase reaction. In the case of a liquid phase reaction, polyaspartic acid or a polyaspartic acid derivative is dissolved in a solvent, or a reagent that can become a pendant group is dissolved and reacted. The solid phase reaction is
Since the reactants need to be mixed to some extent homogeneously, by mixing or shaking or stirring the reactor or the contents, or by forming a solution or a dispersion and removing the solvent, Mix.

The solvent used in the liquid phase reaction is not particularly limited, but is generally water, methanol, ethanol, propanol, isopropanol, butanol,
Alcohols such as 2-methoxyethanol and 2-ethoxyethanol, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; tetrahydrofuran and dioxane Cyclic ether, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N, N'-dimethylimidazolidinone, dimethylsulfoxide, sulfolane and the like. Among these, water, N-methylpyrrolidone, N, N'-dimethylimidazolidinone, dimethylsulfoxide, and sulfolane, which can dissolve the acidic polyamino acid, are preferable.

As a method of introducing a pendant group into a polymer having an acidic group, a method of dehydrating and condensing a polymer capable of becoming a pendant group with a polymer having an acidic group is generally used.

The dehydration condensation may be carried out by 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 with a dehydrating condensing agent, and a method of using an enzyme. Alternatively, a polymer having an acidic group can be mixed uniformly, and the reaction can be carried out in a solid phase state from which the solvent has been 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, bis (2-nitrophenyl ester) phenylphosphonic acid, cyano Diethyl phosphonate,
Phosphorus-containing compounds such as diphenylphosphoroazide; redox condensing agents such as 2-fluoro-1-ethylpyridinium tetrafluoroborate; triphenylphosphine / bis (benzothiazole) disulfide; tributylphosphine / bis (benzothiazole) disulfide; Is mentioned. Examples of enzymes include penicillin acylase,
Lipases such as yeast lipase and the like can be mentioned.

The reaction temperature during the dehydration condensation is not particularly limited, and varies depending on the dehydration condensing agent used. When an acid catalyst or a catalyst is not used, the temperature is preferably from 20 to 250 ° C.
0-180 ° C is particularly preferred. When a dehydrating condensing agent is used, the reaction often proceeds under mild conditions,
The reaction proceeds at about 100 ° C.

Further, the acidic group of the polymer having an acidic group may be activated and used. For example, esterification, amidation, and thioesterification are used. In this case, ordinary reaction conditions used in organic chemistry can be used. Further, examples of the derivative of the acidic group include an acid anhydride and an acid halide.

Examples of these reactions include, for example, a method in which an acid group is subjected to a dehydration condensation reaction with an alcohol, an amine, or a thiol, or a method in which an acid group is activated with an acid anhydride, an acid halide, an acid azide or the like to activate an alcohol, an amine, or the like. A method of reacting with a thiol, a method of reacting with an activated group by reacting an alcohol or an amine, for example, an alcohol is converted to a halide, a sulfonic acid ester or a sulfate, and an amine is converted to a silicon derivative. Method, an alcohol activated with an acidic group, for example, a halide, an ester sulfonate, a sulfate, an amine, a method of reacting as a silicon derivative, an acidic group and an epoxy compound, an isocyanate compound, an aziridine compound,
There are a method of reacting with an alkyl metal or the like, a method of reacting an acid group with a halide or the like as a salt, and a method of reacting an acidic group as an active ester by transesterification or ester-amide exchange.

Examples of the active ester include alcohol components having a small number of carbon atoms, such as methyl and ethyl; alcohol components having an electron-withdrawing group, such as chloromethyl and dichloromethyl;
Alcohols such as -hydroxysuccinimide.

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

As the reaction reagent, there are a reaction reagent containing a betaine group and a reaction reagent containing a betaine precursor group, but a reaction reagent containing a betaine precursor group is easily available industrially. For example, as a reaction reagent containing a betaine precursor group, a compound represented by the following general formula (3) is preferable.

[0090]

Embedded image

[In the formula (3), Y is NH ₂ , NH (R ′)
(R ′ is an alkyl group, an aryl group or an aralkyl group),
OH or SH, and Z is an organic residue. ].

The compound represented by the general formula (3) is
In particular, amine compounds such as lysine and ornithine are preferred.

