WO2002018494A1

WO2002018494A1 - Resin composition

Info

Publication number: WO2002018494A1
Application number: PCT/JP2001/007343
Authority: WO
Inventors: Toshio Shimamoto; Shigeru Sugiyama; Noboru Hoshi
Original assignee: Daido Chemical Corporation; Nisshin Kasei Co., Ltd.
Priority date: 2000-08-29
Filing date: 2001-08-28
Publication date: 2002-03-07
Also published as: AU2001280194A1

Abstract

A resin composition is provided, which is not attacked by solvents used for the dissolution of slightly soluble drugs. This composition is characterized by not being attacked by at least one member selected from the group consisting of polyethylene glycol and derivatives thereof, medium-chain fatty acids and salts thereof, polyoxyethylene sorbitan fatty acid esters polyoxyethylene castor oils, diethylene glycol ether derivatives, and polyhydric alcohols and derivatives thereof, which are soluble or dispersible in water having a pH of 10 or below and liquid at ordinary temperatures.

Description

Specification

Resin composition technology field

The present invention relates to (1) polyethylene glycol and a derivative thereof, wherein the resin film is dissolved or dispersed in water having a pH of 10 or less and is liquid at ordinary temperature, (2) medium-chain fatty acids and salts thereof, and (3) polyoxyethylene. Resin composition which is not affected by at least one selected from the group consisting of sorbitan fatty acid ester, (4) polyoxyethylene castor oil, (5) diethylene glycol ether derivative, and (6) polyhydric alcohol and its derivative. It is about things. Background technology

Features such as solubility and resistance of polymer compounds to various solvents are widely used in various industrial fields.

In pharmaceuticals, resin films that dissolve or disperse under acidic conditions are used as gastric-soluble coating agents and gastric-soluble hard capsule bases, or resin films that do not dissolve under acidic conditions but dissolve or disperse near neutrality. However, it has been used as an enteric coating agent and an enteric octacapsule base.

However, many of the medicinal components of drugs developed in recent years have poor water solubility (poorly soluble drugs), and often cause problems in absorption from the gastrointestinal tract. Various studies have been conducted on how to efficiently absorb such poorly soluble drugs. As a result, polyethylene glycol and its derivatives, medium-chain fatty acids and their salts, polyoxyethylene sorbitan fatty acid esters, The method of encapsulating and formulating a liquid in which a poorly soluble drug was dissolved in a dissolving agent such as oxyethylene castor oil, diethylene glycol ether derivative, polyhydric alcohol and its derivative was found to be effective.

However, if the above-mentioned dissolving agent is encapsulated in gelatin or cellulose derivatives that have been generally used as a base material of capsules, the gelatin has a significant decrease in capsule strength. Penetrate However, there was a problem that a so-called "sweat" phenomenon occurred. Disclosure of the invention

The present inventor has conducted intensive studies in view of the above-mentioned problems of the prior art, and as a result, has found that the following resin composition solves the problems.

Item 1. The resin film dissolves or disperses in water below pH10 and is liquid at room temperature.

(1) polyethylene glycol and its derivatives,

(2) medium-chain fatty acids and salts thereof,

(3) polyoxyethylene sorbitan fatty acid ester,

(4) Polyoxyethylene castor oil,

(5) a diethylene glycol ether derivative, and

(6) Polyhydric alcohol and its derivatives

A resin composition characterized by being unaffected by at least one member selected from the group consisting of:

Term 2. General formula [1]:

[1]

[In the formula, represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 1 to 4 carbon atoms, and R ₃ and R ₄ represent the same or different and represent 1 to 4 carbon atoms. A represents an oxygen atom or NH. ]

10 to 50% by weight of a polymerizable vinyl monomer represented by the following formula: 10 to 50% by weight of an organic acid having a polymerizable vinyl group or a salt thereof and 0 to 80% by weight of another polymerizable vinyl monomer Item 1. The resin composition according to Item 1, which contains a resin obtained by copolymerizing%.

Item 3. (a) From a solution obtained by dissolving chitosan having a degree of deacetylation of 60 mol% or more with an acid, or (mouth) chitosan having a degree of deacetylation of 60 mol% or more is acidified. After dissolving with at least one kind of polymerizable vinyl monomer, polymerize or copolymerize Item 2. The resin composition according to Item 1, which contains a resin obtained from a solution containing the obtained polymer or copolymer.

