JP7155713B2 - COMPOSITION, MEDICAL ADHESIVE OR COATING, CONTAINER, MEDICAL SHEET, AND MEDICAL SHEET MANUFACTURER - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composition, a medical adhesive or coating, a container, a medical sheet, and a medical sheet manufacturing apparatus.

Methods for treating wounds and surgical sites include suturing using a general suture thread, suturing using a stapler, and bonding or covering wounds with medical adhesives or coatings.

Conventionally, cyanoacrylate adhesives, gelatin-aldehyde adhesives, and fibrinogel adhesives have been used as medical adhesives. There is concern that cyanoacrylate adhesives and gelatin-aldehyde adhesives are toxic to living organisms. In addition, cyanoacrylate-based adhesives, known as instant adhesives, are hardened by moisture and form a strong adhesive layer. There is a drawback that it is difficult to Although the fibrinogel-based adhesive has low toxicity, it is said to have the risk of infection.
In response to this situation, adhesives containing UV-curable chitosan derivatives, natural tannins, and polyethylene glycol, which are excellent in safety and have water solubility and are advantageous in adhesiveness to living bodies, have been proposed as medical adhesives. (See, for example, Patent Documents 1 to 3 and Non-Patent Document 1.

An object of the present invention is to provide a composition that has hydrophilicity suitable for adhering to a living body and gives a cured product that is excellent in curability, flexibility and adhesiveness.

ただし、前記一般式（１）中、Ｒ_１は炭素数１～６のアルキル基を表し、Ｘは炭素数１～６のアルキレン基を表し、Ｙは下記一般式（２）又は下記一般式（３）を表す。

ただし、前記一般式（２）中、Ｒ_２は炭素数１～１０のアルキル基を表し、＊は前記Ｘとの結合部位を表す。

ただし、前記一般式（３）中、Ｒ_２は炭素数１～１０のアルキル基を表し、＊は前記Ｘとの結合部位を表す。

ただし、前記一般式（４）中、環Ｘは窒素原子を含む炭素数２～５の環構造を表し、Ｒ^４は単結合、又は炭素数１～３の直鎖若しくは分岐のアルキレン基を表し、Ｒ^５は炭素数１～３の直鎖又は分岐のアルキル基を表す。ただし、環Ｘ、Ｒ^４及びＲ^５の炭素数の合計は３～６である。 The composition of the present invention as a means for solving the above problems comprises an acrylamide compound having an ester structure represented by at least one of the following general formula (1) and the following general formula (4), a polymerization initiator, and Contains viscosity adjusting ingredients.

However, in the general formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms, X represents an alkylene group having 1 to 6 carbon atoms, and Y represents the following general formula (2) or the following general formula ( 3).

However, in the general formula (2), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents the bonding site with X.

However, in the above general formula (3), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents the bonding site with X above.

However, in the general formula (4), ring X represents a ring structure having 2 to 5 carbon atoms containing a nitrogen atom, and R ⁴ represents a single bond or a linear or branched alkylene group having 1 to 3 carbon atoms. , R ⁵ represents a linear or branched alkyl group having 1 to 3 carbon atoms. However, the total number of carbon atoms in ring X, R ⁴ and R ⁵ is 3-6.

ADVANTAGE OF THE INVENTION According to this invention, the composition which has hydrophilicity suitable for adhering a living body and can obtain the hardened|cured material excellent in curability, flexibility, and adhesiveness can be provided.

FIG. 1A is a plan view showing an example of the medical sheet of the present invention. FIG. 1B is a schematic cross-sectional view of FIG. 1A. FIG. 2 is a schematic diagram showing an example of another image forming apparatus (three-dimensional stereoscopic image forming apparatus). FIG. 3 is a schematic explanatory diagram illustrating an example of a method for three-dimensional modeling using a composition.

ただし、前記一般式（１）中、Ｒ_１は炭素数１～６のアルキル基を表し、Ｘは炭素数１～６のアルキレン基を表し、Ｙは下記一般式（２）又は下記一般式（３）を表す。

ただし、前記一般式（２）中、Ｒ_２は炭素数１～１０のアルキル基を表し、＊は前記Ｘとの結合部位を表す。

ただし、前記一般式（３）中、Ｒ_２は炭素数１～１０のアルキル基を表し、＊は前記Ｘとの結合部位を表す。

ただし、前記一般式（４）中、環Ｘは窒素原子を含む炭素数２～５の環構造を表し、Ｒ^４は単結合、又は炭素数１～３の直鎖若しくは分岐のアルキレン基を表し、Ｒ^５は炭素数１～３の直鎖又は分岐のアルキル基を表す。ただし、環Ｘ、Ｒ^４及びＲ^５の炭素数の合計は３～６である。 (Composition)
The composition of the present invention contains an acrylamide compound having an ester structure represented by at least one of the following general formula (1) and the following general formula (4), a polymerization initiator, and a viscosity adjusting component, and if necessary Contains other ingredients as appropriate.

However, in the general formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms, X represents an alkylene group having 1 to 6 carbon atoms, and Y represents the following general formula (2) or the following general formula ( 3).

However, in the general formula (2), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents the bonding site with X.

However, in the above general formula (3), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents the bonding site with X above.

However, in the general formula (4), ring X represents a ring structure having 2 to 5 carbon atoms containing a nitrogen atom, and R ⁴ represents a single bond or a linear or branched alkylene group having 1 to 3 carbon atoms. , R ⁵ represents a linear or branched alkyl group having 1 to 3 carbon atoms. However, the total number of carbon atoms in ring X, R ⁴ and R ⁵ is 3-6.

The composition of the present invention is based on the finding that conventional adhesives containing UV-curable chitosan derivatives or natural tannins and polyethylene glycol take a long time to bond.

The compound represented by at least one of the general formula (1) and general formula (4) contained in the composition of the present invention is a tertiary acrylamide compound with a relatively small molecular weight and has an ester structure in the molecule. Characterized by These compounds have low viscosity and are excellent in photopolymerization by ultraviolet irradiation, etc., but they are highly hydrophilic because they have polar functional groups in their small molecular structures, and some compounds exhibit water solubility. , the polymerized product (cured product) itself also has the characteristic of showing hydrophilicity. Therefore, the composition of the present invention has good compatibility with a living body that retains moisture and has excellent adhesive properties, and is suitable for medical adhesives and medical coatings.

Since the acrylamide compound represented by at least one of the above general formula (1) and general formula (4) has a low viscosity and easy to flow properties, it is used for medical adhesives and medical coatings. Therefore, it is necessary to increase the viscosity with a viscosity adjusting component to make it difficult to flow. For this reason, various thickeners, flocculants, etc. can be used as viscosity adjusting components, but compounds with relatively large molecular weights such as polymer components, oligomer components, and reactive oligomers having polymerizable functional groups are used. It is preferably contained. Furthermore, it is possible to contain a reactive monomer compound having many functional groups such as a polyfunctional (meth)acrylate compound, and by forming a crosslinked structure, the state after curing with active energy rays is more likely to be maintained. Become.

As described above, the composition of the present invention contains an acrylamide compound represented by at least one of general formula (1) and general formula (4), which is highly hydrophilic, in addition to polymers, oligomers, and more as viscosity adjusting components. By blending a polyfunctional (meth)acrylate compound, it is excellent in handling before curing, has moderate hydrophilicity even after curing, and forms a crosslinked structure with polymers, oligomers, and polyfunctional monomers. , the shape of the adhesive can be maintained, and adhesiveness suitable for a moist living body can be expressed.
Further, it was confirmed by testing representative compounds that the compounds represented by at least one of the general formula (1) and general formula (4) used in the present invention are considered to have little skin sensitization concern. ing. Polymers and oligomers with large molecular weights are used as the viscosity adjusting component. Furthermore, since it is possible to select a material with less skin sensitization concern for the compound used as the polyfunctional (meth)acrylate, the composition of the present invention can be formed from a material with less skin sensitization risk. It is considered suitable for medical applications because it causes little damage to the living body.

A curable composition is preferred as the composition of the present invention. Examples of curable compositions include thermosetting compositions and active energy ray-curable compositions, with active energy ray-curable compositions being more preferred.

<Acrylamide compound having an ester structure>
The acrylamide compound having an ester structure is represented by at least one of general formula (1) and general formula (4).
R ₁ in the general formula (1) represents an alkyl group having 1 to 6 carbon atoms which may be linear or branched.
Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, A hexyl group and the like can be mentioned.
X in the general formula (1) represents an alkylene group having 1 to 6 carbon atoms which may be linear or branched.
Examples of the alkylene group having 1 to 6 carbon atoms include methylene group, ethylene group, propylene group and butylene group.
Y in the general formula (1) represents the general formula (2) or the general formula (3).

R ₂ in the general formula (2) represents an alkyl group having 1 to 10 carbon atoms which may be linear or branched.
Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, Examples include hexyl group, heptyl group, octyl group, nonyl group and decyl group.
* in the general formula (2) represents a binding site to the X.

R ₂ in the general formula (3) represents an alkyl group having 1 to 10 carbon atoms which may be linear or branched.
Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, Examples include hexyl group, heptyl group, octyl group, nonyl group and decyl group.
* in the general formula (3) represents a binding site to the X.
It is preferable that the acrylamide compound having an ester structure is represented by the general formula (1), and Y in the general formula (1) is represented by the general formula (3).
R ₂ in the general formula (3) is preferably an alkyl group having 1 to 2 carbon atoms.

The acrylamide compound represented by the general formula (1) has an ester structure at the end of a monofunctional tertiary acrylamide having no ring structure. In general, low-molecular-weight tertiary acrylamide compounds are volatile, and therefore have a strong odor peculiar to monomers, which causes discomfort when handling compositions containing these compounds.

Therefore, the tertiary acrylamide compound represented by the general formula (1) has an ester structure at the end. Therefore, the odor can be suppressed due to the decrease in volatility due to the ester structure. In addition, it is believed that curability is improved due to intermolecular interaction due to the presence of the ester structure.

In the general formula (4), ring X represents a ring structure having 2 to 5 carbon atoms and containing a nitrogen atom. Ring X includes, for example, aziridine, azetidine, pyrrolidine, piperidine and the like, preferably pyrrolidine and piperidine.
In general formula (4), R ⁴ represents a single bond or a linear or branched alkylene group having 1 to 3 carbon atoms. Examples of ^R4 include a single bond, methylene group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane -1,3-diyl group and the like.
In general formula (4), R ⁵ represents a linear or branched alkyl group having 1 to 3 carbon atoms. Examples of ^R5 include methyl group, ethyl group, propyl group, isopropyl group and the like.
However, the total number of carbon atoms in ring X, R ⁴ and R ⁵ is 3-6.

Next, as specific examples of the acrylamide compound represented by the general formula (1), exemplary compounds of groups a to h are shown, but are not limited to these.
Examples of the group a of the compound represented by the general formula (1) include compounds of groups a1 to a6 shown below. These may be used individually by 1 type, and may use 2 or more types together.