Here, in the case of the precursor, it is desirable to reduce the reactivity by adding an acid or attaching a protective group when performing the dehydration condensation or addition reaction.

[Cationization Reaction and Betaininization] In the process for producing the polymer of the present invention, a method of introducing a substituent which becomes a betaine precursor and then changing it to a betaine group is a very effective method.

Useful as a betaine precursor is a substituent having a carboxyl group and an amino group, and the amino group can be converted to betaine by quaternary ammoniumation. Specifically, a method of converting the amino group contained in the precursor into a quaternary ammonium is desirable. Less than,
The cationization reaction will be described.

The cationization reaction and betaine reaction of the present invention are methods in which a precursor that can be a cation group or a betaine group in a pendant group of a polymer is reacted with a cationizing agent or a betaining agent. In the present invention, for the sake of convenience, a substituent that can be a cationic group and / or a betaine group is referred to as a precursor.

First, the introduction reaction of a pendant group containing a precursor will be described. The reaction conditions for the introduction reaction of the pendant group containing the precursor are not particularly limited, but are described in the section of [Method for producing polymer using polysuccinimide] [Method for producing polymer using acidic polyamino acid]. It can be performed under reaction conditions.

The precursor which can be an ammonium ion is
Primary amines, secondary amines, tertiary amines or cationizing agents are not particularly limited, but primary amines, secondary amines, and tertiary amines are preferred, and tertiary amines are particularly preferred from the viewpoint of reactivity, and Primary amines are preferred from the standpoint of easiness. The substitution position of these pendant groups is not particularly limited.

The ammonium formed does not contain a primary amine. Quaternary ammonium, tertiary amine ammonium,
Secondary amines include ammonium. Of these, quaternary ammonium is preferred.

Next, a cationization reaction in which a precursor capable of forming a cationic group is reacted with a cationizing agent will be described. In addition, for the pendant group contained in the polymer,
Of a precursor or a cationizing agent that can be a cationic group,
Either may be included. That is, a cationizing agent may be reacted with a polymer containing a cation group-containing precursor in a pendant group, or a precursor containing a cationizing agent in a pendant group may be added to a polymer containing a cationizing agent in a pendant group. The body may react.

Here, since many cationizing agents are highly toxic, it is not preferable that they remain. That is,
In consideration of the possibility that unreacted groups remain, it is preferable to react a cationizing agent with a pendant group containing a precursor that can be a cationic group.

The cationizing agent is not particularly restricted but includes chlorides, bromides, iodides, sulfonic esters,
Some use substitution reactions of sulfate esters, alkyl metals, azides and the like, and others use addition reactions of reactive unsaturated compounds, epoxy compounds, aziridine, thiirane and the like.

For example, methane chloride, ethane chloride, propane chloride, 2-chloropropane, 1-chlorobutane,
Alkyl chlorides such as chlorobutane, 1-chloropentane, 2-chloropentane, 3-chloropentane, 1-chlorohexane, 2-chlorohexane, 3-chlorohexane, 1-chlorooctane, 1-chlorodecane, 1-chlorotetradecane , Methane bromide, ethane bromide, propane bromide, 2-bromopropane, 1-bromobutane, 2-bromobutane, 1-bromopentane, 2-bromopentane,
3-bromopentane, 1-bromohexane, 2-bromohexane, 3-bromohexane, 1-bromooctane,
Alkyl bromides such as 1-bromodecane and 1-bromotetradecane, iodomethane, iodoethane, iodopropane, 2-iodopropane, 1-iodobutane, 2-iodobutane, 1-iodopentane, 2-iodopentane,
3-iodopentane, 1-iodohexane, 2-iodohexane, 3-iodohexane, 1-iodooctane,
Alkyl iodides such as 1-iododecane and 1-iodotetradecane, monosulfates such as methyl sulfate, ethyl sulfate, propyl sulfate, butyl sulfate, pentyl sulfate, hexyl sulfate, octyl sulfate, decyl sulfate and tetradecyl sulfate, dimethyl sulfate, and sulfuric acid Diethyl, dipropyl sulfate, dibutyl sulfate, dipentyl sulfate, dihexyl sulfate,
Diester sulfates such as dioctyl sulfate, didecyl sulfate and ditetradecyl sulfate, methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, pentyl methanesulfonate, hexyl methanesulfonate, octyl methanesulfonate, decyl methanesulfonate, methanesulfone Acid tetradecyl, methyl ethanesulfonate, ethyl ethanesulfonate, propyl ethanesulfonate, pentyl ethanesulfonate, hexyl ethanesulfonate,
Octyl ethanesulfonate, decyl ethanesulfonate,
Tetradecyl ethanesulfonate, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, propyl trifluoromethanesulfonate, pentyl trifluoromethanesulfonate, hexyl trifluoromethanesulfonate, octyl trifluoromethanesulfonate, decyl trifluoromethanesulfonate, trifluoromethanesulfone Acid tetradecyl, methyl benzenesulfonate, ethyl benzenesulfonate, propylbenzenesulfonate, pentylbenzenesulfonate, hexylbenzenesulfonate, octylbenzenesulfonate, decylbenzenesulfonate, tetradecylbenzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, p
Sulfonic acid esters such as pentyl toluenesulfonate, hexyl p-toluenesulfonate, octyl p-toluenesulfonate, decyl p-toluenesulfonate, and tetradecyl p-toluenesulfonate;

