JP2016056285A - Amphoteric ionic curable compound, active energy ray-curable coating agent, biocompatible material, and production method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an amphoteric ionic curable compound that excels in productivity and exhibits excellent coating film durability and biocompatibility by irradiation with active energy rays, and active energy ray-curable coating agent and a biocompatible material.SOLUTION: The amphoteric ionic curable compound has an ethylenically unsaturated group, a tertiary amino group, and a carboxyl group; and the compound is obtained by subjecting at least a part of ethylenically unsaturated groups of a curable compound (B) having three or more ethylenically unsaturated groups to Michael addition with a secondary amino group of a compound (C) having a secondary amino group and a carboxyl group.SELECTED DRAWING: None

Description

The present invention relates to a zwitterionic curable compound, an active energy ray-curable coating agent, a biocompatible material obtained by curing by irradiation with active energy rays, and a method for producing the same.

In recent years, rapid development of biotechnology has led to the development of biocompatible polymer materials in which biomolecules such as proteins are not adsorbed and activated at the interface between medical devices and healthcare devices and biological components. Actively studied. Above all, polymer materials produced from zwitterionic monomers are attracting attention as materials with excellent biocompatibility because they do not disturb the hydrogen-bonding network of water despite the electrolyte. .
Patent Document 1 discloses a phosphobetaine-type polymer material (MPC polymer) obtained by polymerizing 2-methacrylolyloxyethylphosphocholine. Patent Document 2 discloses a carboxybetaine-type polymer material obtained by polymerizing N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine.
In addition, amino acid molecules having a zwitterionic structure are also attracting attention as materials having excellent biocompatibility like MPC polymers. In Patent Document 3, a zwitterionic monomer (meth) acrylic acid having an amino acid residue is noted. Serine esters and polymer materials obtained by polymerizing them are disclosed.
However, since all of these biocompatible polymer materials have high affinity with water, it is difficult to obtain water resistance of the coating. When a cross-linking agent is used to solve this problem, biocompatibility is deteriorated due to the influence of the cross-linking agent, so that compatibility between film resistance and biocompatibility is a problem.
Moreover, in order to synthesize biocompatible monomers exemplified in these prior documents, complicated synthesis steps and purification steps are required. It is hard to say that there is.

Japanese Patent Laid-Open No. H09-3132 JP 2007-130194 A Japanese Patent Laid-Open No. 1998-251209

  The present invention provides a zwitterionic curable compound and an active energy ray curable coating agent that are excellent in productivity and exhibit excellent film resistance and biocompatibility upon irradiation with active energy rays, and the zwitterionic curable properties. An object is to provide a biocompatible material obtained by curing a compound by irradiation with active energy rays.

That is, the present invention provides a secondary compound (C) having a secondary amino group and a carboxyl group in at least a part of the ethylenically unsaturated group of the curable compound (B) having three or more ethylenically unsaturated groups. An ethylenically unsaturated group, characterized by Michael addition of an amino group,
The present invention relates to a zwitterionic curable compound (A) having a tertiary amino group and a carboxyl group.

The present invention also relates to an active energy ray-curable coating agent comprising the zwitterionic curable compound (A) and a solvent (D).

Moreover, this invention relates to the said active energy ray hardening-type coating agent characterized by including a polymerization initiator (E) further.

Moreover, this invention relates to the cured film formed by apply | coating the said active energy ray hardening-type coating agent on a base material, and making it harden | cure.

In addition, the present invention provides a secondary compound (C) having a secondary amino group and a carboxyl group in at least a part of the ethylenically unsaturated group of the curable compound (B) having three or more ethylenically unsaturated groups. The present invention relates to a method for producing an amphoteric ionic curable compound (A) having an ethylenically unsaturated group, a tertiary amino group and a carboxyl group, wherein the amino group is Michael-added.

  The present invention is a novel curable compound having a zwitterionic structure and has an ethylenically unsaturated group that is cured by active energy rays and a zwitterionic skeleton excellent in biocompatibility. By curing this by irradiation with active energy rays, a biocompatible material having excellent film resistance and biocompatibility can be provided. The biocompatible material has excellent film resistance and is expected to be used in applications that require suppression of protein adhesion, preferably in medical applications and healthcare applications. In the present specification, “biocompatibility” means a property in which proteins are hardly adsorbed.