<<Exemplified compound a1 group>>

<<Exemplified compound a2 group>>

<<Exemplified compound a3 group>>

<<Exemplified compound a4 group>>

<<Exemplified compound a5 group>>

<<Exemplified compound a6 group>>

Examples of the group b of compounds represented by the general formula (1) include compounds of groups b1 to b6 shown below. These may be used individually by 1 type, and may use 2 or more types together.

<<Exemplified compound b1 group>>

<<Exemplified compound b2 group>>

<<Exemplified compound b3 group>>

<<Exemplified compound b4 group>>

<<Exemplified compound b5 group>>

<<Exemplified compound b6 group>>

Examples of the group c of the compounds represented by the general formula (1) include compounds of groups c1 to c6 shown below. These may be used individually by 1 type, and may use 2 or more types together.

<<Exemplified compound c1 group>>

<<Exemplified compound c2 group>>

<<Exemplified compound c3 group>>

<<Exemplified compound c4 group>>

<<Exemplary compound c5 group>>

<<Exemplary compound c6 group>>

Group d of the compound represented by the general formula (1) includes, for example, compounds of groups d1 to d6 shown below. These may be used individually by 1 type, and may use 2 or more types together.

<<Exemplified compound d1 group>>

<<Exemplified compound d2 group>>

<<Exemplified compound d3 group>>

<<Exemplary compound d4 group>>

<<Exemplified compound d5 group>>

<<Exemplified compound d6 group>>

Examples of the group e of the compound represented by the general formula (1) include compounds of groups e1 to e6 shown below. These may be used individually by 1 type, and may use 2 or more types together.

<<Exemplified compound e1 group>>

<<Exemplified compound e2 group>>

<<Exemplified compound e3 group>>

<<Exemplified compound e4 group>>

<<Exemplified compound e5 group>>

<<Exemplified compound e6 group>>

Examples of the group f of the compound represented by the general formula (1) include compounds of groups f1 to f8 shown below. These may be used individually by 1 type, and may use 2 or more types together.

<<Exemplary compound f1 group>>

<<Exemplified compound f2 group>>

<<Exemplified compound f3 group>>

<<Exemplified compound f4 group>>

<<Exemplified compound f5 group>>

<<Exemplified compound f6 group>>

<<Exemplary compound f7 group>>

<<Exemplified compound f8 group>>

Examples of the group g of compounds represented by the general formula (4) include compounds of groups g1 to g2 shown below. These may be used individually by 1 type, and may use 2 or more types together.

<<Exemplified compound g1 group>>

<<Exemplified compound g2 group>>

Among the acrylamide compounds, for example, a1-1, d1-1, and g1-2 were subjected to OECD TG442B (local lymph node proliferation test/concentration 50%), and the SI value, which is an evaluation index of skin sensitization, shows a value of less than 3, and these compounds are considered to have a low risk of developing skin sensitization.

The acrylamide compounds represented by the general formulas (1) and (4) of the present invention can be used by mixing two or more different compounds, and in this case, the different compounds include structural isomers. be A mixing ratio is not particularly limited.
The content of the acrylamide compound is preferably 10% by mass or more and 98% by mass or less, more preferably 30% by mass or more and 90% by mass or less, and still more preferably 30% by mass or more and 70% by mass or less, relative to the total amount of the composition.

<Viscosity adjusting component>
The viscosity adjusting component is an additive that increases the viscosity, and examples thereof include thickeners, thickening stabilizers, various polymers, oligomers, and polymerizable oligomers having a polymerizable functional group.
Among these, a polymerizable oligomer having a polymerizable functional group is preferable because it has a large molecular weight and excellent flexibility and can maintain the shape and strength after curing by forming a crosslinked structure.

Examples of thickening agents include animal gelatin and the like, vegetable polysaccharides, chemical derivatives of cellulose, and the like.
Examples of polymers include polyamines, cellulose, amylose, starch, chitin, natural rubber, polypeptides, proteins, DNA, RNA, some lipids, lignin, natural polymers such as asphaltenes, polyvinyl chloride, polyethylene, and phenolic resins. , silicone resin (silicone rubber, silicone oil), synthetic fiber (nylon, vinylon, polyester, polyethylene terephthalate, etc.) synthetic rubber, polyols such as polyethylene glycol and polypropylene glycol, polyvinyl alcohol, polycyanoacrylate, polylactic acid, poly Synthetic polymers such as glycolic acid, polycaprolactone, polyacrylic acid alkyl ester, polymethacrylic acid alkyl ester, and the like are included.
As the oligomer, those having a relatively small molecular weight with a degree of polymerization of about 10 to 100 relative to the above polymer can be mentioned, and commercially available ones can be used.

Examples of polymerizable oligomers containing a polymerizable functional group include epoxy (meth)acrylate oligomers, urethane (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, and amine-modified oligomers. be done. These may be used individually by 1 type, and may use 2 or more types together. Among these, urethane (meth)acrylate oligomers are preferred from the viewpoint of flexibility, and amine-modified oligomers are preferred from the viewpoint of curing reactivity.
Commercially available products can be used as the polymerizable oligomer, and examples of the commercially available products include urethane oligomers and polyesters described in Sartomer (functional/special monomers & oligomers ver.4.0 2016.06). Oligomers, epoxy acrylate oligomers, hydrophobic oligomers, special type oligomers such as amine-modified oligomers, and polyethylene glycol (manufactured by Tokyo Kasei Kogyo Co., Ltd.).
The content of the viscosity adjusting component is preferably 1% by mass or more and 80% by mass or less, more preferably 5% by mass or more and 70% by mass or less, and even more preferably 10% by mass or more and 60% by mass or less, relative to the total amount of the composition. .
When the content of the viscosity-adjusting component is 1% by mass or more and 80% by mass or less, a cured product having excellent adhesiveness can be obtained.

<Polyfunctional (meth)acrylate compound>
The polyfunctional (meth)acrylate compound is not particularly limited and can be appropriately selected from various commercially available (meth)acrylate compounds.
Examples of commercially available polyfunctional (meth)acrylate compounds include those listed in catalogs issued by monomer manufacturers such as Shin-Nakamura Chemical Co., Ltd., Nippon Kayaku Co., Ltd., and Sartomer Japan Co., Ltd. can be used.
Specific examples of catalogs include the following. It can also include items not listed in the following catalogs.
Sartomer (Functional / Special Monomer & Oligomer ver.4.0 2016.06)
Nippon Kayaku Co., Ltd. (Radiation Curable Products, 1st edition, published in November 2009)
Shin Nakamura Chemical Industry Co., Ltd. (product catalog 131205 2nd edition)
Toagosei Co., Ltd. (Photo-curing resin July 2000)
Kyoeisha Chemical Co., Ltd. (Functional Chemicals 2008.2.1000)
Daiichi Kogyo Seiyaku Co., Ltd. (New Frontier 0607143A20R)

Furthermore, monomer compounds exemplified below can be used, although some of them are not commercially available. When OECD TG442B (local lymph node proliferation test/concentration 50%) was performed on these compounds, the SI value, which is an evaluation index for skin sensitization, showed a value of 3 or less, indicating that these compounds have skin sensitization. are considered to have a low risk of developing, and these are preferable for use as medical adhesives and medical coatings.
A low risk of developing skin sensitization means that the SI value indicating the degree of sensitization is 3 or less in the skin sensitization test by the LLNA method. The above-mentioned "LLNA method" is a skin sensitization test defined as an OECD test guideline, and as shown in the literature (for example, "Functional Material" September 2005, Vol.25, No.9, P55) Secondly, when the Stimulation Index (SI value), which indicates the degree of skin sensitization, is 3 or less, it is judged that there is no problem with regard to sensitization.

（ｎ＝１～２３）
商品名：ｈ１－１－１～１２（ポリエチレングリコールジメタクリレート、新中村化学工業株式会社製）

(n = 1 to 23)
Product name: h1-1-1 to 12 (polyethylene glycol dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

（ｎ＝１～１２）
商品名：ｈ１－２－１～１２（ポリプロピレングリコールジメタクリレート、サートマー社製）

(n = 1 to 12)
Product name: h1-2-1 to 12 (polypropylene glycol dimethacrylate, manufactured by Sartomer)

商品名：ｈ１－３（トリシクロデカンジメタノールジメタクリレート、新中村化学工業株式会社製）

Product name: h1-3 (tricyclodecanedimethanol dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

商品名：ｈ１－４（グリセリンジメタクリレート、新中村化学工業株式会社製）

Product name: h1-4 (glycerine dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

商品名：ｈ１－５（２－アセチルグリセリン－１，３－ジメタクリレート、自社合成品）

Product name: h1-5 (2-acetylglycerin-1,3-dimethacrylate, in-house synthesized product)

（ｍ＋ｎ＝２～３０）
商品名：ｈ１－６（エトキシ化ビスフェノールＡジアクリレート、新中村化学工業株式会社製）

(m+n=2 to 30)
Product name: h1-6 (ethoxylated bisphenol A diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

商品名：ｈ１－７

Product name: h1-7

商品名：ｈ１－８（カプロラクトン変性ペンタエリスリトールヘキサアクリレート（ＤＰＣＡ－６０）、日本化薬株式会社製）

Product name: h1-8 (caprolactone-modified pentaerythritol hexaacrylate (DPCA-60), manufactured by Nippon Kayaku Co., Ltd.)

These polyfunctional (meth)acrylate compounds can be used by mixing two or more different compounds, and the mixing ratio is not particularly limited.
The content of the polyfunctional (meth)acrylate compound is preferably 1% by mass or more and 80% by mass or less, more preferably 5% by mass or more and 70% by mass or less, and 10% by mass or more and 60% by mass, based on the total amount of the composition. More preferred are:

<Polymerization initiator>
The composition of the invention may contain a polymerization initiator. In addition, the polymerization initiator may be simply referred to as an initiator. Polymerization initiators include thermal polymerization initiators and photopolymerization initiators.
Any photopolymerization initiator may be used as long as it can generate active species such as radicals and cations by the energy of active energy rays and initiate polymerization of polymerizable compounds (monomers and oligomers). As the photopolymerization initiator, known radical polymerization initiators, cationic polymerization initiators, base generators, and the like can be used singly or in combination of two or more. Among them, radical polymerization initiators are preferred.
Examples of radical polymerization initiators include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, Examples include ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds.