Item 4. In the presence of polyvinyl alcohol and / or a derivative thereof, at least one selected from the group consisting of an organic acid having a polymerizable vinyl group or a salt thereof and another polymerizable vinyl monomer is polymerized or copolymerized. The resin composition according to claim 1, comprising a resin obtained by polymerization.

In this specification, (meth) acryl means acryl and methacryl. For example, (meth) acrylic acid means acrylic acid and methacrylic acid. Similarly, (meth) acrylate means acrylate and methacrylate. For example, dimethylaminoethyl (meth) acrylate means dimethylaminoethyl acrylate and dimethylaminoethyl methyl acrylate.

The resin composition of the present invention is characterized in that the resin film is dissolved or dispersed in water having a pH of 10 or less and is liquid at ordinary temperature; (1) polyethylene glycol and a derivative thereof; (2) a medium-chain fatty acid and a salt thereof; ) Polyoxyethylene sorbitan fatty acid ester, (4) polyoxyethylene castor oil, (5) diethylene glycol ether derivative, and (6) at least one selected from the group consisting of polyhydric alcohols and derivatives thereof. The thickness of the resin film is appropriately selected according to its use, and for example, refers to a film having a thickness of about 0.01 to 5 mm, preferably about 0.05 to 1 mm. Here, the term “not eroded” means that the resin film does not dissolve in at least one of the compounds (1) to (6), does not show deterioration such as swelling, whitening, and cracking, and (1) to (6) Means that the compound does not pass through the resin film.

Examples of the above polyethylene glycol include polyethylene glycol having an average molecular weight of 2000 or less. Examples of the polyethylene glycol derivative include polyethylene glycol alkyl ethers such as polyethylene glycol tridecyl ether and polyethylene glycol oleyl ether.The above-mentioned medium-chain fatty acid is, for example, a saturated or unsaturated fatty acid having 6 to 12 carbon atoms. Examples include caproic acid, caprylic acid, capric acid, and lauric acid. Salts are sodium salt, lithium salt, potassium salt, ammonium salt, and alkylamine. And salt.

Examples of the polyoxyethylene sorbitan fatty acid ester and the polyoxyethylene castor oil include those commonly used in pharmaceuticals and the like.

Examples of the diethylene glycol ether derivative include diethylene glycol alkyl ethers such as diethylene glycol-diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, and ethylene glycol monomethyl ether.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polypropylene glycol, glycerin and the like. Examples of the polyhydric alcohol derivative include propylene glycol alkyl ethers such as propylene glycol dimethyl ether and propylene glycol dibutyl ether, and glycerin ethers such as 1-methylglycerin ether and 1,3-dimethylglycerin ether. And glycerin fatty acid esters such as ters and glycerin oleate.

The polymerizable vinyl monomer represented by the general formula [1] is a derivative of acrylic acid or methacrylic acid. For example, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, getylaminomethyl methacrylate, and the like. Preferably, it is dimethylaminoethyl methacrylate.

In the invention of Item 2, the amount of the polymerizable vinyl monomer represented by the general formula [1] to be used is determined based on the amount of the vinyl monomer, the organic acid having a polymerizable Bier group or a salt thereof and other polymerizable vinyl monomers It is from 10 to 50% by weight, preferably from 20 to 40% by weight, based on the total amount of the monomers. If the amount used is less than 10% by weight, the dissolution and dispersibility of the resin film under acid conditions may be poor. On the other hand, if the amount used exceeds 50% by weight, the film of the copolymer is affected by humidity, and it may not be possible to obtain sufficient strength under high humidity.

The copolymerization may be random copolymerization, block copolymerization, or graft copolymerization. Preferably, it is a random copolymerization. The organic acid having a polymerizable vinyl group or a salt thereof is, for example, (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, or a sodium salt, potassium salt, ammonium salt, or alkylamine salt thereof. .