<Zwitterionic curable compound (A)>
The zwitterionic curable compound (A) of the present invention is a secondary amino group of the compound (C) having a secondary amino group and a carboxyl group on the ethylenically unsaturated group of the ethylenically unsaturated resin composition (B). Is a zwitterionic curable compound having an ethylenically unsaturated group, a tertiary amino group, and a carboxyl group, which is obtained by a simple synthesis method in which Michael is added.

  The zwitterionic curable compound (A) preferably has a zwitterionic structure represented by the following general formulas (1), (2), and (3) as its partial structure. More preferably, they are general formula (1) and (3).

General formula (1)

(X represents an oxygen atom or an NH group.)

General formula (2)

(X represents an oxygen atom or an NH group.)

General formula (3)

(X represents an oxygen atom or an NH group.)

The zwitterionic curable compound (A) of the present invention has one or more ethylenically unsaturated groups, and an average of 2 ethylenically unsaturated groups per molecule from the viewpoint of durability of the cured film. The number is preferably at least 3, more preferably at least 3. Moreover, the average number of ethylenically unsaturated groups of the zwitterionic curable compound (A) can be obtained by the following formula.
"Zwitterionic curable compound (A) average number of ethylenically unsaturated groups per molecule = curable compound (B) number of ethylenically unsaturated groups-compound having secondary amino group and carboxyl group (C) Number of secondary amino groups of x (number of moles of compound (C) having secondary amino group and carboxyl group / number of moles of curable compound (B)) "

The number of ethylenically unsaturated groups of the zwitterionic curable compound (A) is preferably 1 to 10 and more preferably 1.5 to 5 from the viewpoint of durability of the cured film.

From the viewpoint of biocompatibility, the zwitterionic curable compound (A) of the present invention has a molecular weight per mole of the compound (C) having a secondary amino group and a carboxyl group (hereinafter referred to as zwitterion equivalent) is 100. ˜15,000 is preferable, 100 to 5,000 is more preferable, and 100 to 1,500 is still more preferable.
The zwitterion equivalent of the zwitterionic curable compound (A) can be obtained from the following formula.
“Zwitter ion equivalent of zwitterionic curable compound (A) = (Blend amount of reactive compound (B) (part by weight) + Blend amount of compound (C) having secondary amino group and carboxyl group (part by weight))” / Mole number of compound (C) having secondary amino group and carboxyl group "

<Curable compound (B)>
The curable compound (B) used in the present invention has 3 or more ethylenically unsaturated groups per molecule, more preferably 4 or more. If the number of ethylenically unsaturated groups is less than 3, the number of ethylenically unsaturated groups in the zwitterionic curable compound (A) may decrease, and sufficient resistance of the cured film may not be obtained.

The curable compound (B) used in the present invention is not particularly limited as long as it is a compound having 3 or more ethylenically unsaturated groups, and preferably has 3 or more ethylenically unsaturated groups. Monomer or oligomer. Preferred examples include pentaerythritol tri (meth) acrylate and (meth) acrylamide, pentaerythritol tetra (meth) acrylate and (meth) acrylamide, trimethylolpropane tri (meth) acrylate and (meth) acrylamide, EO-modified trimethylol. Propane tri (meth) acrylate and (meth) acrylamide, PO-modified trimethylolpropane tri (meth) acrylate and (meth) acrylamide, tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, trimethylol Ethanetri (meth) acrylate and (meth) acrylamide, dipentaerythritol tetra (meth) acrylate and (meth) a Rilamide, dipentaerythritol penta (meth) acrylate and (meth) acrylamide, dipentaerythritol hexa (meth) acrylate and (meth) acrylamide, alkyl-modified dipentaerythritol tri (meth) acrylate and (meth) acrylamide, alkyl-modified dipenta Erythritol tetra (meth) acrylate and (meth) acrylamide, alkyl-modified dipentaerythritol penta (meth) acrylate and (meth) acrylamide, caprolactone-modified dipentaerythritol hexa (meth) acrylate and (meth) acrylamide, 1,2,3- Polyhydric alcohols such as cyclohexanetetra (meth) acrylate and (meth) acrylamide and (meth) acrylic acid and (meth) acrylate Ester compound of Riruamido;
Polyurethane poly (meth) acrylate and (meth) acrylamide, polyester poly (meth) acrylate and (meth) acrylamide, polyether poly (meth) acrylate and (meth) acrylamide, polyacryl poly (meth) acrylate and (meth) acrylamide, Polyalkyd poly (meth) acrylate and (meth) acrylamide, polyepoxy poly (meth) acrylate and (meth) acrylamide, polyspiroacetal poly (meth) acrylate and (meth) acrylamide, polybutadiene poly (meth) acrylate and (meth) Polyfunctional compounds such as acrylamide, polythiol polyene poly (meth) acrylate and (meth) acrylamide, polysilicon poly (meth) acrylate Poly (meth) acrylate and (meth) acrylamide compound;
An ester compound synthesized from a polyhydric alcohol, a polybasic acid and (meth) acrylic acid, such as an ester compound synthesized from trimethylolethane / succinic acid / acrylic acid = 2/4 (molar ratio), etc. It is done. These may be used alone or in combination of two or more in any combination.