The radical polymerization initiator is not particularly limited and can be appropriately selected depending on the intended purpose. -Cyclohexyl-phenyl-ketone (manufactured by BASF Japan Ltd. "Irgacure 184"), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl] -1-butanone (manufactured by BASF Japan Ltd. "Irgacure 379"), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by BASF Japan Ltd., "Irgacure 819"), 2-[4-( Methylthio)benzoyl]-2-(4-morpholinyl)propane (manufactured by BASF Japan Ltd., "Irgacure 907"), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF Japan Ltd., "Irgacure TPO ”), polyethylene glycol 200-di(β-4(4-(2-dimethylamino-2-benzyl)butanonylphenyl)piperazine) (manufactured by IGM, “Omnipol 910”, molecular weight 1032), 1,3-di ({α-[1-chloro-9-oxo-9H-thioxanthen-4-yl)oxy]acetylpoly[oxy(1-methylethylene)]}oxy)-2,2-bis({α-[1 -chloro-9-oxo-9H-thioxanthen-4-yl)oxy]acetylpoly[oxy(1-methylethylene)]}oxymethyl)propane (manufactured by Lambson, "Speedcure 7010", molecular weight 1899), 1,3 -di({α-4-(dimethylamino)benzoylpoly[oxy(1-methylethylene)]}oxy)-2,2-bis({α-4-(dimethylamino)benzoylpoly[oxy(1-methyl) ethylene)]}oxymethyl)propane and {α-4-(dimethylamino)benzoylpoly(oxyethylene)-poly[oxy(1-methylethylene)]-poly(oxyethylene)}4-(dimethylamino)benzoate mixture (manufactured by Lambson, "Speedcure 7040", molecular weight 1066), polybutylene glycol bis (9-oxo-9H-thioxanthinyloxy) acetate (manufactured by IGM, "Omnipol TX", molecular weight 820), high molecular weight thio Xanthene compound (manufactured by Lahn AG, "Gene pol TX-2", molecular weight 980), benzene, (1-methylethynyl)-, homopolymer, ar-(2-hydroxy-2-methyl-1-oxopropyl) derivative (manufactured by IGM, "Esacure ONE", molecular weight of 1000 or more). These may be used individually by 1 type, and may use 2 or more types together.
Among these, polymerization initiators having a molecular weight of 800 or more are suitable for medical adhesives or coatings because of their high safety.
The content of the polymerization initiator is preferably 5% by mass or more and 20% by mass or less with respect to the total amount of the composition in order to obtain a sufficient curing speed.

The composition of the present invention may further contain a sensitizer in order to promote decomposition of the photopolymerization initiator by irradiation with active energy rays.
The sensitizer absorbs the active energy ray and becomes an electronically excited state. In this state, the sensitizer comes into contact with the polymerization initiator and undergoes chemical changes (decomposition, radicals, acid or base production). The mass ratio of the sensitizer to the photopolymerization initiator is preferably 5×10 ⁻³ or more and 200 or less, more preferably 0.02 or more and 50 or less.

The sensitizer is not particularly limited, but a sensitizing dye having an absorption wavelength in the wavelength range of 350 nm or more and 450 nm or less can be used. Sensitizers include, for example, polynuclear aromatics (e.g., pyrene, perylene, triphenylene), xanthenes (e.g., fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (e.g., thiacarbocyanine, oxacarbocyanine), merocyanines (e.g. merocyanine, carbomerocyanine), thiazines (e.g. thionine, methylene blue, toluidine blue), acridines (e.g. acridine orange, chloroflavin, acriflavin), anthraquinones (e.g. anthraquinone ), squarylium (eg, squarylium), coumarins (eg, 7-diethylamino-4-methylcoumarin), and the like.

The composition of the invention may further contain a co-sensitizer. The co-sensitizer further improves the sensitivity of the sensitizing dye to active energy rays and suppresses the inhibition of polymerization of the polymerizable compound by oxygen.
The co-sensitizer is not particularly limited and can be appropriately selected depending on the intended purpose. amine compounds, thiols and sulfides such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4(3H)-quinazoline and β-mercaptonaphthalene.

The composition of the present invention may further contain a polymerization inhibitor. This can improve the storage stability (storage stability) of the composition. In addition, head clogging due to thermal polymerization can be prevented when the composition is heated to lower its viscosity and discharged.
The polymerization inhibitor is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include hydroquinone, benzoquinone, p-methoxyphenol, TEMPO, TEMPOL, cupferron complex of aluminum, and the like. The content of the polymerization inhibitor is preferably 200 ppm or more and 20,000 ppm or less with respect to the total amount of the composition.

<Other ingredients>
The composition of the present invention may further contain other components, such as colorants, organic solvents, stabilizers, plasticizers, preservatives, heat release agents, biocompatible substances, fiber reinforcing materials, etc., as necessary. .

As the coloring material, various pigments and dyes that impart black, white, magenta, cyan, yellow, green, orange, lustrous colors such as gold and silver, etc., depending on the purpose and required properties of the composition in the present invention. can be used.
The content of the coloring material may be determined as appropriate in consideration of the desired color density, dispersibility in the composition, etc., and is not particularly limited. % or less is preferable. In addition, the composition of the present invention may be colorless and transparent without containing a coloring material, and in that case, it is suitable as, for example, an overcoat layer for protecting images.
As the pigment, an inorganic pigment or an organic pigment can be used, and one kind may be used alone, or two or more kinds may be used in combination.
Examples of inorganic pigments that can be used include carbon black (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide.
Examples of organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone. Polycyclic pigments such as pigments, dye chelates (e.g., basic dye chelates, acid dye chelates, etc.), dyeing lakes (e.g., basic dye lakes, acid dye lakes, etc.), nitro pigments, nitroso pigments, Aniline black, daylight fluorescent pigments, and the like.
In addition, a dispersant may be further included in order to improve the dispersibility of the pigment. The dispersant is not particularly limited, but includes, for example, dispersants commonly used for preparing pigment dispersions such as polymeric dispersants.
As dyes, for example, acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and they may be used singly or in combination of two or more.

<Organic solvent>
Although the composition of the present invention may contain an organic solvent, it is preferred not to contain it if possible. If the composition does not contain an organic solvent, especially a volatile organic solvent (VOC (Volatile Organic Compounds) free), the safety of the place where the composition is handled is further increased, and it is also possible to prevent environmental pollution. . The term "organic solvent" means general non-reactive organic solvents such as ether, ketone, xylene, ethyl acetate, cyclohexanone, and toluene, and should be distinguished from reactive monomers. be. In addition, "not including" an organic solvent means not including substantially an organic solvent, and it is preferably less than 0.1% by mass.

Plasticizers can impart flexibility to polymers formed by monomers, such as polyethylene glycol esters, end-capped polyesters, butyl stearate, lauric acid, dioctyl glutarate, triglycerides, dioctyl oxalate, triethyl phosphate, acetyltributyl citrate and the like.
Preservatives include those conventionally used that do not initiate the polymerization of monomers, such as potassium sorbate, sodium benzoate, sorbic acid, chlorocresol, and the like.
Fiber reinforcing materials include, but are not limited to, natural or synthetic rubbers such as styrene, acrylonitrile, etc., to enhance the impact resistance of the composition.
Stabilizers serve the purpose of inhibiting polymerization of the monomer during storage and include anionic stabilizers and free radical stabilizers. The former are metaphosphoric acid, maleic acid, maleic anhydride, alkylsulfonic acid, phosphorus pentoxide, iron(III) chloride, antimony oxide, 2,4,6-trinitrophenol, thiol, alkylsulfonyl, alkylsulfone, alkylsulfoxide. , alkyl sulfites, sultones, sulfur dioxide, sulfur trioxide, etc., the latter including hydroquinone, catechol, or derivatives thereof.

In addition, for each component in the composition, low molecular weight components such as polymerizable monomers and polymerization initiators can be identified by gas chromatogram mass spectrometry, etc., and polymer components are precipitated and separated with a poor solvent such as methanol. It is possible to identify the content of the main skeleton and chlorine atoms by infrared spectroscopy or elemental analysis.

<Preparation of composition>
The composition of the present invention can be prepared using the various components described above, and the preparation means and conditions are not particularly limited. Agent, pigment, dispersing agent, etc. are put into a dispersing machine such as a ball mill, Kitty mill, disk mill, pin mill, Dyno mill, etc., and dispersed to prepare a pigment dispersion. It can be prepared by mixing agents and the like.

<Viscosity>
The viscosity of the composition of the present invention may be appropriately adjusted according to the application and application means, and is not particularly limited. The viscosity in the range of ~65°C, desirably at 25°C, is preferably 3 mPa·s or more and 40 mPa·s or less, more preferably 5 mPa·s or more and 15 mPa·s or less, and particularly preferably 6 mPa·s or more and 12 mPa·s or less. Moreover, it is particularly preferable that the viscosity range is satisfied without including the organic solvent. The above viscosity was measured using a cone-plate rotary viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd., using a cone rotor (1°34′×R24), rotating at 50 rpm, and constant-temperature circulating water at a temperature of 20°C. Measurement can be performed by appropriately setting the temperature in the range of ~65°C. VISCOMATE VM-150III can be used to adjust the temperature of the circulating water.

<Curing means>
Curing means for curing the composition of the present invention includes heat curing and curing with active energy rays, and among these, curing with active energy rays is preferable.
As the active energy rays used for curing the composition, in addition to ultraviolet rays, electron beams, α rays, β rays, γ rays, X rays, etc. are necessary for promoting the polymerization reaction of the polymerizable components in the composition. It is not particularly limited as long as it can impart sufficient energy. Especially when using a high-energy light source, the polymerization reaction can proceed without using a polymerization initiator. Further, in the case of ultraviolet irradiation, there is a strong desire to eliminate mercury from the viewpoint of environmental protection, and replacement with GaN-based semiconductor ultraviolet light emitting devices is very useful both industrially and environmentally. Furthermore, ultraviolet light emitting diodes (UV-LEDs) and ultraviolet laser diodes (UV-LDs) are compact, have a long life, are highly efficient, and are low in cost, and are preferred as ultraviolet light sources.
Among these, ultraviolet light having a peak at a wavelength of 285 nm or more and 405 nm or less (preferably 365 nm or more and 405 nm or less) emitted from an ultraviolet light emitting diode (hereinafter also referred to as UV-LED) is preferable from the viewpoint of energy saving and device size reduction. . Incidentally, the light absorption spectrum of the polymerization initiator is generally broad, and the use of a UV-LED that irradiates a narrow specific wavelength region makes it difficult to improve the curability of the composition. Therefore, it is preferable to use the composition of the present invention, which exhibits excellent curability even when UV-LED is used.

<Application>
The application of the composition of the present invention is not particularly limited as long as it is a field where active energy ray-curable materials are generally used, and can be appropriately selected according to the purpose. agents, coatings, medical sheets, medical adhesives, medical coatings, insulating materials, release agents, coating materials, sealing materials, various resists, various optical materials, and the like.
Furthermore, the composition of the present invention can be used not only for forming two-dimensional characters and images, and design coating films on various substrates, but also for forming a three-dimensional three-dimensional image (three-dimensional object). It can also be used as This three-dimensional modeling material may be used, for example, as a binder between powder particles used in a powder lamination method in which three-dimensional modeling is performed by repeating curing and lamination of powder layers. It may be used as a three-dimensional configuration material (model material) or a support member (support material) used in such a layered manufacturing method (stereolithography method). In addition, FIG. 2 shows a method for three-dimensional modeling by discharging the composition of the present invention to a predetermined region, irradiating active energy rays and curing, and then sequentially laminating them (details will be described later). A storage pool (accommodating portion) 1 of the composition 5 of the present invention is irradiated with an active energy ray 4 to form a cured layer 6 having a predetermined shape on a movable stage 3, and these layers are sequentially stacked to form a three-dimensional shape. be.
As a stereolithography apparatus for molding a three-dimensional object using the composition of the present invention, a known apparatus can be used, and is not particularly limited. Examples thereof include those provided with means, active energy ray irradiation means, and the like.
The present invention also includes a molded product obtained by processing a cured product obtained by curing the composition or a structure in which the cured product is formed on a substrate. The molded article is, for example, a sheet-shaped or film-shaped cured product or structure subjected to molding such as heat stretching or punching.・It is suitable for applications that require molding after surface decoration, such as electronic equipment, meters for cameras, and operation panels.
The base material is not particularly limited and can be appropriately selected according to the purpose. Examples include paper, thread, fiber, fabric, leather, metal, plastic, glass, wood, ceramics, composite materials thereof, and the like. and a plastic substrate is preferable from the viewpoint of workability.

