JP2007320975A - Water-soluble gel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid-absorbing polymer that has a property such that it becomes once gel-like when it absorbs a liquid and is dissolved with time and exhibits both high biocompatibility and high biodegradability, and a composition thereof. <P>SOLUTION: The polymer gels when it absorbs a liquid and then can be liquefied with time, where the liquefaction with time proceeds along with lowering of the viscosity with time into a solution. Preferably, the polymer comprises an alkoxysilane derivative and further preferably a polyamino acid derivative having a specific structural unit obtained from a raw material amino acid exhibiting excellent biocompatibility. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a liquid-absorbing polymer and a composition thereof, wherein the liquid-absorbing polymer once gelled dissolves with time and has both high biocompatibility and biodegradability. The present invention relates to a polyamino acid derivative composition.

  Conventionally, a liquid-absorbent gel retains its shape once liquid is absorbed. For example, when applied to cosmetics and external preparations, it is applied to gels and packs. This is effective in maintaining the effect on the skin for a long time. However, since the shape does not change, it is necessary to wash or scrape after use. On the other hand, solution-like lotion can be applied directly onto the skin and does not need to be removed. However, it is not suitable for maintaining the effect for a long time, and has problems such as dripping at the time of application and uncomfortable feeling. . Conventional bases for cosmetics and external preparations have to use the above-mentioned two types of properties depending on the purpose of use and the situation of use.

  On the other hand, when it was used for disaster prevention, the swollen gel used in a fire or spill accident had to be removed later, requiring labor and effort. Further, in the case of medical materials, particularly DDS materials, it is essential to change the shape of the material as the drug is released. However, when a liquid-absorbing gel is applied, the gel once formed remains as it is, so that it is difficult to use.

  In recent years, new materials are constantly demanded in various fields. Since the conventional liquid-absorbent gel retains its shape once liquid has been absorbed, it must be removed after use. For example, in the cosmetics and external preparation fields, liquid-absorbing gels are applied to gels and packs. This is effective for releasing the active ingredient on the skin for a long time and maintaining the effect, but after use it must be removed by washing or rubbing. On the other hand, a solution-like lotion can be directly applied to the skin and does not need to be removed, but the effect cannot be sustained for a long time. In addition, there are problems such as dripping and uncomfortable feeling during application. As a problem to solve the disadvantages of both, it is conceivable that the material stays for an arbitrary time during application on the skin and does not remain thereafter.

  As another example, when a liquid-absorbing gel is used for disaster prevention applications, the gel that has been used in a fire or spill accident and has swollen after liquid absorption needs to be removed, which requires enormous labor and labor. As a problem to solve this drawback, it is considered that the gel does not remain in the environment after exhibiting the function as a gel.

  In addition, in the case of medical materials, particularly DDS materials, it is essential to change the shape of the materials accompanying drug release. However, when a gel is introduced, its state does not change, and thus its use is limited for DDS purposes. In order to solve this problem, it is necessary to change the gel once formed according to the purpose. Furthermore, biocompatibility and biodegradability are also required in these fields, and it is an important issue to be able to use safer and environment-friendly materials.

  These problems can be solved by providing a function in which the absorbed gel retains its form for a certain period of time and then becomes a solution or disappears.

  From the above, that is, the present invention is a liquid-absorbing polymer and a composition thereof, which has a property that the liquid-absorbed polymer once dissolved into a gel form dissolves with time and has high biocompatibility. It aims at providing the polymer which has the property and biodegradability.

  Alkoxysilane compounds are generally well known as silane coupling agents. It is generally well known that the alkoxy moiety is easily hydrolyzed to silanol in the presence of water. As a result of intensive investigations to achieve the above-mentioned object, the present inventors grafted an alkoxysilane derivative residue to a polymer to quickly absorb water into a gel, and once absorbed into water, the gel is formed. A polymer in which the polymer dissolves with time was produced to complete the present invention.

  Furthermore, a material excellent in biocompatibility and biodegradability can be provided by applying a polyamino acid derivative having a specific structural unit using an amino acid as a raw material at the polymer site.

  The present invention relates to a liquid-absorbing polymer and a composition thereof, wherein the liquid-absorbing polymer once gelled dissolves with time and has both high biocompatibility and biodegradability. Polymers and compositions thereof.