  The weight average molecular weight of the curable compound (B) is preferably in the range of 200 to 150,000, more preferably 200 to 20,000, and further preferably in the range of 250 to 10,000. When the weight average molecular weight is less than 200, sufficient resistance of the cured film may not be obtained. When the weight average molecular weight is greater than 150,000, the compound (C) having a secondary amino group and a carboxyl group After the Michael addition reaction, the viscosity becomes too high and handling may be deteriorated, or biocompatibility may be deteriorated due to deterioration of leveling due to an increase in viscosity.

  The number of ethylenically unsaturated groups of the curable compound (B) is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 8 from the viewpoint of durability of the cured film.

<Compound (C) having secondary amino group and carboxyl group>
The compound (C) having a secondary amino group and a carboxyl group in one molecule used in the present invention is more soluble in the solvent during the Michael addition reaction than the case of having a primary amino group, and the amphoteric ions produced. The solvent solubility of the mold curable compound (A) is excellent. The compound (C) is not particularly limited as long as it is an organic compound having a secondary amino group and a carboxyl group, but is preferably soluble in an alcohol solvent from the viewpoint of the production method. It is excellent in solubility in alcohol solvent, and also very excellent in solubility in water, and when it is introduced as a hydrophilic group, it becomes a strong hydrophilic group. Therefore, the following general formulas (4) to (6) The cyclic imino acid represented is preferred. Preferably, it is general formula (4) or (6).

General formula (4)

General formula (5)

General formula (6)

Preferred specific examples represented by the general formulas (4) to (6) include pyrrolidine-2-carboxylic acid, 4-hydroxypyrrolidine-2-carboxylic acid, piperidine-2-carboxylic acid, piperidine-4-carboxylic acid and the like. Pyrrolidine-2-carboxylic acid is more preferable from the viewpoint of solvent solubility.

<Michael addition reaction>
The Michael addition reaction between the curable compound (B) and the compound (C) having a secondary amino group and a carboxyl group, which is performed to obtain the zwitterionic curable compound (A), is preferably performed in the presence of a solvent. Examples of solvents that can be used include alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol;
Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone;
Ester solvents such as ethyl acetate and butyl acetate;
Alcohol solvents such as ethanol, methanol, n-propanol, 2-propanol, butanol, hexanol;
Ether solvents such as diisopropyl ether, butyl cellosolve, tetrahydrofuran, dioxane, butyl carbitol;
Glycol ether solvents such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether;
Examples include glycol ester solvents such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate. These may be used alone or in combination of two or more in any combination. Among them, it is preferable to use an alcohol solvent because the curable compound (B) and the compound (C) having a secondary amino group and a carboxyl group have high solubility and the effect of promoting the Michael addition reaction.

  The Michael addition reaction is preferably carried out in the range of 50 to 90 ° C. in order to maintain the stability of the curable compound (B), and the reaction time is preferably 1 to 15 hours. Moreover, in order to ensure the stability of the curable compound (B), a known polymerization inhibitor such as methoxyphenol or hydroquinone may be used.

The zwitterionic curable compound (A) has an ethylenically unsaturated group that is cured by active energy rays and a zwitterionic skeleton excellent in biocompatibility, and includes a coating containing the zwitterionic curable compound (A). After being formed on the substrate surface, a cured film having both biocompatibility and durability can be easily obtained by a process of curing with active energy rays.