(medical sheet)
The medical sheet of the present invention has a substrate, a layer containing the composition of the present invention or a cured product of the composition on the substrate, and, if necessary, other members.
Medical sheets are suitably used for wounds, protection of surgical sites, adhesion and covering, biorepair materials, artificial membranes, and the like.

<Base material>
The shape, structure, size, and the like of the base material are not particularly limited, and can be appropriately selected according to the purpose. Examples of the shape include a film shape and a sheet shape. Examples of the structure include a single layer structure and a laminated structure. The size can be appropriately selected depending on the application. The base material is not limited to a flat base material, and may be a base material having a curved surface, a base material having unevenness, or the like.

The base material is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include cloth, nonwoven fabric, paper, synthetic resin sheet (film) and the like.
Examples of the synthetic resin sheet include polyolefins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene-2,6-naphthalate; polyamides such as nylon 6 and nylon 12; Vinyl copolymer or its saponified product, polystyrene, polycarbonate, polysulfone, polyphenylene oxide, polyphenylene sulfide, aromatic polyamide, polyimide, polyamideimide, cellulose, cellulose acetate, polyvinylidene chloride, polyacrylonitrile, polyvinyl alcohol, or copolymer thereof Amalgamation etc. are mentioned.

<Layer containing the composition of the present invention or a cured product of the composition>
A layer containing the composition of the present invention or a cured product of the composition is provided on the entire surface or part of the substrate.
The thickness of the layer containing the composition of the present invention or a cured product of the composition is preferably 10 μm or more and 5,000 μm or less.
This layer should retain its shape until use. In this case, for example, the layer can be cured using irradiation means in a medical sheet manufacturing apparatus, which will be described later, so that the shape can be easily maintained. In that case, the degree of curing can be appropriately selected, and it is also possible to take a so-called semi-cured state in the middle of the completely cured state.

<Other parts>
Other members include, for example, a cover material and an intermediate layer.

Here, FIG. 1A is a plan view showing an example of the medical sheet of the present invention, and FIG. 1B is a sectional view showing an example of the medical sheet of the present invention.
A medical sheet 10 in FIG. 1A is provided with a layer 12 containing the composition of the present invention or a cured product of the composition on a substrate 11 .
Although illustration is omitted, a cover material may be provided for protection on the layer 12 containing the cured product of the composition of the present invention.

(Medical sheet manufacturing equipment)
The apparatus for manufacturing a medical sheet of the present invention has a storage unit for storing the composition of the present invention and an applying means for applying the composition, and is a UV-ray having a peak wavelength of 365 nm or more and 405 nm or less. It preferably has illumination means which are LEDs, and optionally other means.

<Accommodation part>
The storage unit means a member in which the composition of the present invention is stored, and examples thereof include containers such as bags, cartridges, and bottles. This eliminates the need for direct contact with the composition during operations such as transportation of the composition and replacement of the composition, thereby preventing contamination of fingers and clothes. In addition, it is possible to prevent foreign matter such as dust from entering the composition.
The shape, size, material, etc. of the container itself are not particularly limited as long as they are suitable for the application and usage. etc. is preferably covered.

<Applying Means>
The application means is the means by which the composition of the invention is applied.
The application method is not particularly limited and can be appropriately selected depending on the intended purpose. method, spray coating method, brush coating method, roller coating method, spray coating method, airless spray method, roll coater method, baking coating method, dip coating method, electrodeposition coating method, ultraviolet curing coating method, and the like.

<Irradiation means>
The irradiation means is a UV-LED that emits ultraviolet rays having a peak wavelength of 365 nm or more and 405 nm or less.
The irradiation means is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include known ultraviolet irradiation devices.

<Other means>
Other means are not particularly limited and can be appropriately selected according to the purpose, and examples thereof include control means.

(Medical Adhesives or Coatings)
The medical adhesive or coating of the present invention contains the composition of the present invention and, if necessary, other ingredients.
From the viewpoint of convenience, the medical adhesive or coating of the present invention preferably comprises a composition A containing a monofunctional acrylamide compound having an ester structure and a viscosity adjusting component, and a composition B containing a polymerization initiator. .
The medical adhesive or coating is not particularly limited and can be appropriately selected according to the purpose. Examples include disinfectants.

The medical adhesives or coatings of the present invention can contain at least one selected from biological agents, therapeutic agents, and antiseptics.

The biologically active substance and therapeutic agent are not particularly limited and can be appropriately selected according to the purpose. Allergy agents, antiulcer agents, antibiotics, antibacterial agents, antiviral agents, antifungal agents, immunosuppressive agents, naturally occurring proteins, genetically engineered proteins, polysaccharides, glycoproteins or lipoproteins, oligonucleotides, polypeptide drugs, Antibodies, antigens, chemotherapeutic agents, coagulants and hemostatic agents such as prothrombin, thrombin, fibrinogen, fibrin, fibronectin, clotting factors, tissue factors, collagen, gelatin, vasopressin, plasminogen activator inhibitors, platelet activating factor , synthetic peptides with hemostatic activity, and the like. These may be used individually by 1 type, and may use 2 or more types together.

The disinfectant is not particularly limited, and various disinfectants can be used. For example, aldehyde-based disinfectants such as glutaraldehyde, sodium hypochlorite, chlorine-based disinfectants such as sodium dichloroisocyanurate, Oxidizing agent disinfectants such as hydrogen oxide, iodine disinfectants such as povidone iodine and boloxamer iodine, alcohol disinfectants such as ethanol, isopropanol, ethanol containing chlorhexidine, biquanide disinfectants such as chlorhexidine, benzalkonium chloride, chloride Examples include quaternary ammonium salt disinfectants such as benzethonium, amphoteric surfactant disinfectants such as alkylpolyaminoethylglycine, and pigment disinfectants such as acrinol. These may be used individually by 1 type, and may use 2 or more types together.

(Container)
The container of the present invention is a container filled with the composition of the present invention.
The storage container of the present invention has the composition of the present invention, a container, and, if necessary, other members such as a composition bag. As a result, there is no need to directly touch the composition during operations such as composition replacement, there is no fear of staining fingers or clothes, and contamination of the composition with foreign matter such as dust can be prevented.
The container is not particularly limited, and its shape, structure, size, material, etc. can be appropriately selected according to the purpose. and the like are suitable.

<<Image Forming Method, Forming Apparatus>>
The image forming method of the present invention may use an active energy ray, or may include heating. In order to cure the composition of the present invention with an active energy ray, an irradiation step of irradiating the active energy ray is provided. and a container for containing the composition of the invention, wherein the container may be contained in the container. Furthermore, it may have a discharge step and discharge means for discharging the composition of the present invention. The method of discharging is not particularly limited, but examples include a continuous injection type, an on-demand type, and the like. The on-demand type includes a piezo system, a thermal system, an electrostatic system, and the like.

FIG. 2 is a schematic diagram showing an example of another image forming apparatus (three-dimensional stereoscopic image forming apparatus) according to the present invention. The image forming apparatus 39 in FIG. 2 uses a head unit (movable in the AB direction) in which inkjet heads are arranged, and the first composition is discharged from the ejection head unit 30 for the support to the ejection head units 31 and 32 for the support. A second composition different in composition from the first composition is ejected from the first composition, and these compositions are laminated while being cured by the adjacent ultraviolet irradiation means 33 and 34 . More specifically, for example, the second composition is ejected from the support ejection head units 31 and 32 onto the shaped object support substrate 37, irradiated with active energy rays, and solidified to form a second composition having a reservoir. After forming one support layer, the first composition is discharged from the discharge head unit 30 for the modeled article into the reservoir, and irradiated with active energy rays to be solidified to form the first modeled article layer. By repeating the process a plurality of times while lowering the vertically movable stage 38 according to the number of layers, the support layer and the object layer are laminated to manufacture the three-dimensional object 35 . After that, the support laminate 36 is removed as needed. In FIG. 2, only one ejection head unit 30 for a modeled object is provided, but two or more may be provided.

Examples of the present invention will be described below, but the present invention is not limited to these examples. ¹ H-NMR spectrum was measured using ¹ H-NMR (500 MHz) (manufactured by JEOL).

(Synthesis example 1)
<Synthesis of monomer d1-1>
Sarcosic acid methyl ester hydrochloride (8.37 g, 60 mmol) manufactured by Tokyo Kasei Kogyo Co., Ltd. was added to 100 mL of dehydrated dichloromethane, and 17.49 g (172 mmol) of triethylamine was added.
Next, after cooling to about −15° C. in an ice-NaCl mixture, 6.52 g (72 mmol) of acrylic acid chloride manufactured by Wako Pure Chemical Industries, Ltd. was diluted with 4 mL of dehydrated dichloromethane and slowly added dropwise. °C) for 3 hours. After the precipitate was removed by filtration, the filtrate was washed with water, saturated aqueous sodium hydrogencarbonate solution and saturated aqueous sodium chloride solution.
It was then dried over sodium sulfate and then concentrated under reduced pressure to give an oil. Furthermore, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. was packed and purified by column chromatography using hexane and ethyl acetate as eluents to obtain a compound represented by the following structural formula (d1-1). 4.69 g (approximately 50% yield) of a pale yellow oil were obtained.

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ３．０５－３．１６（ｍ，３Ｈ），３．７５－３．７８（ｍ，３Ｈ），４．１３－４．２０（ｍ，２Ｈ），５．７０－５．７６（ｍ，１Ｈ），６．３６－６．３９（ｍ，１Ｈ），６．６１－６．６３（ｍ，１Ｈ）

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 3.05-3.16 (m, 3H), 3.75-3.78 (m, 3H), 4.13-4.20 (m, 2H), 5. 70-5.76 (m, 1H), 6.36-6.39 (m, 1H), 6.61-6.63 (m, 1H)

(Synthesis example 2)
<Synthesis of monomer d1-2>
Ethyl sarcosinate hydrochloride (12.29 g, 80 mmol) manufactured by Tokyo Kasei Kogyo Co., Ltd. was added to 110 mL of dehydrated dichloromethane, and 22.34 g (220 mmol) of triethylamine was added. Next, after cooling to about −15° C. in an ice-NaCl mixture, 8.69 g (96 mmol) of acrylic acid chloride manufactured by Wako Pure Chemical Industries, Ltd. was diluted with 5 mL of dehydrated dichloromethane and slowly added dropwise. ) for 3 hours. After the precipitate was removed by filtration, the filtrate was washed with water, saturated aqueous sodium hydrogencarbonate solution and saturated aqueous sodium chloride solution. It was then dried over sodium sulfate and then concentrated under reduced pressure to give an oil. Further, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. was packed, and purified by column chromatography using hexane and ethyl acetate as eluents to obtain a pale yellow compound represented by the following structural formula (d1-2). 7.58 g (approximately 55% yield) of an oil were obtained.

