Compound, polymer, energy ray-curable resin composition, hydrogel, resin composition, and coated article

Abstract

To provide a compound exhibiting specific physical properties when formed into a polymer by having an amino acid structure in the molecule.SOLUTION: A compound represented by formula (1-1): (R1 is hydrogen or methyl; R2 is an amino acid-derived side chain (excluding a case where R2 is H and R3 is CH2CH (OH) CH2); R3 is an alkylene group having 1 to 30 carbon atoms which may have a hydroxyl group, an ether group, or an ester group; R4 is an alkyl group having 1 to 30 carbon atoms which may have an aromatic ring) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound, a polymer, an energy ray-curable resin composition, a hydrogel, a resin composition, and a coated article. [Background technology]

[0002] Polymers with amino acid structures have physical crosslinks due to interactions such as hydrogen bonds between amino acids, resulting in specific physical properties. For example, molded articles of the polymers have elasticity. Furthermore, when made into hydrogels, they exhibit self-organization and temperature responsiveness, and also have the properties of shape-memory materials (Patent Document 1, Non-Patent Document 1).

[0003] Regarding these materials, since the chemical structure of the polymer has a significant effect on the physical properties, various compounds and polymers having an amino acid structure have been investigated. A compound obtained by reacting glycidyl methacrylate with acetylglycine is disclosed in Non-Patent Document 2. However, Non-Patent Document 2 does not disclose obtaining a polymer of this compound. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2019-85483 [Non-patent literature]

[0005] [Non-Patent Document 1] Handbook of Stimuli-Responsive Polymers (First Edition published on December 18, 2018, Supervisor: Takashi Miyata, Publisher: Takashi Yoshida, Publisher: NTS Corporation) pp. 153-159 Chapter 2 Molecular Design Section 14 Design of Stimuli-Responsive Polymers Based on Amino Acids (Doshisha University, Shinnosuke Nishimura, Tomoyuki Koga, Nobuyuki Azuma) [Non-patent document 2] Huang Z, Liao T, Liu X, et al. Modified ethylene / α-octene co-polymer composites based on dual toughening of hydrogen bonding network and nanospheres. Polym Adv Technol. 2022;33(7):2313‐2324. Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a compound that has an amino acid structure in the molecule and thereby exhibits specific physical properties when polymerized. [Means for solving the problem]

[0007] The present invention is a compound represented by the following general formula (1-1) or (1-2).

[0008] [ka]

[0009] [ka]

[0010] (In the formula, R 1 represents hydrogen or a methyl group. R 2 represents a side chain derived from an amino acid. 2 is hydrogen and R 3 Except when is CH2CH(OH)CH2. R 3 represents an alkylene group having 1 to 30 carbon atoms which may have a hydroxyl group, an ether group or an ester group. R 4 represents an alkyl group having 1 to 30 carbon atoms which may have an aromatic ring)

[0011] The present invention also relates to a polymer characterized by having a structural unit derived from a compound represented by the following general formula (2) or (1-2).

[0012] [ka]

[0013] [ka] (In the formula, R 1 represents hydrogen or a methyl group. R 2 represents a side chain derived from an amino acid. R 3 represents an alkylene group having 1 to 30 carbon atoms which may have a hydroxyl group, an ether group or an ester group. R 4 represents an alkyl group having 1 to 30 carbon atoms which may have an aromatic ring)

[0014] The polymer preferably further comprises a structural unit based on a compound represented by the following general formula (3).

[0015] [ka]

[0016] (In the formula, R 11 is a hydrogen or methyl group. R 12 represents an alkylene group having 1 to 20 carbon atoms, which may be branched.

[0017] The present invention also relates to an energy ray-curable resin composition comprising a compound represented by the following general formula (2) and / or a compound represented by the following general formula (1-2), and a photopolymerization initiator:

[0018] [ka]

[0019] [ka]

[0020] (In the formula, R 1 represents hydrogen or a methyl group. R 2 represents a side chain derived from an amino acid. R 3 represents an alkylene group having 1 to 30 carbon atoms which may have a hydroxyl group, an ether group or an ester group. R 4 represents an alkyl group having 1 to 30 carbon atoms which may have an aromatic ring)

[0021] The present invention also relates to a hydrogel comprising the above polymer and water. The present invention also relates to a resin molded article containing the above polymer. The present invention also relates to a coated article having a coating layer containing the above polymer. [Effects of the Invention]

[0022] The compound of the present invention has excellent polymerizability, whether it is polymerized alone or copolymerized with other monomers, and the resulting polymer has excellent elasticity and strength. Furthermore, hydrogels containing such polymers have properties such as temperature responsiveness and self-organizing ability. [Brief explanation of the drawings]

[0023] [Figure 1] 1 shows the results of transmittance measurement of various polymers in the examples with changes in temperature. [Figure 2] Saturated water content of various polymers in the examples. DETAILED DESCRIPTION OF THE INVENTION

[0024] The present invention will be described in detail below. (compound) The novel compound of the present invention is a compound represented by the following general formula (1-1) or (1-2).

[0025] [ka]

[0026] [ka] (In the formula, R 1 represents hydrogen or a methyl group. R 2 represents a side chain derived from an amino acid. 2 is hydrogen and R 3 Except when is CH2CH(OH)CH2. R 3 represents an alkylene group having 1 to 30 carbon atoms which may have a hydroxyl group, an ether group or an ester group. R 4 represents an alkyl group having 1 to 30 carbon atoms which may have an aromatic ring)

[0027] The general formula (1-2) above is a structure corresponding to the amino acid structure of proline.

[0028] The central carbon of the amino acid skeleton is a chiral carbon, but the configuration is not particularly limited, and may be any one of D-form, L-form, racemic form, etc.

[0029] Examples of amino acid-derived side chains include, but are not limited to, isoleucine, leucine, valine, histidine, lysine, methionine, phenylalanine, threonine, tryptophan, asparagine, aspartic acid, alanine, arginine, cysteine / cystine, glutamine, glutamic acid, proline, serine, and tyrosine. The compound of the present invention is R 2 is hydrogen and R 3 Except when is CH2CH(OH)CH2.

[0030] As is clear from the general formula above, the compound of the present invention is a molecule having a (meth)acrylic acid structure, a linking group, and an acetylated amino acid structure. Compounds with such a structure can easily be polymerized by cleavage of the unsaturated bond. Furthermore, copolymerization with other monomers is also possible.