That is, the present invention
[1] A polymer that absorbs liquid and gelates, and then can be liquefied over time.
[2] The polymer according to [1], wherein the liquefaction with time decreases in viscosity with time to become a solution.
[3] The polymer according to [1] or [2], wherein the liquid is water and the solution is an aqueous solution.
[4] The polymer according to any one of [1] to [3], which contains a silicon atom.
[5] The polymer according to any one of [1] to [4], wherein the polymer contains an alkoxysilane derivative.
[6] The polymer according to any one of [1] to [5], wherein the polymer skeleton is a polyamide skeleton.
[7] The polymer according to [6], wherein the polymer is a polyamino acid derivative.
[8] The polymer according to [7], wherein the polyamino acid derivative is a polyglutamic acid derivative or a polyaspartic acid derivative.
[9] The following general formulas (I) to (II)

(Wherein R ¹ represents a silane derivative residue having 1 to 18 carbon atoms including a silicon atom, X and Y each independently represents O and / or NH, and M represents hydrogen, an alkali metal or an alkaline earth) Represents a metal, and m represents an integer of 1 to 2.)
The polymer according to any one of [6] to [8], comprising at least one monomer unit of an α-type, β-type, or γ-type polyamino acid monomer unit represented by:
[10] R ¹ in the general formula (I) is trimethoxysilane, dimethoxysilane, monomethoxysilane, triethoxysilane, diethoxysilane, monoethoxysilane, tripropoxysilane, dipropoxysilane, monopropoxy [9] including at least one selected from the group consisting of silane, dimethoxymethylsilane, diethoxyethylsilane, dimethylmethoxysilane, diethylethoxysilane, trimethylsilane, triethylsilane, or a derivative residue containing a tripropylsilane group The polymer described.
[11] A composition containing the polymer according to any one of [1] to [10].
[12] The polymer composition according to [11], wherein the polymer-containing composition is in a gel state or a solution.
[13] A cosmetic comprising the composition according to [11] or [12].
[14] An external preparation comprising the composition according to [11] or [12].
[15] A medical material comprising the composition according to [11] or [12].
[16] A disaster prevention material comprising the composition according to [11] or [12].
[17] A water-soluble gel comprising the polymer according to any one of [1] to [10] and the polymer composition according to [11] or [12].
About.

  According to the present invention, a liquid-absorbing polymer and a composition thereof having a property that a polymer once absorbed into a gel form dissolves with time, and has high biocompatibility and biodegradability. Can be provided. According to the present invention, a liquid-absorbing polymer and a composition thereof, which has a property that a liquid-absorbed polymer once gelled and dissolves with time can be used. In addition, by applying a polymer having both high biocompatibility and biodegradability, it can be widely used from cosmetics, external preparations, medical materials to disaster prevention materials.

  Hereinafter, the present invention will be described in detail.

  The present invention relates to a liquid-absorbing polymer and a composition thereof, wherein the liquid-absorbed polymer once gelled dissolves with time to form a solution, and further has high biocompatibility. The present invention relates to a polymer capable of adding a function having biodegradability and a composition thereof.

  The present invention is a (soluble) polymer that can absorb liquid and gelate and then liquefy over time. More specifically, liquefaction over time becomes a solution with reduced viscosity over time. Said polymer characterized in that.

  Although it does not restrict | limit especially as a liquid and its liquefied state in this invention, It is preferable that the said liquid is water and the said liquefied state is aqueous solution.

  The polymer of the present invention is not particularly limited as long as it has the above-mentioned properties, but among them, a polymer containing a silicon atom is preferable, and the polymer is more preferably a polymer containing an alkoxysilane derivative. .

  In the present invention, although not particularly limited, as a specific example of a polymer containing an alkoxysilane derivative, a polymer obtained by grafting an alkoxysilane derivative residue to the polymer is cited as one of preferred embodiments. It is done.

  In the present invention, the silane derivative residue includes a group having a silicon atom and having a polysilane structure. An alkoxysilane derivative residue is a derivative residue of a silane compound to which an alkoxy group is bonded, and specifically, the following general formula (III)

(Wherein R ² represents hydrogen and / or a hydrocarbon group having 1 to 8 carbon atoms, Z represents a hydrocarbon chain having 1 to 20 carbon atoms which may contain a hetero atom, and A, B, C represents an oxygen atom or a carbon atom, respectively).