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ１．２６－１．３０（ｍ，３Ｈ），３．０６－３．１６（ｍ，３Ｈ），４．１１－４．２５（ｍ，４Ｈ），５．６８－５．７６（ｍ，１Ｈ），６．２８－６．３９（ｍ，１Ｈ），６．６１－６．６６（ｍ，１Ｈ）

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 1.26-1.30 (m, 3H), 3.06-3.16 (m, 3H), 4.11-4.25 (m, 4H), 5. 68-5.76 (m, 1H), 6.28-6.39 (m, 1H), 6.61-6.66 (m, 1H)

(Synthesis Example 3)
<Synthesis of monomer d1-5>
Tokyo Chemical Industry Co., Ltd. Methylamine 7% THF solution (31.05 g, 70 mmol), potassium carbonate (9.68 g, 70 mmol) was added to THF (15 mL) and stirred at room temperature (25 ° C.), Tokyo Chemical Industry Co., Ltd. A solution obtained by dissolving isopropyl chloroacetate (10.52 g, 77 mmol) manufactured by Co., Ltd. in THF (5 mL) was added dropwise. A solution obtained by dissolving potassium carbonate (9.68 g, 70 mmol) in water (50 mL) was added to the filtrate obtained by filtering the reaction solution, and the mixture was cooled in an ice bath. After slowly dropping acrylic acid chloride (6.96 g, 77 mmol), the mixture was stirred at room temperature (25° C.) for 2 hours. The ethyl acetate layer was washed with a saturated aqueous sodium hydrogencarbonate solution, dried over anhydrous sodium sulfate, and concentrated to obtain 8.4 g of a colorless solution.
Further, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. was packed, and purified by column chromatography using hexane and ethyl acetate as eluents to obtain a compound represented by the following structural formula (d1-5). 3.9 g (yield: about 30%) of a colorless liquid of

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ１．２６（ｄ，６Ｈ），３．０５／３．１５（ｓ，３Ｈ），４．０７／４．１６（ｓ，２Ｈ），５．０４－５．１０（ｍ，１Ｈ），５．６７－５．７５（ｍ，１Ｈ），６．２８－６．４４／６．６１－６．６６（ｍ，２Ｈ）

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 1.26 (d, 6H), 3.05/3.15 (s, 3H), 4.07/4.16 (s, 2H), 5.04-5. 10 (m, 1H), 5.67-5.75 (m, 1H), 6.28-6.44/6.61-6.66 (m, 2H)

(Synthesis Example 4)
<Synthesis of monomer d1-4>
Tokyo Kasei Kogyo Co., Ltd. Methylamine 7 mass% tetrahydrofuran (THF) solution (31.05 g, 70 mmol), potassium carbonate (9.68 g, 70 mmol) was added to THF (15 mL) and stirred at room temperature (25 ° C.). , a solution of normalbutyl chloroacetate (11.60 g, 77 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in THF (5 mL) was added dropwise. A solution obtained by dissolving potassium carbonate (9.68 g, 70 mmol) in water (50 mL) was added to the filtrate obtained by filtering the reaction solution, and the mixture was cooled in an ice bath. After slowly dropping acrylic acid chloride (6.96 g, 77 mmol), the mixture was stirred at room temperature (25° C.) for 2 hours. The ethyl acetate layer was washed with a saturated aqueous sodium hydrogencarbonate solution, dried over anhydrous sodium sulfate, and concentrated to obtain 13.3 g of a colorless solution.
Further, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. was packed, and purified by column chromatography using hexane and ethyl acetate as eluents to obtain a compound represented by the following structural formula (d1-4). 5.5 g (yield: about 39%) of a colorless liquid of

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ０．９３（ｔ，３Ｈ），１．３４－１．４２（ｍ，２Ｈ），１．５９－１．６６（ｍ，２Ｈ），３．０６／３．１６（ｓ，３Ｈ），４．１１－４．１９（ｍ，４Ｈ），５．６８－５．７６（ｍ，１Ｈ），６．２８－６．４４／６．６０－６．６６（ｍ，２Ｈ）

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 0.93 (t, 3H), 1.34-1.42 (m, 2H), 1.59-1.66 (m, 2H), 3.06/3. 16 (s, 3H), 4.11-4.19 (m, 4H), 5.68-5.76 (m, 1H), 6.28-6.44/6.60-6.66 (m , 2H)

(Synthesis Example 5)
<Synthesis of monomer f2-1>
A slurry of N-methyl-DL-alanine (6.19 g, 60 mmol) from Combi-Blocks in methanol (40 mL) was cooled in an ice bath and then treated with thionyl chloride (14.28 g, 120 mmol). ) was slowly added dropwise. The reaction solution became a transparent solution during the dropwise addition, and was stirred overnight at room temperature (25° C.). The reaction mixture was concentrated to give N-methyl-DL-alanine methyl ester hydrochloride as a colorless viscous liquid (8.3 g). The resulting N-methyl-DL-alanine methyl ester hydrochloride was directly used in the next reaction.
N-methyl-DL-alanine methyl ester hydrochloride (8.3 g, 54 mmol) was dissolved in 20 mL of water, and an aqueous solution of potassium carbonate (11.94 g, 86.5 mmol) in water (20 mL) was added. (25° C.) and stirred for 1 hour. After cooling in an ice bath, acrylic acid chloride (5.38 g, 59.4 mmol) was slowly added dropwise, and the mixture was stirred at room temperature (25°C) for 2 hours. The reaction mixture was extracted with ethyl acetate, and the ethyl acetate layer was washed with saturated brine and concentrated to obtain 6.0 g of pale yellow liquid. Furthermore, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. was packed, and purified by column chromatography using hexane and ethyl acetate as eluents to obtain a compound represented by the following structural formula (f2-1). 4.1 g (yield: about 44%) of a colorless liquid of

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ１．４３／１．４９（ｄ，３Ｈ），２．９１／３．０３（ｓ，３Ｈ），３．７２／３．７５（ｓ，３Ｈ），４．６８／５．２９（ｑ，１Ｈ），５．６８－５．７６（ｍ，１Ｈ），６．２２－６．３９（ｍ，１Ｈ），６．４９－６．６３（ｍ，１Ｈ）

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 1.43/1.49 (d, 3H), 2.91/3.03 (s, 3H), 3.72/3.75 (s, 3H), 4. 68/5.29 (q, 1H), 5.68-5.76 (m, 1H), 6.22-6.39 (m, 1H), 6.49-6.63 (m, 1H)

(Synthesis Example 6)
<Synthesis of monomer f2-2>
A slurry of N-methyl-DL-alanine (6.19 g, 60 mmol) from Combi-Blocks in ethanol (40 mL) was cooled in an ice bath and then treated with thionyl chloride (14.28 g, 120 mmol). ) was slowly added dropwise. During the dropwise addition, the reaction solution turned into a transparent solution, after which a white solid precipitated and turned into a slurry state. When the mixture was stirred overnight at room temperature (25°C), the white solid dissolved and became transparent. The reaction mixture was concentrated to obtain 10.3 g of N-methyl-DL-alanine ethyl ester hydrochloride as a colorless solid. The resulting N-methyl-DL-alanine ethyl ester hydrochloride was directly used in the next reaction.
Ethyl ester hydrochloride of N-methyl-DL-alanine (10.3 g, 61.4 mmol) was dissolved in 12 mL of water, and an aqueous solution of potassium carbonate (15.28 g, 110.6 mmol) dissolved in water (25 mL) was added. , and stirred at room temperature (25° C.) for 1 hour. After cooling in an ice bath, acrylic acid chloride (6.11 g, 67.5 mmol) was slowly added dropwise, and the mixture was stirred at room temperature (25°C) for 2 hours. The reaction solution was extracted with ethyl acetate, and the ethyl acetate layer was washed with saturated brine and concentrated to obtain 11.5 g of pale yellow liquid. Further, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. was packed, and purified by column chromatography using hexane and ethyl acetate as eluents to obtain a compound represented by the following structural formula (f2-2). 8.1 g (yield: about 71%) of a colorless liquid of

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ１．２７（ｔ，３Ｈ），１．４３／１．４８（ｄ，３Ｈ），２．９１／３．０３（ｓ，３Ｈ），４．１４－４．２２（ｍ，２Ｈ），４．６６／５．２９（ｑ，１Ｈ），５．６７－５．７５（ｍ，１Ｈ），６．２２－６．３８（ｍ，１Ｈ），６．５０－６．６３（ｍ，１Ｈ）

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 1.27 (t, 3H), 1.43/1.48 (d, 3H), 2.91/3.03 (s, 3H), 4.14-4. 22 (m, 2H), 4.66/5.29 (q, 1H), 5.67-5.75 (m, 1H), 6.22-6.38 (m, 1H), 6.50- 6.63 (m, 1H)

(Synthesis Example 7)
<Synthesis of monomer d4-1>
Isopropylamine (2.95 g, 50 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was dissolved in ethyl acetate (50 mL), potassium carbonate (6.91, 50 mmol) was added, and the mixture was stirred at room temperature (25°C). A solution prepared by dissolving methyl chloroacetate (5.43 g, 50 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. in ethyl acetate (5 mL) was added dropwise at room temperature (25° C.) and stirred for 2 hours. After removing the precipitated salt by filtering the reaction solution, an aqueous solution of potassium carbonate (6.91 g, 50 mmol) dissolved in 50 mL of water was added. After cooling with an ice bath, acrylic acid chloride (4.98 g, 55 mmol) was slowly added dropwise, and the mixture was stirred at room temperature (25°C) for 2 hours. The ethyl acetate layer was washed with a saturated aqueous sodium hydrogencarbonate solution, dried over anhydrous sodium sulfate, and concentrated to obtain 9.8 g of a colorless solution.
Furthermore, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. was packed, and purified by column chromatography using hexane and ethyl acetate as eluents to obtain a compound represented by the following structural formula (d4-1). 3.7 g (yield: about 40%) of a colorless liquid of

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ１．１１／１．２２（ｄ，６Ｈ），３．７４／３．７７（ｓ，３Ｈ），３．９９（ｓ，２Ｈ），４．２６－４．３２（ｍ，１Ｈ），５．６６－５．７３（ｍ，１Ｈ），６．３１－６．３５／６．６２－６．６７（ｍ，２Ｈ）

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 1.11/1.22 (d, 6H), 3.74/3.77 (s, 3H), 3.99 (s, 2H), 4.26-4. 32 (m, 1H), 5.66-5.73 (m, 1H), 6.31-6.35/6.62-6.67 (m, 2H)