Preferably, the amount of the organic acid having a polymerizable vinyl group such as (meth) acrylic acid and sodium (meth) acrylate or a salt thereof is the amount of the polymerizable biel monomer represented by the general formula [1], It is 10 to 50% by weight, preferably 25 to 40% by weight, based on the total amount of the organic acid having a polymerizable vinyl group or its salt and other vinyl monomers. If the amount is less than 10% by weight, the resin film may not have resistance to the dissolving agent. On the other hand, if the amount used exceeds 50% by weight, the copolymer film is affected by humidity and may not be able to obtain sufficient strength under low humidity.

Other vinyl monomers are used as needed in order to impart appropriate hardness and flexibility to the obtained resin composition. The monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Acrylate, acrylonitrile, acrylamide, dimethylacrylamide, styrene, vinyl acetate, hydroxyethyl (meth) acrylate, esters of polyethylene glycol or polypropylene glycol with (meth) acrylic acid, N-vinylpyrrolidone, acryloyl morpholine, etc. is there. Preferably, it is methyl methacrylate.

The polymerization initiator is used as needed, and those commonly used can be used. For example, 2,2'-azobis (2-amidinopropane) hydride, azo compounds such as AIBN (azoisobutyronitrile), persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; t-Butyl hydrid Redox initiators such as organic peroxides such as peroxides, hydrogen peroxide tartaric acid, and sodium hydrogen peroxide tartrate are used.

The amount of the other vinyl monomer used may be a polymerizable vinyl monomer represented by the general formula [1], an organic acid having a polymerizable vinyl group or a salt thereof, and other vinyl monomers. It is 0 to 80% by weight based on the total amount.

In the invention of Item 3, chitosan is obtained by treating chitin, which is contained in a large amount in shells of shellfish such as shrimp and shrimp, in a concentrated alkali to completely or partially deacetylate the acetyl group. However, in the present invention, it is limited to those having a degree of deacetylation of 60 mol% or more. When the degree of deacetylation is less than 60 mol%, the formability of the film may be deteriorated due to poor solubility in an acid solution.

The acid that dissolves chitosan is not particularly limited, as long as it has the ability to dissolve chitosan. For example, formic acid, acetic acid, n-butyric acid, lactic acid, dalconic acid, benzoic acid, hydrochloric acid, oxalic acid, adipic acid, malic acid, tartaric acid, citric acid, (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, Glycolic acid and the like.

Preferably, it is lactic acid.

Further, acidic polymerizable vinyl monomers can also be used. When an acidic polymerizable vinyl monomer is used, the resin composition of the present invention is obtained by dissolving chitosan with at least one kind of acidic polymerizable vinyl monomer and then performing a polymerization reaction. be able to. Examples of the acidic polymerizable vinyl monomer include (meth) acrylic acid, fumaric acid, maleic acid, and itaconic acid.

Preferably, (meth) acrylic acid is used.

The polymerization initiator is used as needed, and those commonly used can be used. For example, 2,2'-azobis (2-amidinopropane) hydride, azo compounds such as AIBN (azoisobutyronitrile), persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; t-Butyl hydride Redox initiators such as organic peroxides such as peroxide, hydrogen peroxide monotartaric acid, and hydrogen peroxide-sodium tartrate are used.

Chitosan is dissolved, for example, under the following conditions.

The amount of the acid used is 0.8 to 2.0 mol%, preferably 0.9 to 1.2 mol%, based on 1 mol of chitosan. However, chitosan has 1 mol of dalcosamine or N-acetyl-D-dalcosamine unit.

The degree of deacetylation of the chitosan used is at least 60%, preferably at least 80% For example, at 60, 23-33 g of lactate is used for 50 g of chitosan with a degree of deacetylation of 85%.

Polyvinyl alcohol (hereinafter abbreviated as PVA) and derivatives thereof used in the invention of Item 4 include, in addition to completely genated products, intermediate saponified products, partially saponified products, amine-modified PVA, ethylene-modified PVA, terminal Various modified PVAs such as thiol-modified PVA can be used. In addition, the average degree of polymerization of PVA is not particularly limited, since it is sufficient to select an optimum concentration and viscosity according to the application.

The organic acid having a polymerizable vinyl group or a salt thereof is, for example, (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, or a sodium salt, potassium salt, ammonium salt, or alkylamine salt thereof. . Preferably, (meth) acrylic acid is used.