In general formula (III), each R ² independently represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different. Specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, and octyl groups are represented, but branched hydrocarbon groups other than those described may be used. Z represents a hydrocarbon chain having 1 to 20 carbon atoms which may contain a heteroatom, and more specifically represents an alkyl chain which may contain a heteroatom, but the heteroatom is derived from nitrogen, oxygen or sulfur atom. Preferably it is selected.

  In the present invention, the polymer refers to all polymers to which the aforementioned silane derivative residues can be bonded, specifically vinyl polymers, and more specifically polyacrylic acid derivatives, polymethacrylic acid derivatives, polyvinyl alcohol derivatives, polystyrene derivatives. , Polyvinyl pyrrolidone derivatives, polyvinyl acetamide derivatives, polyvinyl chloride derivatives, and the like. Or it is an amino acid-type polymer, and a polyaspartic acid derivative, a polyglutamic acid derivative, a polylysine derivative etc. are mentioned in detail. Other examples include ester polymers, polysaccharides, proteins, and the like.

  As a polymer of this invention, it is mentioned as a preferable aspect that the frame | skeleton of the said polymer is a polyamide frame | skeleton, Furthermore, it is mentioned as a preferable aspect that the said polymer is a polyamino acid derivative.

  Particularly in the present invention, the polyamino acid also includes a polymer obtained by peptide condensation polymerization of amino acids. In the present invention, a polymer and a polymer are equivalent to each other. The arrangement of the monomer units constituting the polymer (polymer) may be any of a random copolymer, a block copolymer, and a graft copolymer in the case of a copolymer (copolymer). The molecular chain of the polymer (polymer) may be linear, macrocyclic, branched, star-shaped, or three-dimensional network-shaped. In the present invention, the hydrocarbon group may be linear, branched or cyclic, and atoms other than C and H such as N, O and S may be contained in the atomic group.

  The polyamino acid derivative of the present invention is not particularly limited as long as its basic skeleton is composed of a monomer unit of an amino acid derivative, but is particularly preferably a polyglutamic acid derivative or a polyaspartic acid derivative. Specifically, the following general formula (I) or (II)

(Wherein R ¹ represents a silane derivative residue having 1 to 18 carbon atoms including a silicon atom, X and Y each independently represents O and / or NH, and M represents hydrogen, an alkali metal or an alkaline earth) Represents a metal, and m represents an integer of 1 to 2.)
A polyamino acid derivative containing at least one monomer unit of the α-type, β-type, or γ-type polyamino acid monomer unit represented by

In the monomer unit of the general formula (I), R ¹ represents a silane derivative residue having 1 to 18 carbon atoms including a silicon atom.

The R ¹ is not particularly limited as long as it is selected from silane derivative residues having 1 to 18 carbon atoms including a silicon atom.

  In the above, an alkoxysilane derivative residue is preferable, and more specifically, trimethoxysilane, dimethoxysilane, monomethoxysilane, triethoxysilane, diethoxysilane, monoethoxysilane, tripropoxysilane, dipropoxysilane, Monopropioxysilane, dimethoxymethylsilane, diethoxyethylsilane, dimethylmethoxysilane, diethylethoxysilane, trimethylsilane, triethylsilane, or a derivative residue containing a tripropylsilane group, etc., among which trimethoxysilane, triethoxy Silane, tripropoxyoxysilane, dimethoxymethylsilane, diethoxyethylsilane, trimethylsilane, or a derivative residue containing a triethylsilane group is more preferable.

  In the above general formula, X and Y each independently represent O and / or NH. M represents at least one element selected from hydrogen, alkali metal, or alkaline earth metal.

  Moreover, m shows the integer of 1-2.

  More specifically, Y can be selected from hydrogen, alkali metals or alkaline earth metals, and is preferably selected from alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as beryllium, magnesium and calcium. .

  In the polyamino acid derivative of the present invention, any of α-amide type monomer unit, β-amide type monomer unit and γ-amide type monomer unit may be present. The person may coexist. In the case of coexistence, the ratio of the α-amide type monomer unit to the β-amide type monomer unit and the γ-amide type monomer unit is not particularly limited.

  The polyamino acid derivative used in the present invention can be produced using, for example, polysuccinimide as a raw material.