(Synthesis Example 8)
<Synthesis of monomer d4-5>
A mixture of isopropylamine (2.95 g, 50 mmol), ethyl acetate (50 mL), and potassium carbonate (6.91 g, 50 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was added with isopropyl chloroacetate (6.83, 50 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was diluted with ethyl acetate (5 mL) was added dropwise. After removing the precipitated salt by filtering the reaction solution, an aqueous solution of potassium carbonate (6.91 g, 50 mmol) dissolved in 50 mL of water was added. After cooling with an ice bath, acrylic acid chloride (4.98 g, 55 mmol) was slowly added dropwise, and the mixture was stirred at room temperature (25°C) for 2 hours. The ethyl acetate layer was washed with a saturated aqueous sodium hydrogencarbonate solution, dried over anhydrous sodium sulfate, and concentrated to obtain 8.5 g of a colorless solution.
Further, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. was packed, and purified by column chromatography using hexane and ethyl acetate as eluents to obtain a compound represented by the following structural formula (d4-5). 1.3 g (yield: about 12%) of a colorless liquid of

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ１．１１／１．２１（ｄ，６Ｈ），１．２５（ｄ，６Ｈ），３．９５（ｓ，２Ｈ），４．２８／４．９３（ｍ，１Ｈ），５．０５（ｍ，１Ｈ），５．６５－５．７１（ｍ，１Ｈ），６．２９－６．３４／６．６１－６．６７（ｍ，２Ｈ）

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 1.11/1.21 (d, 6H), 1.25 (d, 6H), 3.95 (s, 2H), 4.28/4.93 (m, 1H), 5.05 (m, 1H), 5.65-5.71 (m, 1H), 6.29-6.34/6.61-6.67 (m, 2H)

(Synthesis Example 9)
<Synthesis of monomer d3-2>
n-Propylamine (5.25 g, 88.8 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was dissolved in ethyl acetate (60 mL), and potassium carbonate (12.27 g, 88.8 mmol) was added. A solution obtained by dissolving ethyl chloroacetate (10.88 g, 88.8 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. in ethyl acetate (10 mL) was added dropwise at room temperature (25° C.) and stirred for 4 hours. After removing the precipitated salt by filtering the reaction solution, it was concentrated to obtain 12.3 g of a colorless solution. This solution was allowed to stand at room temperature (25° C.), and the precipitated colorless crystals were washed with ethyl acetate and dried to obtain 5.8 g of N-propylsarcosine ethyl ester. This compound was directly used for the following reaction.
Water (10 mL) was added to N-propylsarcosine ethyl ester (5.8 g, 40 mmol) followed by a solution of potassium carbonate (6.08 g, 44 mmol) in water (20 mL) and cooled in an ice bath. . Acryloyl chloride (3.98 g, 44 mmol) was slowly added dropwise, and the mixture was stirred at room temperature (25°C) for 2 hours. The ethyl acetate layer was washed with a saturated aqueous sodium hydrogencarbonate solution, dried over anhydrous sodium sulfate, and concentrated to obtain 7.0 g of a colorless solution.
Furthermore, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. was packed, and purified by column chromatography using hexane and ethyl acetate as eluents to obtain a compound represented by the following structural formula (d3-2). 4.9 g (yield: about 62%) of a colorless liquid of

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ０．９０－０．９５（ｍ，３Ｈ），１．２６－１．３０（ｍ，３Ｈ），１．５６－１．７１（ｍ，２Ｈ），３．３７－３．４４（ｍ，２Ｈ），４．０８／４．１２（ｓ，２Ｈ）４．１８－４．２５（ｍ，２Ｈ），５．６７－５．７４（ｍ，１Ｈ），６．２８－６．４２／６．５８－６．６３（ｍ，２Ｈ）

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 0.90-0.95 (m, 3H), 1.26-1.30 (m, 3H), 1.56-1.71 (m, 2H), 3. 37-3.44 (m, 2H), 4.08/4.12 (s, 2H) 4.18-4.25 (m, 2H), 5.67-5.74 (m, 1H), 6 .28-6.42/6.58-6.63 (m, 2H)

(Synthesis Example 10)
<Synthesis of monomer d6-1>
A mixture of n-hexylamine (8.10 g, 80 mmol) available from Tokyo Chemical Industry Co., Ltd., ethyl acetate (55 mL), and potassium carbonate (11.3 g, 81.8 mmol) was added with methyl chloroacetate available from Tokyo Chemical Industry Co., Ltd. (9.8 mmol). 55, 88 mmol) was added dropwise. After removing the precipitated salt by filtering the reaction solution, an aqueous solution of potassium carbonate (11.05 g, 80 mmol) dissolved in 80 mL of water was added. After cooling with an ice bath, acrylic acid chloride (8.0 g, 88 mmol) was slowly added dropwise, and the mixture was stirred at room temperature (25°C) for 2 hours. The ethyl acetate layer was washed with a saturated aqueous sodium hydrogencarbonate solution, dried over anhydrous sodium sulfate, and concentrated to obtain 16.1 g of a colorless solution.
Furthermore, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. was packed, and purified by column chromatography using hexane and ethyl acetate as eluents to obtain a compound represented by the following structural formula (d6-1). 3.5 g (yield: about 19%) of a colorless liquid of

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ０．８９（ｔ，３Ｈ），１．２６－１．３３（ｍ，６Ｈ），１．５８－１．６１（ｍ，２Ｈ），３．４０／３．４４（ｔ，２Ｈ），３．７４／３．７７（ｓ，３Ｈ），４．１０／４．１３（ｓ，２Ｈ），５．６７－５．７５（ｍ，１Ｈ），６．２９－６．４２／６．５７－６．６２（ｍ，２Ｈ）

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 0.89 (t, 3H), 1.26-1.33 (m, 6H), 1.58-1.61 (m, 2H), 3.40/3. 44 (t, 2H), 3.74/3.77 (s, 3H), 4.10/4.13 (s, 2H), 5.67-5.75 (m, 1H), 6.29- 6.42/6.57-6.62 (m, 2H)

(Synthesis Example 11)
<Synthesis of monomer g1-2>
Ethyl 4-piperidinecarboxylate (7.9 g, 50 mmol) was added to dehydrated dichloromethane (100 mL), the inside of the flask was replaced with argon gas, and then triethylamine (7.3 g, 72 mmol) was added. After cooling the mixture to about -10°C, acrylic acid chloride (5.4 g, 60 mmol) was slowly added dropwise so that the temperature in the system was -10°C to -5°C, and then added at room temperature (25°C) for 2 hours. °C). The precipitate was removed by filtration and the filtrate was washed with water, saturated aqueous sodium bicarbonate, saturated aqueous sodium chloride, dried over sodium sulfate, and concentrated under reduced pressure to give a brown oil. The resulting oil was purified by column chromatography (Wakogel C300 300 g) to give a pale yellow oil (5.4 g). This pale yellow oil was confirmed to be a compound represented by the following structural formula (g1-2) from the results of ¹ H-NMR below. Yield after purification was about 51%.

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ１．２６（ｔ，３Ｈ），１．７０（ｍ，２Ｈ），１．９４（ｍ，２Ｈ），２．５６（ｍ，１Ｈ），２．９１（ｔ，１Ｈ），３．１６（ｔ，１Ｈ），３．９０（ｄ，１Ｈ），４．１４（ｍ，２Ｈ），４．４４（ｄ，１Ｈ），５．６７（ｄｄ，１Ｈ），６．２５（ｄｄ，１Ｈ），６．５４－６．６１（ｍ，１Ｈ）

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 1.26 (t, 3H), 1.70 (m, 2H), 1.94 (m, 2H), 2.56 (m, 1H), 2.91 (t , 1H), 3.16 (t, 1H), 3.90 (d, 1H), 4.14 (m, 2H), 4.44 (d, 1H), 5.67 (dd, 1H), 6 .25 (dd, 1H), 6.54-6.61 (m, 1H)

(Synthesis Example 12)
<Synthesis of monomer g2-2>
Ethyl nipecotate (12.6 g, 80 mmol) was added to dehydrated dichloromethane (100 mL), the inside of the flask was replaced with argon gas, and then triethylamine (11.6 g, 115 mmol) was added. After cooling the mixture to about -10°C, acrylic acid chloride (8.7 g, 96 mmol) was slowly added dropwise so that the temperature in the system was -10°C to -5°C, and then added at room temperature (25°C) for 2 hours. °C). The precipitate was removed by filtration and the filtrate was washed with water, saturated aqueous sodium bicarbonate, saturated aqueous sodium chloride, dried over sodium sulfate, and concentrated under reduced pressure to give a brown oil. The resulting oil was purified by column chromatography (Wakogel C300 300 g) to give a pale yellow oil (9.1 g). From the results of ¹ H-NMR below, this pale yellow oil was confirmed to be a compound represented by the following structural formula (g2-2). The yield after purification was about 53%.

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ１．２６（ｓ，２Ｈ），１．４３－１．５９（ｍ，１Ｈ），１．６３－１．８８（ｍ，２Ｈ），２．００－２．２０（ｍ，２Ｈ），２．４４－２．５４（ｍ，１Ｈ），３．０６－３．２４（ｍ，１Ｈ），３．４８－３．５８（ｍ，１Ｈ），３．８２－３．９４（ｄ，１Ｈ），４．１４（ｑ，２Ｈ），５．６９（ｄ，１Ｈ），６．２７（ｄ，１Ｈ），６．５３－６．７１（ｍ，１Ｈ）

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 1.26 (s, 2H), 1.43-1.59 (m, 1H), 1.63-1.88 (m, 2H), 2.00-2. 20 (m, 2H), 2.44-2.54 (m, 1H), 3.06-3.24 (m, 1H), 3.48-3.58 (m, 1H), 3.82- 3.94 (d, 1H), 4.14 (q, 2H), 5.69 (d, 1H), 6.27 (d, 1H), 6.53-6.71 (m, 1H)

(Synthesis Example 13)
<Synthesis of Monomer a1-1>
2-(Methylamino)ethanol (15.02 g, 200 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was added to 200 mL of dehydrated dichloromethane, and 46.8 g (462 mmol) of triethylamine was added. Next, after cooling to about −60° C. in a dry ice-acetone mixture, 15.39 g (170 mmol) of acrylic acid chloride manufactured by Wako Pure Chemical Industries, Ltd. was diluted with 8 mL of dehydrated dichloromethane and slowly added dropwise. 25° C.) for 2 hours. After cooling again to about −60° C. in a dry ice-acetone mixture, acetyl chloride (15.7 g, 200 mmol) was diluted with 8 mL of dehydrated dichloromethane and slowly added dropwise, followed by about 2 hours at room temperature (25° C.). Stirred. After the precipitate was removed by filtration, the filtrate was washed with water, saturated aqueous sodium hydrogencarbonate solution and saturated aqueous sodium chloride solution. It was then dried over sodium sulfate and then concentrated under reduced pressure to give an oil. Furthermore, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. was packed and purified by column chromatography using hexane and ethyl acetate as eluents to obtain a compound represented by the following structural formula (a1-1). 6.1 g (approximately 21% yield) of a pale brown oil were obtained.