The amount of the organic acid having a polymerizable biel group or a salt thereof is preferably 5 to 50, based on the total amount of the organic acid or a salt thereof having a polymerizable bier group and other vinyl monomers. % By weight, more preferably 10 to 40% by weight. When the amount of the organic acid having a polymerizable biel group or a salt thereof is less than 5% by weight, the ability of the obtained resin film to dissolve or disperse in water is slightly reduced as compared with the case where the amount is 5% by weight or more. There is a tendency, but there is no problem. Also, when the amount used exceeds 50% by weight, the obtained resin film tends to be slightly affected at low humidity under the influence of humidity as compared with the case where the amount is 50% by weight or less. No problem.

Other polymerizable vinyl monomers impart appropriate hardness and flexibility to the obtained resin composition. Such monomers include, for example, methyl (meth) acrylate, ethyl (methyl) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate. ) Acrylate, acrylonitrile, acrylamide, dimethylacrylamide, styrene, vinyl acetate, hydroxyethyl (meth) acrylate, ester of poly (ethylene glycol) or polypropylene glycol with (meth) acrylic acid, N-vinylpyrrolidone, a And cryloylmorpholine.

Preferably, it is methyl methacrylate.

The amount of the other polymerizable beer monomer used may be an organic acid having a polymerizable vinyl group or Is preferably 50 to 95% by weight based on the total amount of the salt and other Bier monomers. More preferably, it is 60 to 90% by weight.

The weight ratio of polyvinyl alcohol and Z or a derivative thereof to at least one selected from the group consisting of an organic acid having a polymerizable vinyl group or a salt thereof and another polymerizable vinyl monomer is preferably , 20-95: 80-5, and more preferably 50-90: 50-10.

When the weight ratio of PVA and Z or its derivative is less than 20, the ability of the resulting resin film to dissolve or disperse in water tends to be slightly lower than when it is 20 or more, but this is not a problem. . When the weight ratio exceeds 95, the resulting resin film is affected by humidity and tends to have a slight decrease in high-humidity compared to a case where the weight ratio is 95 or less. Absent.

Item 4. The invention according to Item 4, including a copolymer obtained by copolymerizing an organic acid having a polymerizable vinyl group or a salt thereof and another polymerizable vinyl monomer in the presence of polyvinyl alcohol and Z or a derivative thereof. Resin compositions are preferred.

In addition, in the invention of Item 4, in the presence of polyvinyl alcohol and Z or a derivative thereof, 5 to 50% by weight of an organic acid having a polymerizable vinyl group or a salt thereof and 50 to 95% of another polymerizable vinyl monomer % By weight of a resin composition containing a copolymer obtained by copolymerization with polyvinyl alcohol and / or a derivative thereof and a polymerizable vinyl monomer in a weight ratio of 20 to 95:80 to 5 Is more preferred. As the polymerization or copolymerization method, known methods can be used.For example, PVA and Z or a derivative thereof are added to water, heated and dissolved, and then an organic acid having a polymerizable vinyl group or a salt thereof. And at least one selected from the group consisting of polymerizable biel monomers and a polymerization initiator, and polymerizing or copolymerizing to obtain a resin.

The polymerization initiator is used as needed, and those commonly used can be used. For example, 2,2'-azobis (2-amidinopropane) hydride chloride, azo compounds such as AIBN (azoisobutyronitrile), persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; t-Butyl hydride mouth Peroxides and other organic peroxides, hydrogen peroxide monotartrate, hydrogen peroxide monotartrate A redox initiator such as sodium is used.

The resin composition of the present invention can be used as a base material for hard capsules and soft capsules. It can also be used as a coating agent for coated tablets. Further, the resin composition of the present invention can be used for those conventionally used as microcapsules. For example, it is possible to supply the active ingredient by encapsulating the active ingredient of cosmetics in a capsule and crushing the capsule on a desired body surface. Further, the composition of the present invention can be used for preventing bad breath. That is, bad breath can be prevented by encapsulating a deodorant for preventing bad breath in a capsule produced with the composition of the present invention and dissolving the capsule in the stomach or the like.