[0031] Furthermore, since the polymer has a linking group, the resulting polymer is a compound in which the amino acid structure is located at a suitable distance from the main chain to be formed, allowing the amino acid structure to move relatively freely, which is presumably why self-assembly can be favorably achieved.

[0032] The compound of the present invention is also preferable in that it can be suitably copolymerized with a commonly used general unsaturated monomer. Compounds having an amino acid structure and an unsaturated bond may be difficult to copolymerize with other monomers depending on the structure. The compound of the present invention is preferable in that it is easy to copolymerize, and therefore its physical properties can be easily adjusted, and copolymers with various physical properties can be obtained.

[0033] Furthermore, such compounds are also preferable in that they can be synthesized relatively easily and produced from inexpensive raw materials.

[0034] A more specific example of such a compound is a compound represented by the following general formula (4).

[0035] [ka] (In the formula, R 1 represents hydrogen or a methyl group. R 2 represents a side chain derived from an amino acid. 2 is hydrogen and R 3 Except when is CH2CH(OH)CH2. That is, it is a molecule having a (meth)acrylic acid structure, a glycidyl group, and an acetylated amino acid structure.

[0036] The method for synthesizing such a compound is not particularly limited, but for example, it can be obtained by reacting a compound having a (meth)acrylic acid skeleton and a linking group skeleton with an amino acid in which the amino group is amidated (hereinafter, sometimes referred to as amino acid).

[0037] [ka]

[0038] In the above formula, X is not particularly limited as long as it is a functional group that reacts with a carboxyl group to form an ester bond, and examples thereof include a hydroxyl group, an epoxy group, etc. Known compounds can be used as raw materials for such reactions.

[0039] As a specific example of the above reaction, a method for synthesizing the compound represented by the above general formula (4) will be described in detail below. Such a reaction can be represented by the following general formula:

[0040] [ka]

[0041] The raw material in the above reaction, glycidyl (meth)acrylate, is a known compound. By reacting this with an amino acid, the compound of the present invention can be obtained. The reaction can be carried out under the general reaction conditions for an epoxy group and a carboxyl group.

[0042] After such a reaction, the product may be purified, if necessary, by a known method such as column chromatography.

[0043] (polymer) The polymer of the present invention has a structural unit derived from a compound represented by the following general formula (2) or (1-2).

[0044] [ka]

[0045] [ka]

[0046] (In the formula, R 1 represents hydrogen or a methyl group. R 2 represents a side chain derived from an amino acid. R 3 represents an alkylene group having 1 to 30 carbon atoms which may have a hydroxyl group, an ether group or an ester group. R 4 represents an alkyl group having 1 to 30 carbon atoms which may have an aromatic ring)

[0047] The polymer of the present invention is the above-mentioned R 2 is hydrogen and R 3 is CH2CH(OH)CH2. Such a monomer can also be produced in the same manner as the compound of the present invention described above.

[0048] The compound represented by the above general formula (2) is more preferably a compound represented by the following general formula (4).

[0049] [ka] (In the formula, R 1 represents hydrogen or a methyl group. R 2 represents a side chain derived from an amino acid.

[0050] The polymer of the present invention has a structure derived from amino acids that makes it easy to form a crosslinked structure based on hydrogen bonds, and therefore has excellent elasticity and strength.

[0051] The structure represented by the general formula (2) encompasses many types of compounds with different amino acid structures. The polymer of the present invention may be a homopolymer of a specific compound among such compounds, or a copolymer of multiple types of compounds.

[0052] The polymer of the present invention may have, as a copolymerization component, a structural unit derived from a monomer other than the monomer represented by the above-mentioned general formula (2). Even in such a copolymer, the amino acid structural portion generates an interaction, thereby producing the various effects described above.

[0053] The copolymerization component in the polymer of the present invention is not particularly limited, and any known compound can be used as long as it is a compound that undergoes polymerization by cleavage of an unsaturated bond.

[0054] For example, alkyl (meth)acrylates can be used in designs requiring flexibility. For further compatibilization or hydrogen bonding, the use of hydroxyalkyl (meth)acrylates is even more suitable. Films obtained using such designs have high breaking elongation and strength, and by controlling the Tg, stretched or deformed films can be restored to their original shape at a specified temperature. On the other hand, for designs requiring relatively high resistance to external stimuli, such as scratch resistance on the film surface, the use of oligomers or multifunctional (meth)acrylates, such as epoxy (meth)acrylates or urethane (meth)acrylates, in combination is preferred. Films obtained using such designs have excellent chemical resistance and scratch resistance, and even relatively flexible designs can be made scratch-resistant through their restoration effect. Furthermore, by using them in combination with various plastic materials or resin elastomers, resins can be modified to achieve desired functions. In particular, stress relaxation and improved adhesion and bonding strength between materials can be achieved. Because such a wide range of design possibilities are possible, these films are expected to have a wide range of applications, from general to specialized industrial uses, including electronic materials, displays, adhesive materials, and medical materials, which will be described later.

[0055] When the polymer of the present invention is used as a medical material, it is preferable that the copolymerization component is also a highly biocompatible and safe material, such as hydroxyalkyl (meth)acrylate or alkoxyalkyl (meth)acrylate. The hydroxyalkyl (meth)acrylate and alkoxyalkyl (meth)acrylate are not particularly limited, but preferred examples include hydroxyalkyl (meth)acrylates and alkoxyalkyl (meth)acrylates having an alkoxyalkyl group having 2 to 20 carbon atoms, more preferred examples include hydroxyalkyl (meth)acrylates and / or alkoxyalkyl (meth)acrylates having an alkoxyalkyl group having 2 to 15 carbon atoms, even more preferred examples include hydroxyalkyl (meth)acrylates and / or alkoxyalkyl (meth)acrylates having an alkoxyalkyl group having 2 to 8 carbon atoms, and particularly preferred examples include hydroxyalkyl (meth)acrylates and / or alkoxyalkyl (meth)acrylates having an alkoxyalkyl group having 2 to 5 carbon atoms.