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ２．０４－２．０８（ｍ，３Ｈ），３．０４－３．１５（ｍ，３Ｈ），３．６３－３．７１（ｍ，２Ｈ），４．２０－４．２７（ｍ，２Ｈ），５．６９－５．７２（ｍ，１Ｈ），６．３２－６．３７（ｍ，１Ｈ），６．５６－６．６３（ｍ，１Ｈ）

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 2.04-2.08 (m, 3H), 3.04-3.15 (m, 3H), 3.63-3.71 (m, 2H), 4. 20-4.27 (m, 2H), 5.69-5.72 (m, 1H), 6.32-6.37 (m, 1H), 6.56-6.63 (m, 1H)

(Synthesis Example 14)
<Synthesis of monomer a1-4>
2-(Methylamino)ethanol (6.01 g, 80 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was added to 120 mL of dehydrated dichloromethane, and 18.7 g (185 mmol) of triethylamine was added. Next, after cooling to about −15° C. in an ice-NaCl mixture, 6.15 g (68 mmol) of acrylic acid chloride manufactured by Wako Pure Chemical Industries, Ltd. was diluted with 4.5 mL of dehydrated dichloromethane and slowly added dropwise. (25° C.) and stirred for 2.5 hours. After cooling again to about −15° C. in an ice-NaCl mixture, isobutyl chloride (8.52 g, 80 mmol) was diluted with 4.5 mL of dehydrated dichloromethane and slowly added dropwise, followed by about 3 hours at room temperature (25° C.). Stirred for .5 hours. After the precipitate was removed by filtration, the filtrate was washed with water, saturated aqueous sodium hydrogencarbonate solution and saturated aqueous sodium chloride solution. It was then dried over sodium sulfate and then concentrated under reduced pressure to give an oil. Furthermore, 360 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. was packed and purified by column chromatography using hexane and ethyl acetate as eluents to obtain the compound represented by the following structural formula (a1-4). 2.2 g (approximately 16% yield) of a pale yellow oil were obtained.

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ１．１５－１．２０（ｍ，６Ｈ），２．５２－２．５７（ｍ，１Ｈ），３．０５－３．１５（ｍ，３Ｈ），３．６５－３．７１（ｍ，２Ｈ），４．２０－４．２７（ｍ，２Ｈ），５．６９－５．７２（ｍ，１Ｈ），６．３１－６．３８（ｍ，１Ｈ），６．５５－６．６５（ｍ，１Ｈ）

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 1.15-1.20 (m, 6H), 2.52-2.57 (m, 1H), 3.05-3.15 (m, 3H), 3. 65-3.71 (m, 2H), 4.20-4.27 (m, 2H), 5.69-5.72 (m, 1H), 6.31-6.38 (m, 1H), 6.55-6.65 (m, 1H)

(Synthesis Example 15)
<Synthesis of monomer h1-5>
5.7 g (25 mmol) of glycerol dimethacrylate manufactured by Tokyo Kasei Kogyo Co., Ltd. was added to 100 mL of dehydrated dichloromethane, and after replacing the inside of the flask with argon gas, 3.6 g (36 mmol) of triethylamine was added. Next, after cooling to about -10°C, 2.4g (30mmol) of acetic acid chloride was slowly added dropwise so that the temperature in the system was -10°C to -5°C, and the mixture was cooled to room temperature (25°C) for 2 hours. Stirred for an hour. Furthermore, after removing the precipitate by filtration, the filtrate was washed with water, saturated aqueous sodium hydrogencarbonate solution, and saturated aqueous sodium chloride solution. It was then dried over sodium sulfate and then concentrated under reduced pressure to give a yellow oil. Furthermore, 200 g of Wakogel C300 (manufactured by Wako Pure Chemical Industries, Ltd.) was filled, and the yellow oil was purified by column chromatography using hexane and ethyl acetate as eluents, and the following structural formula (h1-5) was obtained. 3.2 g (approximately 47% yield) of the represented compound were obtained as a colorless oil.

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ１．９５（ｓ，６Ｈ），２．０９（ｄ，３Ｈ），４．２３－４．４２（ｍ，４Ｈ），５．３５－５．４２（ｍ，１Ｈ），５．５９－５．６３（ｍ，２Ｈ），６．１０－６．１５（ｍ，２Ｈ）

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 1.95 (s, 6H), 2.09 (d, 3H), 4.23-4.42 (m, 4H), 5.35-5.42 (m, 1H), 5.59-5.63 (m, 2H), 6.10-6.15 (m, 2H)

(Examples 1 to 37 and Comparative Examples 1 to 6)
<Preparation of composition>
The compounds shown in Tables 1-1 to 1-3 were blended at the compounding ratios (mass ratios) shown in Tables 2-1 to 2-5 to prepare compositions. In addition, although Example 37 has the same formulation as Example 1, one containing no polymerization initiator (composition A) and one containing a polymerization initiator (composition B) of Example 1 were separately prepared and evaluated. It was prepared by mixing the two immediately before.

<LED Curability>
Each composition was applied to a corona-treated PET film (thickness: 100 μm) using Select Roller OSP-13 (manufactured by OSG System Products) to form a film having a thickness of about 10 μm. This film was cured with LED light (395 nm) at an irradiation energy of 2,000 mJ/cm ² using an irradiation device. The cured film placed on a horizontal table was touched with a finger to evaluate the state of the cured film according to the following criteria. The results are shown in Tables 2-1 to 2-5.
[Evaluation criteria]
◎: No tack ○: Tack remains, but maintains a solid state △: Tack remains and has a soft feel, but maintains a solid state ×: Insufficient curing and liquid state be

<Flexibility of cured film>
The state of each cured film produced in the above curability evaluation was visually observed when the substrate (PET film) was folded, and evaluated according to the following criteria. The results are shown in Tables 2-1 to 2-5.
[Evaluation criteria]
◎: No cracks even when folded in half ○: No cracks when wrapped 360° around a metal rod with a diameter of 5 mm △: No cracks when wrapped 360° around a metal rod with a diameter of 10 mm ×: Diameter Cracks occur when wrapped 360° around a 10mm metal rod

<Raw meat adhesion>
A cut of about 1 cm was made in commercially available pork (loin meat with a thickness of 3 mm) with a utility knife. Each of the prepared compositions (approximately 1 g) was placed on the cut portion of the pork and lightly smoothed with a spatula to spread around the cut. Next, LED light (wavelength: 395 nm) was irradiated under the above-mentioned conditions, and the back surface was similarly irradiated to prepare a sample for raw meat adhesion evaluation.
After pulling the sample to the left and right by hand, the adhesive state was observed when the adhesive portion was picked up with tweezers and evaluated according to the following criteria. The results are shown in Tables 2-1 to 2-5.
[Evaluation criteria]
◎: The adhesive state is maintained even by pulling to the left and right and pulling it up. The glued part is peeled off or destroyed by pulling on the left and right

<Evaluation of Odor>
The odor of each composition was evaluated by the following procedures (1) to (3). Evaluation criteria are as follows. The results are shown in Tables 2-1 to 2-5.
(1) About 100 mg (0.1 g) of each composition was weighed into a 50 cc sample bottle (glass bottle), and the bottle was capped.
(2) Left for 30 minutes under room temperature (25°C) conditions.
(3) The nose was brought close to the sample bottle (glass bottle) and the odor was smelled when the lid was opened.
〔Evaluation criteria〕
◎: almost no odor ○: odor is felt but not unpleasant △: specific odor causes discomfort ×: specific odor causes strong discomfort

From the results of Tables 2-1 to 2-5, the compositions of Examples 1 to 37 had less curability, cured film flexibility, adhesion to raw meat, and less odor than Comparative Examples 1 to 6. It is excellent in balance of lack. Furthermore, it can be said that it is suitable for medical use because it can be composed of materials with little risk of skin sensitization.

ただし、前記一般式（１）中、Ｒ_１は炭素数１～６のアルキル基を表し、Ｘは炭素数１～６のアルキレン基を表し、Ｙは下記一般式（２）又は下記一般式（３）を表す。

ただし、前記一般式（２）中、Ｒ_２は炭素数１～１０のアルキル基を表し、＊は前記Ｘとの結合部位を表す。

ただし、前記一般式（３）中、Ｒ_２は炭素数１～１０のアルキル基を表し、＊は前記Ｘとの結合部位を表す。

ただし、前記一般式（４）中、環Ｘは窒素原子を含む炭素数２～５の環構造を表し、Ｒ^４は単結合、又は炭素数１～３の直鎖若しくは分岐のアルキレン基を表し、Ｒ^５は炭素数１～３の直鎖又は分岐のアルキル基を表す。ただし、環Ｘ、Ｒ^４及びＲ^５の炭素数の合計は３～６である。
＜２＞ 前記粘度調整成分が重合性官能基を有する重合性オリゴマーである前記＜１＞に記載の組成物である。
＜３＞ 前記粘度調整成分の含有量が、５質量％以上７０質量％以下である前記＜１＞から＜２＞のいずれかに記載の組成物である。
＜４＞ 更に多官能（メタ）アクリレート化合物を含有する前記＜１＞から＜２＞のいずれかに記載の組成物である。
＜５＞ 前記多官能（メタ）アクリレート化合物の含有量が、５質量％以上７０質量％以下である前記＜１＞から＜４＞のいずれかに記載の組成物である。
＜６＞ 前記エステル構造を有するアクリルアミド化合物が前記一般式（１）で表される化合物である前記＜１＞から＜５＞のいずれかに記載の組成物である。
＜７＞ 前記エステル構造を有するアクリルアミド化合物が前記一般式（１）で表され、前記一般式（１）中のＹが前記一般式（３）で表される前記＜６＞に記載の組成物である。
＜８＞ 前記一般式（３）のＲ_２が炭素数１～２のアルキル基である前記＜７＞に記載の組成物である。
＜９＞ 前記重合開始剤の分子量が８００以上である前記＜１＞から＜８＞のいずれかに記載の組成物である。
＜１０＞ 有機溶剤を含まない前記＜１＞から＜９＞のいずれかに記載の組成物である。
＜１１＞ 活性エネルギー線硬化型組成物である前記＜１＞から＜１０＞のいずれかに記載の組成物である。
＜１２＞ 前記＜１＞から＜１１＞のいずれかに記載の組成物が容器中に収容されてなることを特徴とする収容容器である。
＜１３＞ 前記＜１＞から＜１１＞のいずれかに記載の組成物を収容する収容部と、
前記組成物を付与する付与手段と、
前記組成物を硬化させる硬化手段と、
を有することを特徴とする２次元又は３次元の像形成装置である。
＜１４＞ 前記硬化手段が、波長３６５ｎｍ以上４０５ｎｍ以下にピークを有する紫外線を照射するＵＶ－ＬＥＤである前記＜１３＞に記載の像形成装置である。
＜１５＞ 前記＜１＞から＜１１＞のいずれかに記載の組成物を付与する付与工程と、
前記組成物を硬化させる硬化工程と、
を含むことを特徴とする２次元又は３次元の像形成方法である。
＜１６＞ 前記硬化工程において、波長３６５ｎｍ以上４０５ｎｍ以下にピークを有する紫外線をＵＶ－ＬＥＤで照射する前記＜１５＞に記載の像形成方法である。
＜１７＞ 前記＜１＞から＜１１＞のいずれかに記載の組成物を収容する収容部と、
前記組成物を付与する付与手段と、
を有することを特徴とする医療用シート作製装置である。
＜１８＞ 更に、波長３６５ｎｍ以上４０５ｎｍ以下にピークを有する紫外線を照射するＵＶ－ＬＥＤである照射手段を有する前記＜１７＞に記載の医療用シート作製装置である。
＜１９＞ 基材と、該基材上に前記＜１＞から＜１１＞のいずれかに記載の組成物、又は該組成物の硬化物を含む層と、を有することを特徴とする医療用シートである。
＜２０＞ 前記＜１＞から＜１１＞のいずれかに記載の組成物を含有することを特徴とする医療用接着剤又は被覆剤である。
＜２１＞ 更に、生物学的作用物質、治療薬、及び消毒薬から選択される少なくとも１種を含有する前記＜２０＞に記載の医療用接着剤又は被覆剤である。
＜２２＞ 外科手術用接着剤である前記＜２０＞から＜２１＞のいずれかに記載の医療用接着剤又は被覆剤である。
＜２３＞ 外科手術用シート状接着剤である前記＜２０＞から＜２１＞のいずれかに記載の医療用接着剤又は被覆剤である。
＜２４＞ 創傷保護剤である前記＜２０＞から＜２１＞のいずれかに記載の医療用接着剤又は被覆剤である。
＜２５＞ 接着性を有する消毒剤である前記＜２０＞から＜２１＞のいずれかに記載の医療用接着剤又は被覆剤である。
＜２６＞ エステル構造を有する単官能アクリルアミド化合物及び粘度調整成分を含む組成物Ａと、重合開始剤を含む組成物Ｂとからなる前記＜２０＞から＜２５＞のいずれかに記載の医療用接着剤又は被覆剤である。 Embodiments of the present invention are, for example, as follows.
<1> A composition characterized by containing an acrylamide compound having an ester structure represented by at least one of the following general formula (1) and the following general formula (4), a polymerization initiator, and a viscosity adjusting component. be.