Further, epoxy compounds such as ethylene oxide, propylene oxide and epichlorohydrin can be used.

Among these, it is preferable that the molecular weight of the obtained cation group itself is not high, and that the cation group has high reactivity and is easily removed after the reaction.

After the introduction reaction or the cationization reaction of a pendant group containing a cationic group, the counter ion of the cationic group can be subjected to salt exchange, if necessary.

The cationization reaction temperature is not particularly limited.
What is necessary is just to select the temperature at which the main chain of the polymer is not cleaved and the reaction sufficiently proceeds. For example, 10 to 200C is preferable, 30 to 150C is more preferable, and 40 to 100C is particularly preferable.

The solvent used in the reaction is not particularly limited.
There is no particular limitation as long as the cationizing agent does not react and the reaction proceeds, but those capable of dissolving the raw materials or products are preferable. As examples thereof, the solvents described in the section of (4) [Method for producing polymer using polysuccinimide] and [Method for producing polymer using acidic polyamino acid] can be used.

In the present invention, the betaine-forming reaction means reacting a precursor which can be a betaine group with a betaine-forming agent. For example, there is a method in which a betaine agent is reacted with a polymer containing a pendant group having a precursor that can be a betaine group.

After the reaction for introducing a pendant group containing a betaine group or after the reaction for betaine formation, the anion group in the betaine group may be made nonionic by making the reaction system acidic if necessary.

Acids which make anionic groups nonionic include hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfurous acid, nitric acid,
Inorganic acids such as nitrous acid and phosphoric acid, carboxylic acids such as formic acid, acetic acid, propionic acid and benzoic acid, sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and toluenesulfonic acid, and benzenephosphonic acid. No. In this case, the acid must be stronger than the anion in the pendant group.

On the other hand, the carboxyl group in the betaine group of the polymer of the present invention can be used as a salt, if necessary. The ions forming the carboxylate are not particularly limited. Specific examples of the ion forming the salt of the carboxylic acid include, for example, alkali metal ions such as sodium, potassium and lithium, tetramethylammonium, tetraethylammonium, tetrapropylammonium,
Tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, ethyltrimethylammonium, trimethylpropylammonium, butyltrimethylammonium, pentyltrimethylammonium, hexyltrimethylammonium, cyclohexyltrimethylammonium, benzyltrimethylammonium, triethylpropylammonium, triethylbutylammonium, triethylpentyl Ammonium, ammonium ions such as triethylhexylammonium, cyclohexyltriethylammonium, benzyltriethylammonium, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triethanolamine, triethanolamine Lopananolamine, tributanolamine, tripentanolamine, trihexanolamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dicyclohexylamine, dibenzylamine, ethylmethylamine, methylpropylamine, butylmethyl Amine, methylpentylamine, methylhexylamine, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine,
Examples thereof include amine ions such as octylamine, decylamine, dodecylamine, and hexadecylamine.