[0056] Specific preferred examples of the hydroxyalkyl(meth)acrylate and / or alkoxyalkyl(meth)acrylate include compounds represented by the following general formula (1). CH2=CR 11 -COO-R 12 -OR 13 (1) (In the formula, R 11 represents a hydrogen atom or a methyl group. 12 represents an alkylene group having 1 to 10 carbon atoms. 13 represents an alkyl group having 1 to 10 carbon atoms or H. R 12 As the alkylene group, an alkylene group having 1 to 5 carbon atoms is preferred, and an alkylene group having 1 to 3 carbon atoms is more preferred. R 13 is preferably an alkyl group having 1 to 5 carbon atoms or hydrogen, more preferably an alkyl group having 1 to 3 carbon atoms.

[0057] The alkoxyalkyl (meth)acrylate is preferably a compound represented by the following general formula (3). [ka] (In the formula, R 11 is a hydrogen or methyl group. R 12 represents an alkylene group having 1 to 20 carbon atoms, which may be branched.

[0058] More specifically, alkoxyalkyl (meth)acrylates are particularly preferably 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. Among these, those having a secondary hydroxyl group are preferred because they have a moderate hydrogen bond that is not too strong compared to a primary hydroxyl group. Examples of such monomers include:

[0059] Specific preferred examples of the alkoxyalkyl (meth)acrylate include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxypropyl (meth)acrylate, methoxybutyl (meth)acrylate, ethoxymethyl (meth)acrylate, ethoxyethyl (meth)acrylate, ethoxypropyl (meth)acrylate, ethoxybutyl (meth)acrylate, etc. Among these, methoxyethyl (meth)acrylate is preferred, and 2-methoxyethyl acrylate is more preferred, in that it can provide a polymer that has even better biocompatibility and can provide a hydrogel with excellent elongation. The monomer composition of the present invention may contain only one type of the alkoxyalkyl (meth)acrylate, or may contain two or more types of the alkoxyalkyl (meth)acrylate.

[0060] Furthermore, a monomer having an ether group may be used. Such a monomer can also form a hydrogen bond, and therefore, the same effect as the above-mentioned hydroxyl group-containing monomer can be obtained. Examples of such a monomer having an ether group include a vinyl alkyl ether compound and an alkyl ether compound of hydroxyalkyl (meth)acrylic acid.

[0061] Hydroxyalkyl (meth)acrylates are not only biologically safe but also have hydroxyl groups in the monomers that can form hydrogen bonds, making them preferable for achieving the effects of the present invention based on the hydrogen bonds described above.

[0062] The polymer of the present invention is preferable in that it can constitute a hydrogel containing water therein. Hydrogels have flexibility and stretchability similar to those of biological tissues, and are therefore used as medical materials, and are expected to be applied to new uses in the future. The polymer of the present invention has an amino acid structure, and therefore has excellent biocompatibility, making it suitable for use as a medical material.

[0063] Furthermore, the hydrogel has properties such as temperature responsiveness and self-organizing ability, and therefore can be suitably used in fields where these properties are required.

[0064] The polymer of the present invention may be a polymer consisting of only the compound represented by the above general formula (1), or may be used as a copolymer with other monomers.

[0065] The other monomer is not particularly limited, and can be copolymerized with any compound having a polymerizable unsaturated bond. When the polymer of the present invention is used as a medical material, it is preferable that the monomer used in combination also has excellent biocompatibility.

[0066] When the polymer of the present invention is a copolymer, the blending ratio of the monomer represented by the above-mentioned general formula (1-1) or (1-2) in the polymer is not particularly limited, but is preferably 10 mol % or more. By adjusting the blending ratio within this range, various effects resulting from the use of the monomer represented by the above-mentioned general formula (1-1) or (1-2) can be suitably obtained.

[0067] The polymerization method for the polymer of the present invention is not particularly limited, and can be carried out by a general method. Specific examples include thermal radical polymerization, photoradical polymerization, anionic polymerization, and cationic polymerization. Among these, radical polymerization is particularly preferred.

[0068] When the radical polymerization is carried out by light, it is preferable to use a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and examples thereof include acetophenone-based initiators such as 1-hydroxycyclohexyl phenyl ketone (trade name: IRGACURE 184), 2-hydroxy-2-methylpropiophenone (trade name: IRGACURE 1173), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one; benzoin-based initiators such as benzoin and 2,2-dimethoxy-1,2-diphenylethan-1-one; benzophenone, [4-(methylphenylthio)phenyl]phenylmethanone, 4-hydroxybenzophenone, and 4-phenylbenzophenone. Examples of initiators that can be used include benzophenone initiators such as 2-chlorothioxanthone and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone initiators such as 2-chlorothioxanthone and 2,4-diethylthioxanthone; acylphosphine oxide initiators such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; and oxime ester initiators such as 1,2-octanedione, 1-[4-(phenylthio)phenyl], 2-(0-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazoyl-3-yl], and 1-(0-acetyloxime). The amount of the photopolymerization initiator used is preferably 0.1 to 10% by weight based on the total amount of monomers constituting the polymer (B).

[0069] The conditions for photopolymerization are not particularly limited, and examples of light sources include a high-pressure mercury lamp, an LED lamp, and a metal halide lamp.

[0070] When the radical polymerization reaction is carried out by thermal reaction, it is preferable to use a radical polymerization initiator. The radical polymerization initiator is not particularly limited, and examples thereof include azobisisobutyronitrile (AIBN), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2-methylpropionate)dimethyl, 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, and cumene hydroperoxide. The amount of the thermal polymerization initiator used is preferably 0.1 to 10% by weight based on the total amount of monomers constituting the polymer (B).

[0071] (Heat and energy ray curable resin composition) The present invention also relates to a heat- and energy ray-curable resin composition (hereinafter referred to as energy ray-curable resin composition, etc.) containing the compound represented by the above-mentioned general formula (2) and a heat- and photopolymerization initiator.

[0072] Such energy ray-curable resin compositions can be used to form cured coatings by coating a substrate and then curing the coating with heat or energy rays. Alternatively, a molded product can be obtained by curing the coating with heat or energy rays.

[0073] The thermal or photopolymerization initiator is not particularly limited, and the compounds exemplified above can be used alone or in combination.

[0074] The energy ray-curable resin composition of the present invention may be one in which two or more compounds represented by general formula (1-1) or (1-2) are used in combination. Furthermore, a monomer other than the compounds represented by general formulas (1-1) and (1-2) may also be used in combination. In this case, it is preferable that the compound represented by general formula (1-1) or (1-2) accounts for 1 mass % or more of the total amount of monomers.

[0075] When the energy ray-curable resin composition or the like of the present invention uses a monomer other than the compound represented by the general formula (1-1) or (1-2) in combination, the monomer to be used is particularly preferably the compound exemplified as one that can be used as a copolymerization component in the above-mentioned polymer.