  A method for forming a film containing the zwitterionic curable compound (A) used in the present invention on the substrate surface is not particularly limited. For example, a coating agent containing the zwitterionic curable compound (A) is used. , Bar coating, blade coating, spin coating, reverse coating, die coating, spray coating, roll coating, gravure coating, micro gravure coating, lip coating, air knife coating, dipping and the like. Although the film thickness of a film is not specifically limited, About 1-30 micrometers is preferable.

  Examples of the material constituting the substrate include polyethylene, polypropylene, polystyrene, polyvinyl chloride, nylon, polyurethane, polyurea, polylactic acid, polyglycolic acid, polyvinyl alcohol, polyvinyl acetate, poly (meth) acrylic acid, poly (Meth) acrylic acid derivative, polyacrylonitrile, poly (meth) acrylamide, poly (meth) acrylamide derivative, polysulfone, polycarbonate, cellulose, cellulose derivative, polysilicone, glass, ceramic, metal and the like. These materials may be used alone or in combination of two or more in any combination.

<Coating agent>
The coating agent containing the zwitterionic curable compound (A) preferably uses a solvent (D) so as to have an optimum coating viscosity for the coating method. The solvent (D) used by this invention can use the solvent illustrated by the solvent which can be used at the time of the above-mentioned Michael addition reaction, for example. These may be used alone or in any combination. Especially, it is preferable to use an alcohol solvent from the point that the solubility of the zwitterionic curable compound (A) is good. The solvent used in the Michael addition reaction and the solvent (D) used in the coating agent may be the same or different.

After applying the coating agent containing the zwitterionic curable compound (A) to the substrate surface by the above-described coating method, the solvent contained in the coating agent is heated and dried as necessary and irradiated with active energy rays. Thus, a cured film can be obtained. The “active energy ray” in the present invention means an energy ray that affects the electron orbit of the polymerizable component of the irradiated object and can induce a radical polymerization reaction. Examples of the active energy ray include ultraviolet rays emitted from a light source such as a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, and an LED, or a cockro walton of usually 20 to 2000 KeV. Electron beams, α rays, β rays, γ rays and the like extracted from electron beam accelerators such as a type, a bandegraph type, a resonance transformation type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used.

  When the film containing the zwitterionic curable compound (A) used in the present invention is cured by ultraviolet rays, it is preferable to use a polymerization initiator (E) in order to allow the curing reaction to proceed efficiently. The polymerization initiator (E) is not particularly limited as long as it has a function capable of initiating radical polymerization by photoexcitation. For example, acetophenone compound, benzoin compound, benzophenone compound, phosphine oxide compound, ketal compound, anthraquinone compound, thioxanthone compound Etc. Specifically, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diethoxyacetophenone, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2,4,6-trimethylbenzoin diphenylphosphine oxide, N , N-dimethylaminobenzoic acid isoamine, 2-chlorothioxanthone, 2,4-diethylthioxanthone and the like. These may be used alone or in combination of two or more in any combination. Moreover, a well-known organic amine can also be added as a photosensitizer.

  As a compounding quantity of the polymerization initiator (E) used by this invention, the range of 0.1-20 weight part is preferable with respect to 100 weight part of zwitterionic curable compound (A), and 1-10 weight part. Part is more preferred. When the amount of the polymerization initiator (E) is less than 0.1 parts by weight or more than 20 parts by weight, the durability of the cured coating film may be deteriorated.

  In the coating agent containing the zwitterionic curable compound (A) used in the present invention, an average of 2 or more per molecule within a range not impairing the effect of the present invention in order to adjust the hardness of the cured film. The ethylenically unsaturated resin composition (F) having an ethylenically unsaturated group and having no zwitterionic structure may be used in combination. Examples of the ethylenically unsaturated resin composition (F) that can be used in the present invention include polyfunctional ethylenically unsaturated compounds having a structure exemplified by the above-mentioned curable compound (B). These may be used alone or in combination of two or more in any combination.

The blending amount of the ethylenically unsaturated resin composition (F) that can be used together in the present invention is preferably 200 parts by weight or less, more preferably 100 parts by weight with respect to 100 parts by weight of the zwitterionic curable compound (A). Is 100 parts by weight or less. When there are more compounding quantities of the ethylenically unsaturated resin composition (F) which can be used together than 200 weight part, there exists a possibility that the biocompatibility of a cured coating film may deteriorate.