Among these, considering the influence of the amino group on the reactivity, those having a small molecular weight and a weak acidity of the conjugate acid are preferred. When there is a possibility of touching human skin or the like, it is preferable that skin irritation is low. From these points, it is preferable to use sodium, potassium, lithium, and ammonium.
The use of potassium is particularly preferred in terms of cost.

[Post-treatment after Production of Polymer] The method of isolating the produced polymer from the reaction solution after the completion of the reaction employed in the production method of the polymer of the present invention substantially removes the reaction product from the desired product. There is no particular limitation as long as it can be isolated with a purity. 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.

(5) Uses of the Polymer The use of the polymer of the present invention is not particularly limited. However, 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, examples of the interface-acting type high molecular drug include:
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.

[0118] The surface-acting high-molecular-weight agents mainly used for surface protection include coating polymers, floor polishing polymers, tablet coating agents, masking agents, and the like.
Coating agents for optical fibers, plastic / hard coat agents, polymers for photoresists, moisture-proof coating agents for printed wiring boards, etc., are mainly used for surface modification, such as paper sizing agents, paper strength agents, Polishing coating agents, textile anti-staining agents, antistatic agents / conductive agents, electromagnetic wave shielding coating agents, concrete waterproofing agents, primers, and the like.

[0119] As the internally acting polymer chemicals, the ones mainly for thickening include printing pastes, polymers for increasing crude oil, polymers for civil engineering, polymers for quenching oil, polymers for hydraulic fluid. , 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 polymer having a binding action include a builder, a chelate polymer, a dye fixing agent, an epoxy resin curing agent and the like.

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

(6) Uses of cosmetics (materials) and cosmetics (materials) The polymer of the present invention can be usefully used for cosmetics and cosmetics.

As used herein, the concepts of “cosmetics”, “cosmetics”, “cosmetics” and “cosmetics” include:
For example, "Text of the 26th New Employee Cosmetic Technology Seminar" (co-sponsored by the Tokyo Cosmetic Industry Association and Tokyo Cosmetic Engineers Association, co-sponsored by the Japan Cosmetic Industry Association, June 1994, Asahi Life Hall), pages 34 and 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 terms “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.

[0126]

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”. The evaluation methods (1) to (6) employed in 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 produced polymer, the monomer and pendant obtained by hydrolysis were subjected to high performance liquid chromatography (hereinafter referred to as HPLC). Abbreviation).
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.) All basic amino acid derivatives were calculated as basic amino acid derivatives.

(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 (2), 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: N2 20 ml / min. Detector: FID103 × 8 Sample size: 0.4 μL.

(4) Skin irritation The test was carried out using three white rabbits per polymer according to the Draize method (OECD guideline; No. 404). 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 (%). Here, some of the samples that are easily biodegradable promote the decomposition of even the carbon content in the inocula, and in this case, some of the samples have a value exceeding 100%.

(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 sodium polyoxyethylene (20 mol addition) lauryl ether sulfate Wt%, ethanol 8.0 wt%, glycerin 5.
0% by mass, 4.0% by mass of propylene glycol, 0.2% by mass of citric acid, residue of purified water 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 of 10 parts of polysuccinimide (hereinafter abbreviated as PSI) having an Mw of 96,000 in 20 parts of N, N-dimethylformamide (hereinafter abbreviated as DMF). Add 4 parts at 60 ° C
Allowed to react for hours. The reaction solution was discharged into 200 parts of distilled water, and the precipitate was collected by suction filtration and washed with 50 parts of distilled water.
The obtained wet cake was dispersed in 50 parts of water and 20 parts of methanol, and 20.9 parts of a 50% aqueous lysine solution was added.
The reaction was performed at a temperature of 3 ° C. for 3 hours. The obtained reaction product is treated with acetone 40
The mixture was discharged to 0 part, and the precipitate was collected by suction filtration and dried at 60 ° C.

Further, after drying, the obtained polymer was suspended in 100 parts of ethanol, charged with 33.8 parts of methyl iodide and 50 parts of pyridine, and reacted at 40 ° C. for 8 hours.
After the reaction, the mixture was cooled to room temperature, discharged into 500 parts of acetone, and the precipitate was collected by suction filtration, washed with 200 parts of acetone, and dried at 60 ° C. to obtain 27.4 parts of a polymer. .