[0076] The energy ray-curable resin composition of the present invention may contain other components as needed, such as polymerizable unsaturated compounds and organic or inorganic fillers, and an organic solvent may also be used as needed.

[0077] (hydrogel) The present invention is a hydrogel containing the above polymer and water. The hydrogel of the present invention exhibits reversible phase separation behavior, i.e., it becomes cloudy when heated above its lower critical solution temperature (LCST), and dissolves and returns to a transparent state when cooled below that temperature. This behavior provides favorable properties in terms of controlling the mechanical properties and network structure of the gel.

[0078] Conversely, polymers are also known that exhibit an upper critical solution temperature (UCST), which means that they undergo phase separation at low temperatures and dissolve at high temperatures. Even hydrogels made from polymers having amino acid structures have significantly different physical properties depending on the structure of the compound. Therefore, the performance of the hydrogel made from the polymer of the present invention cannot be predicted by a person skilled in the art from the performance of polymers having known amino acid structures.

[0079] Such a gel composition preferably contains the polymer in an amount of 10 to 50% by mass relative to the total amount of the composition. By keeping the amount within this range, excellent performance can be achieved.

[0080] The hydrogel of the present invention may consist of only the above polymer and water, or may contain other components as required. In this case, the other components include organic solvents, biopolymers such as proteins, polysaccharides, and nucleic acids, and low molecular weight drugs.

[0081] The hydrogel preferably contains the polymer in an amount of 10 to 90% by mass relative to the total amount of the hydrogel, and preferably contains water in an amount of 90 to 10% by mass.

[0082] The hydrogel of the present invention has excellent performance in terms of temperature responsiveness and self-organizing ability, and therefore can be suitably used in fields such as medical materials, cosmetic materials, and optical materials, utilizing such performances as shape-fixed / memory gels, self-repairing gels, reshapeable gels, and injectable gels.

[0083] Among these, the hydrogel of the present invention can be particularly suitably used as a medical material. Among medical materials, it can be particularly suitably used in fields where it comes into direct contact with living bodies. When used in this application, the excellent bioadaptability of the polymer of the present invention can be effectively utilized.

[0084] (Medical materials) The polymer, energy ray-curable resin composition, or hydrogel of the present invention can be particularly suitably used as a medical material. Specific examples of such a medical material include the following:

[0085] Catheters inserted or left in the digestive tract via the mouth or nose, such as gastric catheters, nutritional catheters, and enteral feeding (ED) tubes; catheters inserted or left in the airway or trachea via the mouth or nose, such as oxygen catheters, oxygen cannulas, endotracheal tube tubes and cuffs, tracheostomy tube tubes and cuffs, and endotracheal suction catheters; catheters inserted or left in the urethra or ureter, such as urinary catheters, urinary catheters, and balloon catheters; catheters inserted or left in various body cavities, organs, and tissues, such as suction catheters, drainage catheters, and rectal catheters; indwelling needles Catheters that are inserted or left in blood vessels, such as thermodilution catheters, IVH catheters, angiography catheters, vasodilator catheters, and dilators or introducers; or guide wires, stylets, etc. for these catheters; examination instruments and treatment instruments for insertion into various organs; stents, artificial blood vessels, artificial tracheas, artificial bronchi, etc.; medical devices for extracorporeal circulation treatment (artificial hearts, artificial lungs, artificial kidneys, artificial valves, etc.) and their circuits; artificial joints, artificial femoral heads, sutures, dental materials, various adsorbents, plasma exchange membranes, CAPD, IABP, pacemakers, blood bags, urine collection bags, blood transfusion sets, etc.

[0086] When the polymer of the present invention is used as a medical material, it is preferably used in applications that involve direct contact with biological tissues or body fluids. Because the polymer of the present invention has an amino acid structure, it has excellent biocompatibility. Furthermore, it can also have physical properties similar to those of biological materials. Therefore, by using it as it is with existing highly biocompatible medical polymer materials or by using it in combination with a modifier, it can become a highly functional membrane, and can be suitably used as a material for artificial organs, artificial blood vessels, etc., and further as a surface treatment material for medical devices that are used in direct contact with biological tissues or body fluids. [Example]

[0087] The present invention will be described below based on examples. The present invention is not limited to the following examples. Unless otherwise specified, the terms "%" and "parts" refer to "% by mass" and "parts by mass."

[0088] (Reagents used) In the following examples, the reagents used are as follows: Hexane, ethyl acetate, acetone, 2,2-azobisisobutyronitrile (AIBN), sea sand A, and N,N-dimethylformamide (DMF) were purchased from Nacalai Tesque, Inc. Wakogel® C-400HG, ultra-dehydrated N,N-dimethylformamide (DMF), and 2-hydroxyethyl methacrylate (HEMA) were purchased from Fujifilm Wako Pure Chemical Industries, Ltd. Ultra-dehydrated DMF was purified using a solvent purification system (Nikko Hansen GC3S).

[0089] Synthesis Example 1 A four-neck flask equipped with a thermometer, a stirrer, and a water-cooled condenser was charged with 117.1 g (1.0 mol) of N-acetylglycine, 156.4 g (1.1 mol) of glycidyl methacrylate, 0.27 g of 4-methoxyphenol, 0.14 g of 2,6-di-tert-butylcresol, and 2.7 g of trimethylglycine, and the mixture was reacted at 80°C for 14 hours. The reaction was terminated when the acid value reached 5 or less, and the resulting reaction product was purified by column chromatography to obtain N-acetylglycine monomer (Ac-Gly-GMA).

[0090] Synthesis Example 2 A four-necked flask equipped with a thermometer, a stirrer, and a water-cooled condenser was charged with 89.1 g (1.0 mol) of L-alanine, 127.6 g (1.25 mol) of acetic anhydride, and 108.4 g of acetic acid, and the mixture was reacted at 55° C. for 1 hour. To this was added 325.0 g of toluene, and after cooling to 10° C., the mixture was stirred for 1 hour while maintaining the temperature. The precipitate was collected by filtration and dried under reduced pressure to obtain N-acetyl-L-alanine. A four-neck flask equipped with a thermometer, a stirrer, and a water-cooled condenser was charged with 131.1 g (1.0 mol) of N-acetyl-L-alanine, 149.1 g (1.05 mol) of glycidyl methacrylate, 0.28 g of 4-methoxyphenol, 0.14 g of 2,6-di-tert-butylcresol, and 2.8 g of trimethylglycine, and the mixture was reacted at 80°C for 14 hours. The reaction was terminated when the acid value reached 5 or less, and the resulting reaction product was purified by column chromatography to obtain N-acetyl-L-alanine monomer (Ac-L-Ala-GMA).