In the coating agent containing the zwitterionic curable compound (A) of the present invention, known additives such as a lubricant, a leveling agent, an antifoaming agent, a polymerization inhibitor, and a filler are used as long as the effects of the present invention are not impaired. can do.

EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight” and “%” represents “% by weight”.

The number of ethylenically unsaturated groups and the zwitterion equivalent of the compound (A) were calculated by the calculation formula described in this specification.
<Weight average molecular weight>
To measure the weight average molecular weight, Tosoh GPC (gel permeation chromatography) “HPC-8020” was used. Tosoh SUPER AW3000 was connected in series as a column, and triethylamine 30 mM and lithium bromide were added as additives. Measurement was performed at 40 ° C. using a dimethylformamide solution dissolved to 10 mM as an eluent. The weight average molecular weight was calculated in terms of standard polystyrene.

<Synthesis of zwitterionic ethylenically unsaturated compounds (A-1) to (A'-6)>
Various zwitterionic ethylenically unsaturated compounds (A) were synthesized with the formulations shown in Table 1. Specific reaction steps are shown below.

(Example 1)
<Synthesis of zwitterionic ethylenically unsaturated compound (A-1)>
In a reaction vessel equipped with a reflux and a stirrer, A-TMPT (trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., 3 ethylenically unsaturated groups per molecule, weight average as curable compound (B) 42.0 parts of molecular weight 300) was charged as 8.0 parts of pyrrolidine-2-carboxylic acid as a compound (C) having a secondary amino group and a carboxyl group, and 50 parts of ethanol as a solvent (D). Next, the mixture was stirred while blowing air, and the temperature was raised to 70 ° C. Then, the reaction was terminated when the reaction was held at 70 ° C. for 5 hours.
Thus, a zwitterionic ethylenically unsaturated compound (A-1) solution having a solid content of 50% and 2.5 ethylenically unsaturated groups per molecule was obtained.

(Example 2)
<Synthesis of zwitterionic ethylenically unsaturated compound (A-2)>
In a reaction vessel equipped with a reflux condenser and a stirrer, AD-TMP (ditrimethylolpropane tetraacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., number of ethylenically unsaturated groups per molecule, weight average as curable compound (B) 39.2 parts of molecular weight 470) 10.8 parts of piperidine-2-carboxylic acid as compound (C) having secondary amino group and carboxyl group, 25 parts of propylene glycol monomethyl ether (PGM) as solvent (D) , 25 parts of methanol was charged. Next, the mixture was stirred while blowing air, and the temperature was raised to 70 ° C. Then, the reaction was terminated when the reaction was held at 70 ° C. for 5 hours.
Thus, a zwitterionic ethylenically unsaturated compound (A-2) solution having a solid content of 50% and three ethylenically unsaturated groups per molecule was obtained.

(Example 3)
<Synthesis of zwitterionic ethylenically unsaturated compound (A-3)>
In a reaction vessel equipped with a reflux and a stirrer, A-DPH (Shin Nakamura Chemical Co., Ltd. dipentaerythritol hexaacrylate, number of ethylenically unsaturated groups per molecule, 6 weight average, as a curable compound (B) 33.4 parts of molecular weight 580) was charged as compound (C) having a secondary amino group and a carboxyl group, 16.6 parts of pyrrolidine-2-carboxylic acid, and 50 parts of ethanol as solvent (D). Next, the mixture was stirred while blowing air, and the temperature was raised to 70 ° C. Then, the reaction was terminated when the reaction was held at 70 ° C. for 5 hours.
Thus, a zwitterionic ethylenically unsaturated compound (A-3) solution having a solid content of 50% and an ethylenically unsaturated group number of 3.5 per molecule was obtained.

Example 4
<Synthesis of zwitterionic ethylenically unsaturated compound (A-4)>
In a reaction vessel equipped with a reflux condenser and a stirrer, UV-7610B (urethane acrylate manufactured by Nippon Synthetic Chemical Co., Ltd., number of ethylenically unsaturated groups per molecule, weight average molecular weight 11,000 as curable compound (B). ) 47.5 parts, pyrrolidine-2-carboxylic acid 2.5 parts, and ethanol 50 parts. Next, the mixture was stirred while blowing air, and the temperature was raised to 70 ° C. Then, the reaction was terminated when the reaction was held at 70 ° C. for 5 hours.
Thus, a zwitterionic ethylenically unsaturated compound (A-4) solution having a solid content of 50% and 4 ethylenically unsaturated groups per molecule was obtained.