  Polysuccinimide can be produced by various conventionally known methods. For example, in J. Am. Chem. Soc., 80, 3361 (1985), aspartic acid is heated and condensed at 200 ° C. for 2 to 3 hours. Thus, a method for producing polysuccinimide is disclosed. Japanese Patent Publication No. 48-20638 discloses a method of obtaining a high molecular weight polysuccinimide by reacting aspartic acid in a thin film using a rotary evaporator with 85% phosphoric acid as a catalyst. Yes. US Pat. No. 5,057,597 discloses a method for industrially obtaining polysuccinimide by heat condensation of polyaspartic acid in a fluidized bed. Also. Further, when a high molecular weight polysuccinimide is required, the polysuccinimide obtained by the above method can be linked by treating with a condensing agent such as dicyclohexylcarbodiimide.

  The molecular weight of the polysuccinimide used for producing the polyamino acid derivative of the present invention is not particularly limited as long as a product having desired characteristics is substantially obtained. Generally, the molecular weight of polysuccinimide is preferably about 2000 to 500000, more preferably about 10000 to 400000, and particularly preferably about 15000 to 200000. This molecular weight is a value obtained by measuring with a gel permeation chromatography at 45 ° C. in an N, N-dimethylformamide solution and using a polystyrene standard. If the molecular weight of the polysuccinimide used is low, the molecular weight of the resulting polyamino acid derivative will be low, and if the molecular weight of the polysuccinimide is high, the molecular weight of the polyamino acid derivative obtained will also be high.

  The method in particular when manufacturing a polyamino acid derivative from the polysuccinimide of this invention is not restrict | limited, For example, the following manufacturing methods are mentioned. First, polysuccinimide is dissolved in a suitable solvent. The solvent is not particularly limited as long as polysuccinimide is dissolved and no side reaction is caused by reaction with amines. For example, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane and the like are used.

  In this solvent, amines having alkoxysilane are reacted with the imide ring of polysuccinimide. When the reaction is performed by adding 1 mole of amine to the number of moles of the imide ring of polysuccinimide, the amine is added by opening the imide ring to form a side chain graft structure. Although the ratio to introduce | transduce can be selected arbitrarily, 0.1-99 mol% is preferable with respect to the raw material polysuccinimide, and 1-60 mol% is still more preferable. If the introduction rate is lower than this, the ability to form an initial gel is lost, and if the introduction rate is higher than this, water solubility after gel formation is lost.

  Next, the remaining unreacted imide ring is opened with an alkali. The alkali to be used may be alkaline having a pH of 7 or more in an aqueous solution, but is preferably selected from an inorganic base or a water-soluble amine derivative. In particular, it is preferable to select from basic sodium salt, basic potassium salt, basic calcium salt, and basic magnesium salt. Ring opening other than alkali is difficult and economically unsuitable.

  The resulting reaction mixture is then discharged into a poor solvent. The poor solvent is not particularly limited as long as the polyamino acid derivative is precipitated and then filtered and dried so that it does not remain in the crystal of the polyamino acid derivative. For example, acetonitrile, acetone, methanol, ethanol, ethyl acetate, hexane, or a mixed solvent thereof is used. The target polyamino acid derivative is obtained by filtering the precipitate obtained as described above, washing with a poor solvent, and drying.

  The polymer composition of the present invention contains at least one kind of the above-mentioned polymers, and usually a solution in which these are dissolved in an appropriate solvent is preferable. The composition of the present invention may contain other polymer components. In addition to the above, auxiliary components (additives) such as fragrances, preservatives, stabilizers, mineral components, colorants, and cleaning agents may be included as necessary.

  Although it does not specifically limit as a solvent which comprises the polymer composition of this invention, For example, the following inorganic and organic solvents are mentioned. More specifically, for example, water, ethanol, methanol, isopropanol, ethylene glycol and other alcohols, ethylene glycol methyl ether, ethers such as ethylene glycol ethyl ether, esters such as ethyl acetate and butyl acetate, plant extract water, Examples include plant-derived liquids such as plant extracts and vegetable oils, and silicone-based oils. Among these, water and ethanol are preferable.

  In the composition of the present invention, the mixing ratio of the polymer and the solvent is not particularly limited, and any mixing ratio may be used. Usually, the polymer concentration is 0.1 ppm to 60% by weight, preferably 1 ppm to 30% by weight. In some cases, only the polymer may be used.

  The polymer composition of the present invention is preferably in a gel state or a solution.

  Moreover, this invention is the water-soluble gel which comprises the said polymer or polymer composition.