[0091] Synthesis Example 3 A four-necked flask equipped with a thermometer, a stirrer, and a water-cooled condenser was charged with 89.1 g (1.0 mol) of DL-alanine, 127.6 g (1.25 mol) of acetic anhydride, and 122.5 g of acetic acid, and the mixture was reacted at 55° C. for 1 hour. 340.0 g of methyl isobutyl ketone was added to the mixture, which was then cooled to 10° C. and stirred for 1 hour while maintaining the temperature. The precipitate was collected by filtration and dried under reduced pressure to obtain N-acetyl-DL-alanine. A four-neck flask equipped with a thermometer, a stirrer, and a water-cooled condenser was charged with 131.1 g (1.0 mol) of N-acetyl-DL-alanine, 149.1 g (1.05 mol) of glycidyl methacrylate, 0.28 g of 4-methoxyphenol, 0.14 g of 2,6-di-tert-butylcresol, and 2.8 g of trimethylglycine, and the mixture was reacted at 80°C for 14 hours. The reaction was terminated when the acid value reached 5 or less, and the resulting reaction product was purified by column chromatography to obtain N-acetyl-DL-alanine monomer (Ac-DL-Ala-GMA).

[0092] Synthesis Example 4 In a four-neck flask equipped with a thermometer, stirrer, and water-cooled condenser, add 117.2g of L-valine. g (1.0 mol), 127.6 g (1.25 mol) of acetic anhydride, and 244.8 g of acetic acid were charged, and the mixture was reacted at 55° C. for 1 hour. To this was added 490.0 g of toluene, and after cooling to 10° C., the mixture was stirred for 1 hour while maintaining the temperature. The precipitate was collected by filtration and dried under reduced pressure to obtain N-acetyl-L-valine. A four-neck flask equipped with a thermometer, a stirrer, and a water-cooled condenser was charged with 159.2 g (1.0 mol) of N-acetyl-L-valine, 156.4 g (1.1 mol) of glycidyl methacrylate, 0.32 g of 4-methoxyphenol, 0.16 g of 2,6-di-tert-butylcresol, and 3.2 g of trimethylglycine, and the mixture was reacted at 80°C for 14 hours. The reaction was terminated when the acid value reached 5 or less, and the resulting reaction product was purified by column chromatography to obtain N-acetyl-L-valine monomer (Ac-L-Val-GMA).

[0093] Synthesis Example 5 In a four-neck flask equipped with a thermometer, stirrer, and water-cooled condenser, 131.2g of L-leucine was added. g (1.0 mol), 127.6 g (1.25 mol) of acetic anhydride, 258.8 g of acetic acid, and 4.18 g of methanesulfonic acid were charged, and the mixture was reacted at 60° C. for 1 hour. To this was added 520.0 g of toluene, and after cooling to 10°C, the mixture was stirred for 1 hour while maintaining the temperature. The precipitate was collected by filtration and dried under reduced pressure to obtain N-acetyl-L-leucine. A four-neck flask equipped with a thermometer, a stirrer, and a water-cooled condenser was charged with 173.2 g (1.0 mol) of N-acetyl-L-leucine, 156.4 g (1.1 mol) of glycidyl methacrylate, 0.33 g of 4-methoxyphenol, 0.16 g of 2,6-di-tert-butylcresol, and 3.3 g of trimethylglycine, and the mixture was reacted at 80°C for 14 hours. The reaction was terminated when the acid value reached 5 or less, and the resulting reaction product was purified by column chromatography to obtain N-acetyl-L-leucine monomer (Ac-L-Leu-GMA).

[0094] The structure of the obtained compound was confirmed as follows: Ac-Gly-GMA is HH COSY, HMQC, 1H-NMR, 13 C-NMR spectroscopy was performed, and the results for Ac-L-Ala-GMA, Ac-DL-Ala-GMA, Ac-Val-GMA, and Ac-Leu-GMA were 1 The NMR data for each compound obtained is shown below. In addition, 1 H-NMR spectra were measured at 500 MHz using a JNM-ECA500 manufactured by JEOL Ltd. A φ5 × 7 inch NMR test tube was used for the measurements, the temperature was 25 °C, and the number of accumulations was 16. DMSO-d6 was used as the deuterated solvent, and TMS was used as the reference substance. 13 C-NMR was measured using a JNM-ECA500 manufactured by JEOL Ltd. A φ5 x 7 inch NMR test tube was used for the measurement, the temperature was 25 °C, and the number of accumulations was 1024. DMSO-d6 was used as the deuterated solvent, and TMS was used as the reference substance.

[0095] Ac-Gly-GMA 13 C-NMR (DMSO-d6, TMS): 18ppm (CH3CCH2-), 22 ppm (CH3CONH-), 41 ppm (-COCH2NH-), 60, 65 ppm (-CHOHCH2OCO-), 66 ppm (-CH2CHOHCH2-), 126 ppm (CH2CCH3-), 136 ppm (CH2CCH3-), 166 ppm (-CCOOCH2-), 170,171 ppm (-OCO-) 1 H-NMR (DMSO-d6, TMS): 1.8-1.9 ppm (3H, -COCH3, acetyl group), 1.9-2.0 ppm (3H, CH3C(CH2), methyl), 3.8-3.9 ppm (2H, -CH2NH-, side chain of Gly), 3.5-5.1 ppm (5H, -CH2CHOHCH2- ), 5.3-5.4 ppm ( 1H, -OH, hydroxy group), 5.6-5.7, 6.0-6.1 ppm (2H, CH2C-, vinyl group), 8.2-8.3 ppm (1 H, -NH-, amide).

[0096] Ac-L-Ala-GMA 1 H-NMR (DMSO-d6, TMS) : 1.1-1.3 ppm (3H, -CHCH3NH-, side chain of L-Ala), 1.8-ppm (3H, -COCH3, acetyl group), 1.9 ppm (3H, CH3C(CH2), methyl), 3.5-5.1 ppm (6H, -CH2CHOHCH2OCOCH- ), 5.3-5.4 ppm (1H, -OH, hydroxy group), 5.6-5.7, 6.0-6.1 ppm (2H, CH2C-, vinyl group), 8.2-8.3 ppm (1H, -NH-, amide).