However, in the general formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms, X represents an alkylene group having 1 to 6 carbon atoms, and Y represents the following general formula (2) or the following general formula ( 3).

However, in the general formula (2), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents the bonding site with X.

However, in the above general formula (3), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents the bonding site with X above.

However, in the general formula (4), ring X represents a ring structure having 2 to 5 carbon atoms containing a nitrogen atom, and R ⁴ represents a single bond or a linear or branched alkylene group having 1 to 3 carbon atoms. , R ⁵ represents a linear or branched alkyl group having 1 to 3 carbon atoms. However, the total number of carbon atoms in ring X, R ⁴ and R ⁵ is 3-6.
<2> The composition according to <1>, wherein the viscosity adjusting component is a polymerizable oligomer having a polymerizable functional group.
<3> The composition according to any one of <1> to <2>, wherein the content of the viscosity adjusting component is 5% by mass or more and 70% by mass or less.
<4> The composition according to any one of <1> to <2>, further comprising a polyfunctional (meth)acrylate compound.
<5> The composition according to any one of <1> to <4>, wherein the content of the polyfunctional (meth)acrylate compound is 5% by mass or more and 70% by mass or less.
<6> The composition according to any one of <1> to <5>, wherein the acrylamide compound having an ester structure is a compound represented by the general formula (1).
<7> The composition according to <6>, wherein the acrylamide compound having an ester structure is represented by the general formula (1), and Y in the general formula (1) is represented by the general formula (3). is.
<8> The composition according to <7>, wherein R ₂ in formula (3) is an alkyl group having 1 to 2 carbon atoms.
<9> The composition according to any one of <1> to <8>, wherein the polymerization initiator has a molecular weight of 800 or more.
<10> The composition according to any one of <1> to <9>, which does not contain an organic solvent.
<11> The composition according to any one of <1> to <10>, which is an active energy ray-curable composition.
<12> A container containing the composition according to any one of <1> to <11>.
<13> a container for containing the composition according to any one of <1> to <11>;
applying means for applying the composition;
Curing means for curing the composition;
A two-dimensional or three-dimensional image forming apparatus comprising:
<14> The image forming apparatus according to <13>, wherein the curing unit is a UV-LED that emits ultraviolet light having a peak wavelength of 365 nm or more and 405 nm or less.
<15> A step of applying the composition according to any one of <1> to <11>;
A curing step of curing the composition;
A two-dimensional or three-dimensional imaging method comprising:
<16> The image forming method according to <15>, wherein in the curing step, ultraviolet rays having a peak wavelength of 365 nm or more and 405 nm or less are irradiated with a UV-LED.
<17> a container for containing the composition according to any one of <1> to <11>;
applying means for applying the composition;
A medical sheet manufacturing apparatus characterized by having
<18> The apparatus for manufacturing a medical sheet according to <17>, further comprising an irradiation means that is a UV-LED that emits ultraviolet light having a peak wavelength of 365 nm or more and 405 nm or less.
<19> A medical device comprising a substrate and a layer containing the composition according to any one of <1> to <11> above the substrate, or a cured product of the composition. is a sheet.
<20> A medical adhesive or coating comprising the composition according to any one of <1> to <11>.
<21> The medical adhesive or coating according to <20>, further containing at least one selected from biological agents, therapeutic agents, and disinfectants.
<22> The medical adhesive or coating according to any one of <20> to <21>, which is a surgical adhesive.
<23> The medical adhesive or coating according to any one of <20> to <21>, which is a surgical sheet adhesive.
<24> The medical adhesive or coating according to any one of <20> to <21>, which is a wound protectant.
<25> The medical adhesive or coating according to any one of <20> to <21>, which is an adhesive disinfectant.
<26> The medical adhesive according to any one of <20> to <25>, comprising a composition A containing a monofunctional acrylamide compound having an ester structure and a viscosity adjusting component, and a composition B containing a polymerization initiator. agent or coating.

The composition according to any one of <1> to <11>, the container according to <12>, and the two-dimensional or three-dimensional image forming apparatus according to any one of <13> to <14>. , the two-dimensional or three-dimensional image forming method according to any one of <15> to <16>, the medical sheet manufacturing apparatus according to any one of <17> to <18>, and the <19> According to the medical sheet described above and the medical adhesive or coating agent described in any one of <20> to <26>, various problems in the past can be solved and the object of the present invention can be achieved.

1 Storage pool (accommodation part)
3 Movable stage 4 Active energy ray 5 Composition 6 Curing layer 30 Discharge head unit for model 31, 32 Discharge head unit for support 33, 34 Ultraviolet irradiation means 35 Three-dimensional model 36 Support laminated part 37 Model support substrate

JP 2005-154477 A JP 2010-180377 A Japanese translation of PCT publication No. 2013-538280

Trends in Glycoscience and Glycotechnology Vol. 14 No. 80 pp. 331-341

Claims (18)

A medical adhesive or coating comprising an acrylamide compound having an ester structure represented by at least one of the following general formulas (1) and (4), a polymerization initiator, and a viscosity adjusting component. agent .

However, in the general formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms, X represents an alkylene group having 1 to 6 carbon atoms, and Y represents the following general formula (2) or the following general formula ( 3).

However, in the general formula (2), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents the bonding site with X.

However, in the above general formula (3), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents the bonding site with X above.

However, in the general formula (4), ring X represents a ring structure having 2 to 5 carbon atoms containing a nitrogen atom, and R ⁴ represents a single bond or a linear or branched alkylene group having 1 to 3 carbon atoms. , R ⁵ represents a linear or branched alkyl group having 1 to 3 carbon atoms. However, the total number of carbon atoms in ring X, R ⁴ and R ⁵ is 3-6. 2. The medical adhesive or coating according to claim 1, wherein the viscosity adjusting component is a polymerizable oligomer having a polymerizable functional group. The medical adhesive or coating according to any one of claims 1 and 2, further comprising a polyfunctional (meth)acrylate compound. 4. The medical adhesive or coating according to any one of claims 1 to 3, wherein the acrylamide compound having an ester structure is a compound represented by the general formula (1). The medical adhesive or coating according to claim 4, wherein the acrylamide compound having an ester structure is represented by the general formula (1), and Y in the general formula (1) is represented by the general formula (3). agent . 6. The medical adhesive or coating according to claim 5, wherein R ₂ in said general formula (3) is an alkyl group having 1 to 2 carbon atoms. The medical adhesive or coating according to any one of claims 1 to 6, wherein the polymerization initiator has a molecular weight of 800 or more. The medical adhesive or coating according to any one of claims 1 to 7, which is an active energy ray-curable composition. A container comprising the medical adhesive or coating according to any one of claims 1 to 8, which is contained in the container. a storage unit that stores a composition containing an acrylamide compound having an ester structure represented by at least one of the following general formula (1) and the following general formula (4), a polymerization initiator, and a viscosity adjusting component ;
applying means for applying the composition;
A medical sheet manufacturing apparatus characterized by comprising:

However, in the general formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms, X represents an alkylene group having 1 to 6 carbon atoms, and Y represents the following general formula (2) or the following general formula ( 3).

However, in the general formula (2), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents the bonding site with X.

However, in the above general formula (3), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents the bonding site with X above.

However, in the general formula (4), ring X represents a ring structure having 2 to 5 carbon atoms containing a nitrogen atom, and R ⁴ represents a single bond or a linear or branched alkylene group having 1 to 3 carbon atoms. , R ⁵ represents a linear or branched alkyl group having 1 to 3 carbon atoms. However, the total number of carbon atoms in ring X, R ⁴ and R ⁵ is 3-6. 11. The medical sheet manufacturing apparatus according to claim 10, further comprising an irradiation means which is a UV-LED for irradiating ultraviolet rays having a peak wavelength of 365 nm or more and 405 nm or less. A composition comprising a base material, an acrylamide compound having an ester structure represented by at least one of the following general formula (1) and the following general formula (4) on the base material, a polymerization initiator, and a viscosity adjusting component. or a layer containing a cured product of the composition.

However, in the general formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms, X represents an alkylene group having 1 to 6 carbon atoms, and Y represents the following general formula (2) or general formula (3).

However, in the general formula (2), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a bonding site with the aforementioned X.

However, in the general formula (3), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a bonding site with the aforementioned X.

However, in the general formula (4), ring X represents a ring structure having 2 to 5 carbon atoms containing a nitrogen atom; ⁴ represents a single bond or a linear or branched alkylene group having 1 to 3 carbon atoms, and R ⁵ represents a linear or branched alkyl group having 1 to 3 carbon atoms. However, ring X, R ⁴ and R ⁵ The total number of carbon atoms in is 3-6. 9. The medical adhesive or coating according to any one of claims 1 to 8, further comprising at least one selected from biological agents, therapeutic agents and antiseptics. 14. A medical adhesive or coating according to any one of claims 1 to 8 and 13 which is a surgical adhesive. 14. The medical adhesive or coating according to any one of claims 1 to 8 and 13, which is a surgical adhesive sheet. 14. A medical adhesive or dressing according to any one of claims 1 to 8 and 13 which is a wound protectant. The medical adhesive or coating according to any one of claims 1 to 8 and 13, which is an adhesive antiseptic. 18. The medical adhesive according to any one of claims 1 to 8 and 13 to 17, comprising composition A containing a monofunctional acrylamide compound having an ester structure and a viscosity adjusting component, and composition B containing a polymerization initiator, or coating.

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