  In the water-soluble gel of the present invention, the liquid absorption rate of the soluble gel is not particularly limited as long as it is a polymer concentration that finally becomes a solution, and it is 1 or more times by weight, preferably 2 or more times, more preferably 5 times or more. If the liquid absorption is lower than this, the polymer concentration is high and the solubility itself is poor.

  The water-soluble gel of the present invention is characterized in that when a polymer absorbs liquid, it becomes a gel state, and the gel increases in solution properties over time and then becomes a solution. There is a method of measuring viscosity to capture this physical phenomenon. A specific method for measuring the viscosity is as follows. First, water or other solvent is absorbed into the polymer to prepare a liquid-absorbing gel as a sample. The viscosity of this sample is measured with a rheometer at a constant temperature. The result is obtained by the phenomenon that the viscosity of the sample that initially showed high viscosity decreases with time.

  In the polymer of the present invention, that is, the (water) soluble gel, after the polymer absorbs the liquid to become a gel state, the gel liquefies with time to form a solution. It is also possible to define a so-called (water) solution state or a state having fluidity, that is, a state where the viscosity is not more than a specific viscosity. In the present invention, the gel state indicates a state having no fluidity, and includes a highly viscous liquid material. For simplicity, the container is shown upside down so that the composition does not fall. Further, the state of the normal (water) solution is not particularly limited as long as it has fluidity, but the viscosity is preferably 5 Pa · s or less.

  Further, the retention time of the gelled state and the time required for liquefaction over time can be appropriately adjusted depending on the polymer used and its use, and are not particularly limited.

  In the polymer and the (water) soluble gel of the present invention, for example, for cosmetics and external preparations, the gelation state retention time may be liquefied after several seconds to several hours. The holding time can be appropriately set according to the application, such as about 1 to 10 seconds and 1 to 60 minutes for an attachment. For medical materials, the gelation state retention time may be liquefied after several minutes to several days, for example, 1 minute to 1 day for a drug sustained release agent, 1 to 60 for an attached agent. It is possible to set the holding time as appropriate according to the application, such as minutes. In addition, in the use for disaster prevention materials, the gelled state retention time is assumed to be several hours to several months, for example, 1 to 60 minutes for fires, and 1 hour to several days for spill accidents, etc. It is possible to set. Although it can set suitably according to a use as above-mentioned in this invention, it is not specifically limited to these.

  The water-soluble gel obtained by containing the polymer composition of the present invention contains, as necessary, a dye, a fragrance, an alcohol, an antiseptic, a pigment, an antioxidant, a liquid paraffin, a surfactant, and a water-soluble polymer. Further, salts, mineral components, pH adjusters and the like may be added within a range not impairing the function of the polymer of the present invention, and compositions to which these are added are also included in the present invention. The form of the composition is not particularly limited, and a conventionally known method can be adopted for production. The polymer composition of the present invention is used by blending in cosmetics and external preparations, or by adding to agents that require thickening and foaming properties.

  The composition of the polymer composition forming the water-soluble gel of the present invention is generally used in cosmetics, specifically, pack agents, facial cleansing agents, cleaning agents, moisturizing agents, cleansing agents, massage agents, shaving care agents, sunscreens. Agents, hair care agents, fragrances, hair styling agents, hair dyes and the like.

  Examples of the external preparation of the present invention include all of those blended in external medicines, such as poultices, analgesics, cooling agents, heat removal agents, heat retention agents, disinfecting disinfectants, keratin softeners, antifungal agents, sunscreen agents, Examples include skin bleaching agents, skin coloring agents, granulation agents, epidermis forming agents, hair nourishing agents, deodorants, antiperspirants, vitamins and the like.

  Examples of the medical material of the present invention include those that use gel in relation to medical treatment, such as sustained-release drug base materials, regenerative medical materials, surgical adhesives, hemostatic agents, wound dressings, artificial organs. And anti-adhesion materials.

  The disaster prevention material of the present invention includes all materials that prevent or buffer in connection with disasters, such as flood buffering, flood mitigation, oil recovery, subsoil replacement, fire extinguishing, fire spread prevention, various equipment liquids. One with functions such as leak emergency response.

  As a compounding quantity of the said polymer composition in the cosmetics, external preparation, medical material, or disaster prevention material of this invention, 0.5 mass% or more of polymer content is preferable, More preferably, it is 1 mass% or more. If the content is less than this, a sufficient gel may not be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples.