[0097] Ac-DL-Ala-GMA 1 H-NMR (DMSO-d6, TMS) : 1.1-1.3 ppm (3H, -CHCH3NH-, side chain of DL-Ala), 1.8-ppm (3H, -COCH3, acetyl group), 1.9 ppm (3H, CH3C(CH2), methyl), 3.5-5.1 ppm (6H, -CH2CHOHCH2OCOCH- ), 5.3-5.4 ppm (1H, -OH, hydroxy group), 5.6-5.7, 6.0-6.1 ppm (2H, CH2C-, vinyl group), 8.2-8.3 ppm (1H, -NH-, amide).

[0098] Ac-L-Val-GMA 1H-NMR (DMSO-d6, TMS): 0.8 - 0.9 ppm (6H, -CHCH3CH3, 2-methyl of side chain of LVal), 1.8 - ppm (3H, -COCH3, acetyl group), 1.9 ppm (3H, CH3C(CH2), methyl), 2.0 - 2.1 ppm (1H, -CHCH(CH3)2-, side chain of L-Val), 3.5 - 5.1 ppm (6H, -CH2CHOHCH2OCOCH-), 5.3 - 5.4 ppm (1H, -OH, hydroxy group), 5.6 - 5.7, 6.0 - 6.1 ppm (2H, CH2C-, vinyl group), 8.2 - 8.3 ppm (1H, -NH-, amide).

[0099] Ac-L-Leu-GMA 1 H-NMR (DMSO-d6, TMS) : 0.8 - 0.9 ppm (6H, -CHCH3CH3, 2-methyl of side chain of LLeu), 1.4 - 1.5 ppm (1H, -CHCH(CH3)2-, side chain of LLeu), 1.6 ppm (2H, -CHCH2CH(CH3)2-, side chain of LLeu), 1.8 - ppm (3H, -COCH3, acetyl group), 1.9 ppm (3H, CH3C(CH2), methyl), 3.5 - 5.1 ppm (6H, -CH2CHOHCH2OCOCH-), 5.3 - 5.4 ppm (1H, -OH, hydroxy group), 5.6 - 5.7, 6.0 - 6.1 ppm (2H, CH2C-, vinyl group), 8.2 - 8.3 ppm (1H, -NH-, amide).

[0100] (Example 1: Preparation of Polymer) Homopolymers (pHEMA, p(Ac-XaaGMA) (Xaa = Gly, L-Ala, DL-Ala, L-Val, L-Leu)) were synthesized by free radical polymerization using AIBN as an initiator. The amounts of each component are shown in Table 1. As an example, the synthesis procedure for pHEMA is shown below.

[0101] [Table 1]

[0102] (Polymerization method and hydrogel manufacturing method) 0.65 g (5.0 mmol) of HEMA as a monomer and 0.00410 g (0.025 mmol) of AIBN as an initiator were dissolved in ultra-dehydrated DMF to a total volume of 5 mL. The solution was transferred to a test tube. Dissolved oxygen was removed by repeated freeze-degassing using liquid nitrogen as a cryogen under a N2 atmosphere. The tube was then sealed under reduced pressure and polymerized in an oil bath at 60 °C for 24 hours. After polymerization, the product was purified by reprecipitation using DMF as a good solvent and ethyl acetate as a poor solvent, followed by drying under reduced pressure in a desiccator. After drying under reduced pressure, the product was swollen in distilled water and freeze-dried to remove the water, yielding the desired pHEMA as a white solid. The synthesized polymer was then soaked in a sufficient amount of distilled water and allowed to stand overnight at 25 °C to prepare a hydrogel.

[0103] The NMR measurement results for each homopolymer obtained in this manner are shown below.

[0104] pHEMA Yield: 0.4831 g Yield: 74% 11H-NMR (DMSO-d6, TMS): 0.7 - 1.3 ppm (3H, -CH3, main chain of polymer), 1.3 - 2.3 ppm (2H, -CH2C(CH3)-, main chain of polymer), 3.6 - 3.8 ppm (2H, -CH2OH, side chain of polymer), 3.8 - 4.0 ppm (2H, -OCH2CH2-, side chain of polymer), 4.7 - 4.9 ppm ( 1 H, -OH, hydroxy group).

[0105] p(Ac-Gly-GMA) Yield: 0.8142 g, Yield rate: 63% 1 1H-NMR (DMSO-d6, TMS): 0.5 - 1.3 ppm (3H, CH3C(CH2)-, main chain of polymer), 1.5 - 2.3 ppm (5H, -CH2C(CH3)-, CH3CO-), 3.5 - 5.1 ppm (7H, -OCH2CHOHCH2O-, -CH2NH-), 5.2 - 5.4 ppm (1H, -OH, hydroxy group), 8.2 - 8.4 ppm ( 1 H, -NH-, amide).

[0106] p(Ac-L-Ala-GMA) Yield: 0.7325 g, Yield rate: 54% 1H-NMR (DMSO-d6, TMS): 0.5 - 1.2 ppm (3H, CH3C(CH2)-, main chain of polymer), 1.2 - 1.5 ppm (3H, -C(CH3)NH-, side chain of L-Ala), 1.5 - 2.3 ppm (5H, -CH2C(CH3)-, CH3CO-), 3.5 - 5.1 ppm (6H, -OCH2CHOHCH2O-, -CHNH-), 5.2 - 5.4 ppm (1H, -OH, hydroxy group), 8.2 - 8.4 ppm (1H, -NH-, amide).

[0107] p(Ac-DL-Ala-GMA) Yield: 0.8001 g, Yield rate: 59% 1 H-NMR (DMSO-d6, TMS): 0.5 - 1.2 ppm (3H, CH3C(CH2)-, main chain of polymer), 1.2 - 1.5 ppm (3H, -C(CH3)NH-, side chain of DL-Ala), 1.5 - 2.3 ppm (5H, -CH2C(CH3)-, CH3CO-), 3.5 - 5.1 ppm (6H, -OCH2CHOHCH2O-, -CHNH-), 5.2 - 5.4 ppm ( 1 H, -OH, hydroxy group), 8.2 - 8.4 ppm ( 1 H, -NH-, amide).