(Example 5)
<Synthesis of zwitterionic ethylenically unsaturated compound (A-5)>
In a reaction vessel equipped with a reflux and a stirrer, UN-905 (a urethane acrylate manufactured by Negami Kogyo Co., Ltd., number of ethylenically unsaturated groups per molecule, weight average molecular weight of 120,000) as a curable compound (B). Of pyrrolidine-2-carboxylic acid as compound (C) having 49.5 parts of secondary amino group and carboxyl group, and 50 parts of ethanol as solvent (D). Next, the mixture was stirred while blowing air, and the temperature was raised to 70 ° C. Then, the reaction was terminated when the reaction was held at 70 ° C. for 5 hours.
Thus, a zwitterionic ethylenically unsaturated compound (A-5) solution having a solid content of 50% and 4 ethylenically unsaturated groups per molecule was obtained.

(Comparative Example 1)
In a reaction vessel equipped with a reflux condenser and a stirrer, A-HD-N (1,6-hexanediol diacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., number of ethylenically unsaturated groups per molecule as curable compound (B) 25.0, 25.0 parts of weight average molecular weight 230), 25.0 parts of pyrrolidine-2-carboxylic acid as compound (C) having secondary amino group and carboxyl group, and 50 parts of ethanol as solvent (D) It is. Next, the mixture was stirred while blowing air, and the temperature was raised to 70 ° C. Then, the reaction was terminated when the reaction was held at 70 ° C. for 5 hours.
In this way, a zwitterionic compound (A′-6) solution having a solid content of 50% and no ethylenically unsaturated groups with no ethylenically unsaturated groups per molecule was obtained.

(Comparative Example 2)
In a reaction vessel equipped with a reflux and a stirrer, A-DPH (Shin Nakamura Chemical Co., Ltd. dipentaerythritol hexaacrylate, number of ethylenically unsaturated groups per molecule, 6 weight average, as a curable compound (B) Ethanol with molecular weight 580) of 36.1 parts instead of compound (C) having secondary amino group and carboxyl group, 13.9 parts of alanine which is a compound having primary amino group and carboxyl group, and solvent (D) 50 copies were prepared. Next, the mixture was stirred while blowing air, and the temperature was raised to 70 ° C. Thereafter, the mixture was kept at 70 ° C. and reacted for 5 hours. However, since the solubility of alanine in ethanol was poor, the Michael addition reaction did not proceed, and the reaction was terminated halfway and the reaction product was not tested.

A-TMPT: trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
AD-TMP: Ditrimethylolpropane tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-DPH: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
UV-7610B: urethane acrylate (manufactured by Nippon Synthetic Chemical Co., Ltd.)
UN-905: Urethane acrylate (manufactured by Negami Kogyo Co., Ltd.)
A-HD-N: 1,6-hexanediol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
・ PGM: Propylene glycol monomethyl ether

(Example 6)
<Preparation of coating agent 1>
In a mixing vessel equipped with a stirrer, 40 parts of the zwitterionic ethylenically unsaturated compound (A-1) solution as the zwitterionic ethylenically unsaturated compound (A) and Irgacure 184 (BASF) as the polymerization initiator (E) 11.5 parts) and 11.5 parts of ethanol as solvent (D) were added and stirred until uniform.
Thus, the coating agent 1 adjusted to a solid content of 40% was obtained.

(Example 7)
<Preparation of coating agent 2>
In a mixing vessel equipped with a stirrer, 40 parts of the zwitterionic ethylenically unsaturated compound (A-2) solution as the zwitterionic ethylenically unsaturated compound (A) and Irgacure 184 (BASF) as the polymerization initiator (E) 11.5 parts) and 11.5 parts of ethanol as solvent (D) were added and stirred until uniform.
Thus, coating agent 2 adjusted to a solid content of 40% was obtained.

(Example 8)
<Preparation of coating agent 3>
In a mixing vessel equipped with a stirrer, 40 parts of the zwitterionic ethylenically unsaturated compound (A-2) solution as the zwitterionic ethylenically unsaturated compound (A) and Irgacure 184 (BASF) as the polymerization initiator (E) A-DPH as an ethylenically unsaturated compound (F) (dipentaerythritol hexaacrylate made by Shin-Nakamura Chemical Co., Ltd., number of ethylenically unsaturated groups per molecule, weight average molecular weight 580) 4 parts and 37.5 parts of ethanol as a solvent (D) were added and stirred until uniform.
Thus, coating agent 3 adjusted to a solid content of 40% was obtained.

Example 9
<Preparation of coating agent 4>
In a mixing vessel equipped with a stirrer, 40 parts of the zwitterionic ethylenically unsaturated compound (A-3) solution as the zwitterionic ethylenically unsaturated compound (A) and Irgacure 184 (BASF) as the polymerization initiator (E) 11.5 parts) and 11.5 parts of ethanol as solvent (D) were added and stirred until uniform.
Thus, the coating agent 4 adjusted to a solid content of 40% was obtained.

(Example 10)
<Preparation of coating agent 5>
To a mixing vessel equipped with a stirrer, uniformly add 40 parts of the zwitterionic ethylenically unsaturated compound (A-3) solution as the zwitterionic ethylenically unsaturated compound (A) and 10 parts of ethanol as the solvent (D). Stir until.
Thus, the coating agent 5 adjusted to a solid content of 40% was obtained.

(Example 11)
<Preparation of coating agent 6>
In a mixing vessel equipped with a stirrer, 40 parts of the zwitterionic ethylenically unsaturated compound (A-4) solution as the zwitterionic ethylenically unsaturated compound (A) and Irgacure 184 (BASF) as the polymerization initiator (E) 11.5 parts) and 11.5 parts of ethanol as solvent (D) were added and stirred until uniform.
Thus, the coating agent 6 adjusted to a solid content of 40% was obtained.

Example 12
<Preparation of coating agent 7>
In a mixing vessel equipped with a stirrer, 40 parts of the zwitterionic ethylenically unsaturated compound (A-5) solution as the zwitterionic ethylenically unsaturated compound (A) and Irgacure 184 (BASF) as the polymerization initiator (E) 11.5 parts) and 11.5 parts of ethanol as solvent (D) were added and stirred until uniform.
Thus, the coating agent 7 adjusted to a solid content of 40% was obtained.

(Comparative Example 3)
<Preparation of coating agent 8>
40 parts of the zwitterionic compound (A′-6) solution prepared in Comparative Example 1 in a mixing vessel equipped with a stirrer, 1 part of Irgacure 184 (manufactured by BASF) as a polymerization initiator (E), solvent (D ) 11.5 parts of ethanol was added and stirred until uniform.
Thus, a coating agent 8 adjusted to a solid content of 40% was obtained.

(Examples 13 to 18, Comparative Example 4)
<Production of ecologically compatible materials>

Various coating agents shown in Table 2 were applied to a sufficiently sterilized polystyrene substrate (length: 30 mm, width: 30 mm, thickness: 2 mm) using a bar coater so that the dry film thickness was about 5 μm. After sufficiently drying in an oven and removing the solvent, a cured film (biocompatible material) was obtained by irradiating ultraviolet rays at a distance of 10 cm from the coated surface with a high-pressure mercury lamp with an output of 120 w / cm ² . In Example 17, a cured film was obtained by irradiating an electron beam under conditions of 150 keV and 50 kGy using an electron beam irradiation apparatus instead of ultraviolet irradiation by a high-pressure mercury lamp in the cured film production process. Next, each sample was subjected to ultrasonic cleaning while being immersed in ethanol for 30 seconds, and then the sample taken out was immersed in purified water for 10 minutes and then dried with nitrogen gas. The sample thus prepared was used as a test piece to evaluate wear resistance, water resistance, and biocompatibility. The results are shown in Table 2.

<Evaluation of wear resistance>
The surface condition of the test piece was visually evaluated after 1000 reciprocations using Kimwipe S-200 manufactured by Nippon Paper Crecia Co., Ltd. while applying a load of 500 g to each test piece.
○: No scratch or peeling (no change in appearance, good)
×: Scratches, peeling (change in appearance, defective)

<Evaluation of water resistance>
While applying a load of 500 g to each test piece, the surface condition of the test piece was visually evaluated after rubbing 1000 times using Nippon Paper Crecia Kimwipe S-200 wetted with water.
○: No scratch or peeling (no change in appearance, good)
×: Scratches, peeling (change in appearance, defective)

<Evaluation of biocompatibility>
Bovine serum albumin was used as the protein. Each test piece was placed in 0.5 wt% bovine serum albumin phosphate buffered saline (PBS), incubated for 24 hours, washed with purified water, and dried with nitrogen gas. The absorbance at a wavelength of 562 nm was measured using a Micro BCA Protein Assay Kit manufactured by Takara Bio Inc. The same operation was performed on the polystyrene base material used in the test piece preparation, and the biocompatibility of each test piece was evaluated from the ratio of the absorbance of each test piece to the absorbance measured on the polystyrene base material (hereinafter, measured on the polystyrene base material). The ratio of the absorbance of each test piece to the measured absorbance is called the absorbance ratio). The smaller the absorbance ratio value, the smaller the amount of protein adsorbed and the better the biocompatibility.

A: Absorbance ratio is less than 0.4 (excellent in biocompatibility)
○: Absorbance ratio is 0.4 or more and less than 0.6 (can be used) ×: Absorbance ratio is 0.6 or more (cannot be used)

・ Irg184: Irgacure 184 (manufactured by BASF)
A-DPH: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

As shown in Table 2, in Comparative Example 4, since the zwitterionic compound (A′-6) contained in the used coating agent 8 does not have an ethylenically unsaturated group, the curing reaction does not proceed, and the ultrasonic wave The cured film was eluted in the washing process, and the wear resistance, water resistance, and biocompatibility were significantly reduced.
On the other hand, the coating agents of Examples 6 to 12 shown in Table 2 contain secondary amino groups and carboxyl groups on at least part of the ethylenically unsaturated groups of the curable compound (B) having 3 or more ethylenically unsaturated groups. A zwitterionic curable compound (A) having an ethylenically unsaturated group, a tertiary amino group and a carboxyl group, wherein the secondary amino group of the compound (C) having a group is Michael-added Therefore, all of them had a well-balanced wear resistance, water resistance and biocompatibility. Among these, the coating agents of Examples 6 to 11 were compared with the coating agent of Example 12 and the weight average molecular weight of the curable compound (B) used when synthesizing the zwitterionic curable compound (A) contained therein. Is in a suitable range of 200 to 20,000, and the amphoteric ion equivalent of the zwitterionic curable compound (A) was 100 to 5,000, so that excellent biocompatibility was obtained. Furthermore, compared with the coating agent of Example 11, the coating agent of Examples 6-10 is a weight average molecular weight of the curable compound (B) used when synthesize | combining the zwitterionic curable compound (A) to contain. Is in a more preferable range of 250 to 10,000, and the zwitterionic equivalent of the zwitterionic curable compound (A) was 100 to 1,500, and thus further excellent biocompatibility was obtained.

The zwitterionic curable compound of the present invention is applied to the surface of a substrate made of a material such as glass, metal, or resin, and is cured by irradiation with active energy rays. Since a cured film excellent in compatibility can be formed, it can be suitably used for a biocompatible material having durability in which adhesion of proteins, cells and the like is suppressed.

Claims (5)

Michael addition of the secondary amino group of the compound (C) having a secondary amino group and a carboxyl group to at least a part of the ethylenic unsaturated group of the curable compound (B) having three or more ethylenically unsaturated groups A zwitterionic curable compound (A) having an ethylenically unsaturated group, a tertiary amino group and a carboxyl group.   An active energy ray-curable coating agent comprising the zwitterionic curable compound (A) according to claim 1 and a solvent (D).   The active energy ray-curable coating agent according to claim 2, further comprising a polymerization initiator (E).   A cured film obtained by applying and curing the active energy ray-curable coating agent according to claim 2 or 3 on a substrate. Michael addition of the secondary amino group of the compound (C) having a secondary amino group and a carboxyl group to at least a part of the ethylenically unsaturated group of the curable compound (B) having three or more ethylenically unsaturated groups A process for producing an amphoteric ionic curable compound (A) having an ethylenically unsaturated group, a tertiary amino group and a carboxyl group.