The decomposition product of the obtained polymer was analyzed by HPLC and G
When analyzed by C, the composition of the polymer was aspartic acid:
Lysine derivative: laurylamine = 100: 71: 28
(Mol / mol / mol). The skin irritation of the obtained polymer was ○, and the biodegradability was 98%, indicating good biodegradability. In the sensory test, smoothness was 2.8, moist feeling was 2.9, and sticky feeling was 2.7.

[Example 2] In Example 1, Mw9.
Processing was performed in the same manner as in Example 1 except that a PSI of Mw 56,000 was used instead of the PSI of 60,000. After drying, 26.9 parts of polymer were obtained. The composition of the obtained polymer was aspartic acid: lysine derivative: laurylamine = 10
0:69:27 (mol / mol / mol). The skin irritation of the obtained polymer was ○, and the biodegradation rate was 101%.
And good biodegradability. The sensory test was 2.7 for smoothness, 2.9 for moist feeling, and 2.6 for sticky feeling.
Good results.

[Embodiment 3] In the embodiment 1, Mw9.
Processing was performed in the same manner as in Example 1 except that a PSI of Mw 16,000 was used instead of the PSI of 60,000. After drying, 26.2 parts of polymer were obtained. The composition of the obtained polymer was aspartic acid: lysine derivative: laurylamine = 10
0:65:27 (mol / mol / mol). The skin irritation of the obtained polymer was ○, and the biodegradation rate was 101%.
And good biodegradability. In the sensory test, the smoothness was 2.6, the moist feeling was 2.8, and the stickiness was 2.4.
Good results.

Example 4 In Example 1, lysine
A treatment was carried out in the same manner as in Example 1 except that an aqueous solution in which 13.03 parts of ornithine monohydrochloride and 2.88 parts of sodium hydroxide were dissolved in 20 parts of distilled water was used instead of the monohydrochloride. After drying, 26.9 parts of polymer were obtained. The composition of the obtained polymer was aspartic acid: ornithine derivative: laurylamine = 100: 72: 28 (mol / mol / mol). The skin irritation of the obtained polymer was ○, and the biodegradability was 98%, indicating good biodegradability. In the sensory test, smoothness was 2.8, moist feeling was 2.8, and sticky feeling was 2.7.

Example 5 The procedure of Example 1 was repeated except that 7.64 parts of laurylamine and 17.95 of a 50% aqueous lysine solution were used.
And 29.0 parts of methyl iodide. After drying, 29.5 parts of polymer were obtained. The composition of the obtained polymer was aspartic acid: lysine derivative: laurylamine = 100: 58: 39 (mol / mol / mol). The skin irritation of the obtained polymer was ○, and the biodegradability was 98%, indicating good biodegradability. In addition, in the sensory test, smoothness 2.7 and moist feeling 2.
6. The sticky feeling was 2.8, which was a good result.

[Example 6] In Example 1, 9.55 parts of laurylamine, 10.35 parts of lysine monohydrochloride in lysine aqueous solution, 2.27 parts of sodium hydroxide and 24.1 parts of methyl iodide were used. Processing was performed in the same manner as in Example 1 except that the parts were changed. After drying, 28.1 parts of polymer were obtained. The composition of the obtained polymer was aspartic acid: lysine: laurylamine = 100: 48: 48 (mol / mol / mol). The skin irritation of the obtained polymer was ○, and the biodegradability was 107%, indicating good biodegradability. The organoleptic test showed a smoothness of 2.6, a moist feeling of 2.9, and a sticky feeling of 2.5, which were favorable results.

Example 7 The procedure of Example 1 was repeated, except that 7.46 parts of stearylamine was used instead of laurylamine. After drying, 30.6 parts of polymer were obtained. The composition of the obtained polymer was aspartic acid: lysine: stearylamine = 100: 7.
2:26 (mol / mol / mol). The skin irritation of the obtained polymer was ○, and the biodegradability was 96%, indicating good biodegradability. In addition, the sensory test showed smoothness of 2.
8, a moist feeling of 2.6 and a sticky feeling of 2.8 were good results.