[0108] p(Ac-Val-GMA) Yield: 0.6123 g, Yield rate: 41% 1H-NMR (DMSO-d6, TMS): 0.5-1.2 ppm (9H, CH3C(CH2)-, -C(CH3)2, main chain of polymer, side chain of Val), 1.3-2.3 ppm (6H, -CH2C(CH3)-, -COCH3, -CHCH(CH3)2), 3.5-5.1 ppm (6H, -OCH2CHOHCH2O-, -CHNH-), 5.2-5.4 ppm (1H, -OH, hydroxy group), 8.2-8.4 ppm (1H, -NH-, amide).

[0109] p(Ac-Leu-GMA) Yield: 0.4453g Yield: 28% 1 H-NMR (DMSO-d6, TMS): 0.5-1.2 ppm (9H, CH3C(CH2)-, -C(CH3)2, main chain of polymer, side chain of Leu), 1.4-1.6 ppm (1H, -CH(CH3)2), 1.6-1.8 ppm (2H, -CH2C(CH3)2), 1.8-2.3 ppm (5H, -CH2C(CH3)-, -COCH3,), 3.5-5.1 ppm (6H, -OCH2CHOHCH2O-, -CHNH-), 5.2-5.4 ppm (1H, -OH, hydroxy group), 8.2-8.4 ppm (1H, -NH-, amide).

[0110] (Example 2: Co-overlapping compound HEMA1-x-co-(Ac-Xaa-GMA)x) (Xaa=Gly, L-Ala, DL-Ala, L-Val, L-Leu) (x = 0.1, 0.3, 0.5)Synthetic とハイドロゲルのproduced) Each copolymer was synthesized by free radical polymerization using AIBN as an initiator. The amounts of each polymer are shown in Tables 2–6. As an example, the synthesis procedure for p(HEMA1-x-co-(Ac-Gly-GMA)x) (x = 0.1) is shown below. 0.1295 g (0.5,000 mmol) of Ac-Gly-GMA and 0.585 g (4.50 mmol) of HEMA were dissolved as monomers, and 0.00410 g (0.025 mmol) of AIBN was dissolved as initiator in ultra-anhydrous DMF. The total volume was adjusted to 5 mL, and the solution was transferred to a test tube.

[0111] The tube was then repeatedly freeze-degassed in a N2 atmosphere using liquid nitrogen as a cryogen to remove dissolved oxygen. The tube was then sealed under reduced pressure and polymerized in an oil bath at 60°C for 24 hours. After polymerization, the polymer was purified by reprecipitation using DMF as a good solvent and ethyl acetate as a poor solvent, and then dried under reduced pressure in a desiccator. After drying under reduced pressure, the polymer was swollen in distilled water and freeze-dried to remove the water, yielding the desired p(HEMA1-x-co-(Ac-Gly-GMA)x) (x = 0.1) as a white solid. Other samples were synthesized using a similar procedure. Hydrogels were prepared by adding a sufficient amount of distilled water to the synthesized polymers and leaving them at 25°C overnight.

[0112] [Table 2]

[0113] [Table 3]

[0114] [Table 4]

[0115] [Table 5]

[0116] [Table 6]

[0117] The obtained polymers and hydrogels were evaluated based on the following criteria. (Evaluation of transmittance by measuring absorption spectrum) The temperature dependence of transmittance for polymers dissolved in water was evaluated using a JASCO V650 UV-Vis spectrophotometer. The quartz cell used for the measurements had an optical path length of 1 cm. Measurements were performed at a sample concentration of 1 wt%, at a wavelength of 600 nm, and at temperatures ranging from 10°C to 70°C (Figure 1).

[0118] [Table 7]

[0119] Focusing on the temperature rise process, it is found that p(Ac-L-Ala-GMA) and p(Ac-DL-Ala-GMA) exhibit LCST-type behavior, in which the transmittance decreases with increasing temperature and phase separation occurs. This is because below the phase transition temperature (Tt), the polymer / water interactions are stronger than the polymer / polymer interactions, and the polymer chains are hydrated with water molecules. However, above the phase transition temperature, the polymer / polymer interactions dominate over the polymer / water interactions, and the polymer chains dehydrate and aggregate.

[0120] The phase transition temperatures for both p(Ac-DL-Ala-GMA) and p(Ac-L-Ala-GMA) are around 30°C, but p(Ac-DL-Ala-GMA) exhibits a slightly higher temperature. The only difference between the two polymers is the structure of the alanine in the side chain. Therefore, the results indicate that the racemic p(Ac-DL-Ala-GMA) exhibits slightly weaker intermolecular and intermolecular interactions than p(Ac-L-Ala-GMA). Next, examining the phase transition temperatures during the heating and cooling processes, we found that the temperature during the cooling process was approximately 2°C lower than during the heating process. This is known to be due to the aggregation of polymer chains, which forms intramolecular and intramolecular hydrogen bonds, making it difficult for water molecules to form hydrogen bonds with the polymer chains, delaying rehydration. p(Ac-Gly-GMA) did not undergo a phase transition between 10°C and 70°C. This is thought to be because p(Ac-Gly-GMA) has many hydrogen bond acceptors within the molecule, so hydration with water takes precedence over intermolecular and intramolecular interactions. Furthermore, p(Ac-Ala-GMA) has one methyl group in the amino acid side chain, whereas p(Ac-Gly-GMA) does not. This means that the balance of polymer / polymer and polymer / water interactions changes depending on the presence or absence of a methyl group (changes in hydrophobicity and steric hindrance).

[0121] (Measurement of saturated water content of hydrogel) The dry mass (Wd) of each polymer was measured. Then, the gel mass (Ws) was measured after immersing it in distilled water and allowing it to swell overnight in an incubator at 25°C. From these measurements, the saturated water content of the gel for each polymer was calculated using the following equation (1). Saturation water content (%) = ((amount of water absorbed by the hydrogel) / (weight of the gel in the dry state)) × 100 = ((Ws-Wd) / Wd)×100 (Figure 2)

[0122] For p(HEMA1-x-co-(Ac-Gly-GMA)x) (x = 0.5), the saturated water content was not measured because it was a viscous liquid that was not completely soluble in water but did not form a hydrogel. Focusing on p(HEMA-co-(Ac-Gly-GMA)), p(HEMA-co-(Ac-L-ALa-GMA)), and p(HEMA-co-(Ac-DL-ALa-GMA)), we found that the saturated water content generally increased as the amino acid-derived monomer composition ratio increased. Since both the homopolymers of glycine- and alanine-derived monomers were soluble in water, the three polymers, p(HEMA-co-(Ac-Gly-GMA)), p(HEMA-co-(Ac-L-ALa-GMA)), and p(HEMA-co-(Ac-DL-ALa-GMA)), are highly hydrophilic, and hydration with water is considered to be dominant over intramolecular and intermolecular interactions within the polymer. Therefore, it is thought that the water content of the copolymer increased with increasing content of the highly hydrophilic glycine- and alanine-derived monomers, even when the copolymerization ratio was changed. On the other hand, for p(HEMA-co-(Ac-Val-GMA)) and p(HEMA-co-(Ac-Leu-GMA)), the saturated water content was lowest when x = 0.5. The side chains of valine and leucine are CH(CH3)2 and CH2CH(CH3)2, respectively, which are more hydrophobic than glycine and alanine. In copolymerization of HEMA with glycine and alanine-derived monomers, hydrogen bonding between water and the polymer occurs, resulting in low crosslink density. However, in the case of valine and leucine, the hydrophobic interactions of the side chains prevent water molecules from approaching the polymer chain. Therefore, when the incorporation ratio of valine and leucine-derived monomers exceeded 50%, hydrophobic interactions between polymers prevailed over hydrogen bonding between water and polymers, resulting in a low saturated water content.

[0123] Example 3: Photocurable resin composition A photoreaction initiator was mixed with each monomer in the mixing ratio shown in Table 8 below, and a 0.5 mm thick silicone sheet with the inside cut out to 3 cm x 5 cm was used as a spacer. The mixture was sandwiched between polyethylene terephthalate films with one side treated for release, and the wavelength was 365 nm and the light intensity was 1000 mJ / cm.2 ×7 passes (total 7000mj / cm 2 ) irradiation In this way, a resin film with a thickness of 0.5 mm was obtained.

[0124] (Tensile test) The obtained resin film was subjected to a tensile test under the following conditions. Temperature: 23℃ Measurement sample cutout size: 10mm x 30mm Film thickness: 0.5 mm Chuck distance: 20mm Tensile speed: 60 mm / min The maximum tensile elongation and the tensile curve are shown in the table.

[0125] (gel fraction) The gel fraction was measured as the remaining weight % of the film by dissolving the film obtained in each example in refluxing THF for 30 minutes using a Soxhlet. The results obtained are shown below.

[0126] [Table 8]

[0127] [Table 9]

[0128] [Table 10]

[0129] [Table 11]

[0130] In Comparative Examples 3-1 and 3-4, a monomer having a urethane bond was blended in place of the amino acid monomer. In these Comparative Examples, the strength of the film was low, suggesting that the interaction of the amino acid monomer was stronger than the interaction of the urethane bond. Examples 3-6 to 3-11 show experimental results for copolymer photocurable resin compositions containing hydroxyethyl acrylate (HEA). When HEA is used as a copolymerization component, strength is increased compared to Examples 3-1 to 3-5, which are homopolymers. This is presumably due to stronger interactions, as HEA is a monomer capable of hydrogen bonding. Comparative Examples 3-2, 3-3, 3-5, and 3-6 did not use the compound of the present invention, but instead used ethyl acrylate with a general bifunctional unsaturated compound. Compared to the compositions containing the compound of the present invention, even at low strength levels, the elongation was significantly lower. This is presumably because the crosslinking was due to covalent bonding, and therefore sufficient elongation was not obtained. From the above results, it is clear that the use of the compound of the present invention can improve both elongation and strength.

[0131] Furthermore, for Example 12, the tensile test was performed up to 250% and then stopped. When the application of stress was stopped, the test specimen returned to its original shape. The test specimen that had returned to its original shape was then subjected to a tensile test under the same conditions again. This test was repeated five times, and the sixth time the test was performed until fracture. The results of the six tensile tests are shown in Table 12.

[0132] [Table 12]

[0133] As shown in Table 12, the curable resin obtained using the compound of the present invention reproducibly returned to its original state even after repeated use. This is presumably due to the strong interaction of the compound.

[0134] From the above results, it is clear that the curable resin obtained by energy curing the thermosetting resin composition of the present invention has excellent elasticity and also excellent recovery. [Industrial Applicability]

[0135] The polymer obtained using the compound of the present invention as a raw material can be suitably used as a medical material and various industrial materials.

Claims

1. A compound represented by the following general formula (1-1) or (1-2): 【Chemistry 1】 【Chemistry 2】 (In the formula, R １ represents hydrogen or a methyl group. R ２ represents a side chain derived from an amino acid. ２ is hydrogen and R ３ is CH 2 CH(OH)CH 2 Except when: R ３ represents an alkylene group having 1 to 30 carbon atoms which may have a hydroxyl group, an ether group or an ester group. R ４ represents an alkyl group having 1 to 30 carbon atoms which may have an aromatic ring)

2. A polymer characterized by having a structural unit derived from a compound represented by the following general formula (2) or (1-2): 【Transformation 3】 【Chemistry 4】 (In the formula, R １ represents hydrogen or a methyl group. R ２ represents a side chain derived from an amino acid. R ３ represents an alkylene group having 1 to 30 carbon atoms which may have a hydroxyl group, an ether group or an ester group. R ４ represents an alkyl group having 1 to 30 carbon atoms which may have an aromatic ring)

3. The polymer according to claim 2, further comprising a structural unit based on a compound represented by the following general formula (3): 【Transformation 5】 (In the formula, R １１ is a hydrogen or methyl group. R １２ represents an alkylene group having 1 to 20 carbon atoms, which may be branched.

4. An energy ray-curable resin composition comprising a compound represented by the following general formula (2) and / or a compound represented by the following general formula (1-2), and a photopolymerization initiator: 【Transformation 6】 【Transformation 7】 (In the formula, R １ represents hydrogen or a methyl group. R ２ represents a side chain derived from an amino acid. R ３ represents an alkylene group having 1 to 30 carbon atoms which may have a hydroxyl group, an ether group or an ester group. R ４ represents an alkyl group having 1 to 30 carbon atoms which may have an aromatic ring)

5. A hydrogel comprising the polymer according to claim 2 or 3 and water.

6. A resin molded article comprising the polymer of claim 2 or 3.

7. A coated article having a coating layer containing the polymer of claim 2 or 3.

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