Further, the resin composition of the present invention can be used in foods. For example, it can be used as microcapsules to be put into a gum or the like. Further, the resin composition of the present invention can be used as microcapsules in mouthwash and toothpaste. BEST MODE FOR CARRYING OUT THE INVENTION

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, all% indicate weight%.

Example 1

25 g of acrylic acid, 20 g of dimethylaminoethyl methacrylate, 55 g of methyl methacrylate, 400 g of dimethylformamide in a separable flask equipped with a cooling reflux tube, a dropping funnel, a thermometer, a nitrogen inlet tube and a stirrer Then, a mixture consisting of 0.2 g of azobisisobutyronitrile was charged, and polymerization was carried out at 80 for 4 hours while blowing nitrogen. After the reaction, the solution cooled to room temperature was separated in acetone, and the separated product was dissolved in ion-exchanged water while neutralizing with sodium hydroxide to obtain a reaction product. Using this, a film having a thickness of about 0.1 mm was formed on a glass plate, and the following evaluation tests 1 to 5 were performed. Table 1 shows the results.

Example 2

50 g of flaky chitosan (degree of deacetylation: 85%) in a separable flask equipped with a cooling reflux tube, a dropping funnel, a thermometer, a nitrogen inlet tube, and a stirrer, and ion exchange water, 42 g, 23 g of lactic acid was charged and dissolved under stirring at 7 O for 1 hour to react. I got something. Using this, a film having a thickness of about 0.1 mm was formed on a glass plate, and evaluation tests 1 to 5 were performed. Table 1 shows the results.

Example 3

50 g of flaky chitosan (85% deacetylation degree), 431.5 g of ion-exchanged water, acrylic acid in a separable flask equipped with a cooling reflux tube, a dropping funnel, a thermometer, a nitrogen inlet tube and a stirrer 18.5 g was charged and dissolved with stirring for 70 hours and 1 hour. After purging with nitrogen, 0.37 g of sodium persulfate was added and the reaction was completed in 4 hours to obtain a reaction product. Using this, a film having a thickness of about 0.1 mm was formed on a glass plate, and evaluation tests 1 to 5 were performed. Table 1 shows the results.

Example 4

In a separable flask equipped with a cooling reflux tube, a dropping funnel, a thermometer, a nitrogen inlet tube and a stirrer, add M-205 (PVA having a thiol group at the end, polymerization degree 500, degree of saponification 88%, ) 5.9 g, M-215 (PVA with a terminal thiol group, polymerization degree 1500, degree of generification 88%, manufactured by Kuraray) 53.2 g and ion-exchanged water 236.9 g were charged 95 Completely dissolved at ° C. Next, 5.6 g of acrylic acid and 13. l g of methyl methacrylate were added, and the temperature was raised to 80 ° C after purging with nitrogen. 3 g of tert-butyl hydroxide was added, and the reaction was completed in 4 hours to obtain a reaction product. Using this, a film having a thickness of about 0.1 mm was formed on a glass plate, and evaluation tests 1 to 5 were performed. Table 1 shows the results.

Example 5

A reaction product was obtained in the same manner as in Example 4, except that acrylic acid was changed to methacrylic acid. Using this, a film having a thickness of about 0.1 mm was formed on a glass plate, and evaluation tests 1 to 5 were performed. Table 1 shows the results.

Example 6

In Example 4, PVA M-205 was replaced with EG-05 (partially saponified PVA, polymerization degree 500, saponification degree 88%, manufactured by Nippon Gosei), and M-215 was replaced with EG-25 (partially saponified PVA, A reaction product was obtained in the same manner as in Example 4 except that the polymerization degree was changed to 1700, the saponification degree was 88%, and manufactured by Nippon Gosei. Using this, a film having a thickness of about 0.1 mm was produced on a glass plate, and evaluation tests 1 to 5 were performed. Table 1 shows the results. Comparative Example 1

A reaction product was obtained in the same manner as in Example 1 except that the amount of acrylic acid was changed to 10 g and the amount of methyl methacrylate was changed to 70 g. Using this, a film having a thickness of about 0.1 mm was formed on a glass plate, and evaluation tests 1 to 5 were performed. The results are shown in Table 1. In evaluation tests 4 and 5, the films dissolved.