Example 8 The procedure of Example 1 was repeated, except that 4.00 parts of octylamine was used instead of laurylamine. After drying, 26.2 parts of polymer were obtained. The composition of the obtained polymer was aspartic acid: lysine: octylamine = 100: 70:
29 (mol / mol / mol). The skin irritation of the obtained polymer was ○, and the biodegradability was 103%, indicating good biodegradability. In addition, the sensory test showed a smoothness of 2.6,
The wet feeling was 2.8 and the sticky feeling was 2.6, which was a good result.

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 an 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.

[0149]

As described above, according to the present invention,
It is excellent in biodegradability, has no irritation to the living body, is excellent in safety after decomposition, and is further improved in terms of moisturizing properties, etc., and can satisfy various required characteristics in a wide range of applications. A polymer and a method for producing the polymer can be provided.

That is, the acidic polyamino acid derivative having a betaine group or a pendant group containing a salt thereof, which has high biocompatibility and safety to the living body and can impart high hydrophilicity, and which is obtained by the present invention, is useful for the living body (for example, 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 Takeshi Ishitoku 580-32, Takuji Nagaura, Sodegaura City, Chiba Prefecture (72) Inside the Mitsui Chemicals Co., Ltd. (72) Keisuke Takuma 580-32, Takuji Nagaura, Sodegaura City, Chiba Prefecture Mitsui Chemicals, Inc. F term (reference) 4J043 QB06 RA08 RA34 SA05 SA62 SB01 YB24 YB32 ZA03 ZA60 ZB01 ZB03 ZB33 ZB34 ZB44

Claims (14)

[Claims] 1. A polymer in which at least a part of the repeating units constituting a molecule has a betaine group represented by the following general formula (1) or a pendant group containing a salt thereof. Embedded image [In the formula (1), R ¹ , R ² , and R ³ are hydrogen, an alkyl group, an aryl group, or an aralkyl group, and any ^{two of} R ¹ , R ² , and R ³ are bonded to form a ring. Is also good. ] 2. The polymer according to claim 1, which is a polymer having a carboxyl group or a sulfonic acid group in the molecule. 3. The polymer according to claim 1, which has biodegradability. 4. The polymer according to claim 1, which has a repeating unit represented by the following general formula (2a) and / or a repeating unit represented by the following general formula (2b) in the molecule. Embedded image [In the formulas (2a) and (2b), R is an organic residue, X ¹ is NH, N (R ′) (R ′ is an alkyl group, an aryl group or an aralkyl group), O or S, and R ¹ , R ² and R ³ are hydrogen, an alkyl group, an aryl group or an aralkyl group;
Any ^{two of} R ¹ , R ² and R ³ may combine to form a ring, and n is 1 or 2. ] 5. In general formulas (2a) and (2b), n is
The polymer according to claim 4, which is 1. 6. X in the general formulas (2a) and (2b)
6. The polymer according to claim 4, wherein ¹ is NH. 7. The polymer according to claim 1, which is water-soluble, water-swellable, oil-soluble, or oil-swellable. 8. A non-crosslinked or finely crosslinked body.
8. The polymer according to claim 7. 9. A method for producing a polymer according to claim 1, wherein the polysuccinimide is reacted with a compound represented by the following general formula (3), and the amino group is further quaternized. A method for producing a polymer, comprising: Embedded image [In the formula (3), Y is NH ₂ , NH (R ′) (R ′ is an alkyl group, an aryl group or an aralkyl group), OH or SH
And Z is an organic residue. ] 10. A method for producing a polymer according to claim 1, wherein the polymer having an acidic group is reacted with a compound represented by the following general formula (3), and the amino group is further quaternized. A method for producing a polymer, comprising: Embedded image [In the formula (3), Y is NH ₂ , NH (R ′) (R ′ is an alkyl group, an aryl group or an aralkyl group), OH or SH
And Z is an organic residue. ] 11. The method according to claim 10, wherein the polymer having an acidic group is an acidic polyamino acid. 12. The method according to claim 10, wherein the polymer having an acidic group is polyaspartic acid. 13. A compound represented by the general formula (3):
The method for producing a polymer according to any one of claims 9 to 12, which is an amine compound. 14. A compound represented by the general formula (3):
The method for producing a polymer according to any one of claims 9 to 12, which is lysine or ornithine.