  In this example, a raw material polysuccinimide (hereinafter abbreviated as PSI) having a weight average molecular weight (hereinafter abbreviated as Mw) of 97000 was used. This Mw is a value obtained by gel permeation chromatography, measured at 45 ° C. in an N, N-dimethylformamide (hereinafter abbreviated as DMF) solution, and obtained with a polystyrene standard. In addition, a separable flask equipped with a stirrer, a heater, a thermometer, and a nitrogen line was used as the reaction vessel, and the reaction system was sufficiently stirred during the reaction.

  In this example, a raw material polysuccinimide (hereinafter abbreviated as PSI) having a weight average molecular weight (hereinafter abbreviated as Mw) of 95,000 was used. This Mw is a value obtained by gel permeation chromatography, measured at 45 ° C. in an N, N-dimethylformamide (hereinafter abbreviated as DMF) solution, and obtained with a polystyrene standard. In addition, a separable flask equipped with a stirrer, a heater, a thermometer, and a nitrogen line was used as the reaction vessel, and the reaction system was sufficiently stirred during the reaction.

  First, PSI (9.40 g) and DMF (34.00 g) were placed in a 100 ml reaction vessel and completely dissolved under heating at 70 ° C. Next, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (1.04 g; 5 mol% based on succinimide unit) was added, and the temperature in the reaction vessel was kept at 50 ° C. The solution gelled when reacted for a period of time. The gel was then crushed and transferred to a 300 ml reaction vessel equipped with a pH meter, and methanol (100 ml) and water (100 ml) were added. While stirring at room temperature, a 20 mass% aqueous sodium hydroxide solution was gradually added dropwise. An aqueous sodium hydroxide solution (21.24 g, 0.1 mmol) was added while controlling the addition rate so as not to exceed pH 12. At this point, the pH did not drop and the gel dissolved. Thereafter, the reaction solution was discharged into acetonitrile (1.5 L) while stirring, thereby precipitating the reaction product. After standing at an appropriate time, the supernatant was removed by decantation. Subsequently, methanol (1 L) was added to sludge the solid content, and the solid content was collected by filtration. After drying under reduced pressure, a white polyaspartic acid derivative (10.4 g, yield 72%) was obtained.

  The obtained polyaspartic acid derivative turned into a gel at a water absorption ratio of 20 to 100 when water was added, and the gel became a solution when left at room temperature for 3 hours. When the viscosity of the gel prepared with a polymer concentration of 5% was measured in a solution, it was 3.6 mPa · s.

  As a result of preparing a 1% aqueous solution of the polymer synthesized in Example 1 and measuring the viscosity, a viscosity of 1.9 kPa · s was obtained. This solution was allowed to stand at room temperature for 3 hours, and the viscosity was measured and found to be 3.2 mPa · s.

  PSI (9.4 g) and DMF (40 g) were placed in a 100 ml reaction vessel and completely dissolved. Next, 3-aminopropyltriethoxysilane (1.11 g; 5 mol% based on the succinimide unit) was added and reacted at room temperature for 5 hours. The viscosity increased. Subsequently, the reaction solution obtained in a beaker charged with acetone (600 ml) was dropped and reprecipitated. It was then filtered, washed with acetone (100 ml) and dried. The obtained powder (10.1 g) was added and dispersed in a 10 ml reaction vessel into which water (50 ml) was inserted. While stirring at room temperature, a 20 mass% aqueous sodium hydroxide solution was gradually added dropwise. An aqueous sodium hydroxide solution (16.9 g) was added while controlling the addition rate so as not to exceed pH 12. At this point, the pH did not drop and the gel dissolved. Thereafter, the reaction solution was discharged into a mixed solvent of methanol (150 ml) and acetone (600 ml) and reprecipitated. The residue obtained by filtration was washed with methanol, filtered and dried again to obtain a pale yellow polyaspartic acid derivative (3.5 g, yield 24%).

  As a result of preparing a 3% aqueous solution of this polyaspartic acid derivative and measuring the viscosity with a rheometer at a temperature of 20 ° C. and a stress of 1 Pa, a gel having a viscosity of an initial value of 20 kPa · s was found to be 40 Pa · s after 30 minutes. And changed to a fluid liquid. (See Figure 1)

  According to the present invention, a liquid-absorbing polymer and a composition thereof having a property that a polymer once absorbed into a gel form dissolves with time, and has high biocompatibility and biodegradability. Can be provided.

  According to the present invention, a liquid-absorbing polymer and a composition thereof, which has a property that a liquid-absorbed polymer once dissolved into a gel can dissolve with time, can be utilized. By applying a polymer having both high biocompatibility and biodegradability, it can be widely used from cosmetics, external preparations, medical materials to disaster prevention materials.

  That is, the polymer composition of the present invention is a biocompatible material that does not affect the living body, such as daily life products, hygiene products, medical supplies, disaster prevention materials, etc. It can be suitably formulated and applied even in the field of materials that require biocompatibility and biodegradability in situations where it has a great influence.

    Therefore, examples of the composition of the composition of the present invention include, for example, cosmetics such as lotion, moisturizing liquid, facial cleansing oil, cleansing oil, cleansing milk, cleansing lotion, massage oil, moisture cream, shaving oil, shaving lotion. , Shampoo, sunscreen lotion, tanning oil, body lotion, body shampoo, hair shampoo, hair rinse, hair treatment, hair nourishing oil, hair oil, hair mousse, perfume oil, hair liquid, set lotion, hair spray, hair bleach, color rinse, Color spray, permanent wave liquid, hand lotion, etc. are listed. External preparations include poultices, analgesics, cooling agents, heat removal agents, heat retention agents, disinfecting disinfectants, keratin softeners, antifungal agents, sun protection , Skin bleaching agents, skin coloring agents, granulation generator, skin forming agents, hair tonic hair growth agents, deodorants, antiperspirants, include general those formulated for external use medicines such as vitamins. Examples of medical materials include those that use gels, such as sustained-release drug base materials, regenerative medical materials, surgical adhesives, hemostatic agents, wound dressings, and anti-adhesion materials such as artificial organs. It is done. In addition, disaster prevention materials generally include those that prevent or buffer in connection with disasters, such as flood buffering, flood mitigation, oil recovery, soil replacement, fire extinguishing, fire spread prevention, liquids for various facilities. One with functions such as leak emergency response.

It is a figure explaining the time-dependent change of the viscosity in the polymer composition of this application.

Claims (17)

  A polymer that absorbs liquid and gelates, and can be liquefied over time.   2. The polymer according to claim 1, wherein the liquefaction with time decreases the viscosity with time to become a solution.   The polymer according to claim 1 or 2, wherein the liquid is water and the solution is an aqueous solution.   The polymer according to any one of claims 1 to 3, comprising a silicon atom.   The polymer according to any one of claims 1 to 4, wherein the polymer contains an alkoxysilane derivative.   The polymer according to any one of claims 1 to 5, wherein the polymer skeleton is a polyamide skeleton.   The polymer according to claim 6, wherein the polymer is a polyamino acid derivative.   The polymer according to claim 7, wherein the polyamino acid derivative is a polyglutamic acid derivative or a polyaspartic acid derivative. The following general formulas (I) to (II)

(Wherein R ¹ represents a silane derivative residue having 1 to 18 carbon atoms including a silicon atom, X and Y each independently represents O and / or NH, and M represents hydrogen, an alkali metal or an alkaline earth) Represents a metal, and m represents an integer of 1 to 2.)
The polymer according to any one of claims 6 to 8, comprising at least one monomer unit of an α-type, β-type, or γ-type polyamino acid monomer unit represented by: R ¹ in the general formula (I) is trimethoxysilane, dimethoxysilane, monomethoxysilane, triethoxysilane, diethoxysilane, monoethoxysilane, tripropoxyoxysilane, dipropoxyoxysilane, monopropoxysilane, dimethoxy 10. The polymer according to claim 9, comprising at least one selected from the group consisting of methylsilane, diethoxyethylsilane, dimethylmethoxysilane, diethylethoxysilane, trimethylsilane, triethylsilane, or a derivative residue containing a tripropylsilane group. .   The composition containing the polymer in any one of Claims 1-10.   The polymer composition according to claim 11, wherein the polymer-containing composition is in a gel state or a solution.   A cosmetic comprising the composition according to claim 11 or 12.   An external preparation comprising the composition according to claim 11 or 12.   A medical material comprising the composition according to claim 11 or 12.   A composition for disaster prevention comprising the composition according to claim 11 or 12.   A water-soluble gel comprising the polymer according to any one of claims 1 to 10 and the polymer composition according to claim 11 or 12.

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