Comparative Example 2

The adjustment was carried out in the same manner as in Example 2 except that the degree of deacetylation of chitosan was changed to 55%, but the film could not be produced because chitosan could not be completely dissolved.

Comparative Example 3

Commercially available gelatin (gelatin from cattle, pigs or fish with a bloom strength of 200-300 grams) was dissolved in deionized water. Using this, a film having a thickness of about 0.1 mm was formed on a glass plate, and evaluation tests 1 to 5 were performed. Table 1 shows the results. In Evaluation Test 4, the film was embrittled, and in Evaluation Test 5, polyethylene glycol permeated the film and bleed out.

Comparative Example 4

Hydroxypropylmethylcellulose (viscosity of a 2% aqueous solution at 20 ° C of 2.4-5.4 centistokes) was dissolved in deionized water. Using this, a film having a thickness of about 0.1 mm was formed on a glass plate, and evaluation tests 1 to 5 were performed. Table 1 shows the results. In Evaluation Test 5, polyethylene glycol permeated the film and oozed out.

Evaluation test 1: Water dissolution test of film

A film with a size of 2 O mm square was immersed in 10 ml of water and gently shaken to confirm that the film dissolved or dispersed.

Evaluation test 2: Acid dissolution test of film

A 20 mm square film was immersed in 10 ml of water of pH 1.2 prepared with hydrochloric acid and deionized water, and gently shaken to confirm whether the film dissolved or dispersed.

Evaluation test 3: Neutral area dissolution test of coating A 2 Omm square film was immersed in 10 ml of PH6.8 water prepared with potassium dihydrogen phosphate, sodium hydroxide, and deionized water, and gently shaken to confirm that the film dissolved or dispersed. .

Evaluation test 4: Polyethylene glycol (PEG) resistance test of the film

A 20 mm square film was immersed in 10 ml of polyethylene glycol (molecular weight: 400) and left at 60 for one week to check whether the film deteriorated. ,

Evaluation test 5: Film permeability test

The film was supported horizontally, and an appropriate amount of PEG was dropped on the upper surface of the film, and allowed to stand for one week to check whether PEG permeated the film.

Water, acidic, neutral dissolution test: 溶解 completely dissolved or disintegrated

X does not dissolve or disintegrate

PEG resistance test: No change

X Degradation such as melting and embrittlement

Membrane permeability test: No film penetration

X Film penetrated (Comparative Example 1 dissolves the film) Industrial applicability

According to the present invention, it is possible to provide a resin composition which is dissolved or dispersed in water having a pH of 10 or less and which is not affected by a liquid solvent at room temperature.

Claims

The scope of the claims

1. The resin film dissolves or disperses in water of pH

(1) polyethylene glycol and its derivatives,

(2) medium-chain fatty acids and salts thereof,

(3) polyoxyethylene sorbitan fatty acid ester,

(4) polyoxyethylene castor oil,

(5) a diethylene glycol ether derivative, and

(6) Polyhydric alcohol and its derivatives

2. General formula [1]:

[1]

[In the formula, represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 1 to 4 carbon atoms, and R ₃ and R ₄ represent the same or different and have 1 to 4 carbon atoms. A represents an oxygen atom or NH. ]

10 to 50% by weight of a polymerizable vinyl monomer represented by the following formula, 10 to 50% by weight of an organic acid having a polymerizable vinyl group or a salt thereof, and 0 to 80% by weight of another polymerizable Bier monomer The resin composition according to claim 1, comprising a resin obtained by copolymerizing% by weight.

3. (a) Acidic polymerization of chitosan with a degree of deacetylation of 60 mol% or more from a solution obtained by dissolving chitosan with an acid or (mouth) chitosan with a degree of deacetylation of 60 mol% or more 2. The resin composition according to claim 1, comprising a resin obtained from a solution containing a polymer or a copolymer obtained by dissolving with at least one kind of a vinyl monomer and then polymerizing or copolymerizing.

4. A group consisting of an organic acid having a polymerizable vinyl group or a salt thereof and other polymerizable vinyl monomers in the presence of polyvinyl alcohol and / or a derivative thereof. The resin composition according to claim 1, comprising a resin obtained by polymerizing or copolymerizing at least one selected from the group consisting of: