JP5541902B2 - Photocurable low shrinkage monomer compound - Google Patents

Description

  The present invention relates to a photocurable monomer compound, and more particularly to a photocurable monomer compound in which volume shrinkage during polymerization is suppressed.

  Various (meth) acrylic monomers are known as photocurable monomers by taking advantage of the good transparency of the cured product. For example, ethylene glycol glycerol diacrylate, glycerol propylene oxide diacrylate, ethylene oxide-added trimethylolpropane diacrylate, propylene oxide-added trimethylolpropane diacrylate, pentaerythritol diacrylate, ethylene glycolated pentaerythritol diacrylate, and the like have been used. (See Patent Document 1)

  However, conventional photopolymerizable (meth) acrylic monomers undergo considerable volume shrinkage upon curing, which is a significant drawback depending on the application of the cured product. In recent years, electronic devices are becoming lighter and smaller, and flexible substrates are becoming lighter and thinner. Along with this, the effect of curing shrinkage of the resin composition to be overcoated is becoming more prominent. For this reason, the curing type overcoat agent cannot satisfy the required performance in terms of warpage due to curing shrinkage (see Patent Document 2).

JP2003-246818 Japanese Patent Application No. 2003-403958

  In the above background, an object of the present invention is to provide a (meth) acrylic monomer compound in which volume shrinkage occurring during photocuring is suppressed.

  As a result of the study for the above purpose, the present inventors surprisingly found that a novel (meth) acrylic monomer compound obtained by introducing an amide methylol structure portion into a (meth) acrylic monomer was subjected to photocuring. It has been found that the volume shrinkage of the cured product that occurs is greatly suppressed compared to the corresponding conventional (meth) acrylic monomers that do not introduce such a chemical structure. The present invention has been completed by further investigation based on the discovery.

That is, the present invention provides the following.
1. A (meth) acrylic monomer compound containing at least one amidomethylol structure moiety consisting of —CO—NH—CH ₂ —O— in the molecule.
2. The (meth) acrylic monomer compound according to 1 above, which has a carbon number in the range of 5 to 99.
3. The following formula (1),

[Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a plurality of carbon atoms each having two or more carbon atoms by inserting one or two or more oxygen atoms between adjacent carbon atoms. X ¹ represents a saturated hydrocarbon group having 1 to 30 carbon atoms, may represent an aromatic group having 6 to 25 carbon atoms, or a combination thereof, and X ¹ Represents a hydrogen atom, a hydroxyl group, a linear or branched alkyloxy group having 1 to 30 carbon atoms, a phenoxy group, a glycidyloxy group, an allyloxy group, or a vinyloxy group. The (meth) acrylic monomer compound as described in 1 or 2 above.
4). The following formula (2),

[Wherein R ¹ represents a hydrogen atom or a methyl group, Y represents an oxygen atom or —NH—, and R ³ represents that one or more oxygen atoms are inserted between adjacent carbon atoms. Or a saturated hydrocarbon group having 1 to 18 carbon atoms, an aromatic group having 6 to 25 carbon atoms, or two or more of these, which may be divided into a plurality of hydrocarbon group portions each consisting of two or more carbon atoms R ⁴ is divided into a plurality of hydrocarbon group parts each consisting of two or more carbon atoms by inserting one or more oxygen atoms between adjacent carbon atoms. Represents a saturated hydrocarbon group having 1 to 30 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof, and X ² is a hydrogen atom, a hydroxyl group, a straight chain having 1 to 30 carbon atoms. Chain or branched alkyloxy group, phenoxy group, grease Jiruokishi group, an allyloxy group, or vinyloxy group. The (meth) acrylic monomer compound as described in 1 or 2 above.
5. The following equation (3),

[Wherein R ¹ represents a hydrogen atom or a methyl group, Y represents an oxygen atom or —NH—, and R ⁵ represents that one or more oxygen atoms are inserted between adjacent carbon atoms. Or a saturated hydrocarbon group having 1 to 15 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or two of these, which may be divided into a plurality of hydrocarbon group portions each having two or more carbon atoms Composed of the above combination, R ⁶ is a single bond, or a plurality of two or more carbon atoms each formed by inserting one or two or more oxygen atoms between adjacent carbon atoms. Represents a saturated hydrocarbon group having 1 to 15 carbon atoms, an aromatic group having 6 to 25 carbon atoms, or a combination thereof, which may be divided into the hydrocarbon group portions of R ⁵ and R ⁶ , Any one of these atoms may be covalently bonded to form a ring. The (meth) acrylic monomer compound as described in 1 or 2 above.
6). The following equation (4),

[Wherein R ¹ represents a hydrogen atom or a methyl group, Y may be either an oxygen atom or —NH—, and the ring indicated by a broken line may be a condensed ring having 6 to 14 carbon atoms. Represents a family ring. The (meth) acrylic monomer compound as described in 1 or 2 above.

  The (meth) acrylic monomer compound having an amidomethylol structure portion of the present invention having the above-described configuration is significantly suppressed in volume shrinkage during photocuring as compared with a (meth) acrylic monomer compound having no such portion. There is an effect that. For this reason, when the monomer compound of the present invention is used in, for example, a UV curable ink, curling generated on the substrate due to shrinkage of the resin after printing can be suppressed as compared with the case of using a conventional (meth) acrylic monomer. Therefore, it is particularly suitable as a material for the production of such inks, and furthermore, resist materials and nanoimprint materials that require highly precise molding, and hologram memory materials that are complex and sophisticated optical recording media. Also ideal for.

In this specification, the term “(meth) acrylic acid” is a comprehensive term that does not distinguish between acrylic acid (H ₂ C═CH—COOH) and methacrylic acid (H ₂ C═CCH ₃ —COOH). Show. In addition, the term “(meth) acrylic group” comprehensively indicates both an acrylic group (H ₂ C═CH—CO—) and a methacrylic group (H ₂ C═CCH ₃ —CO—) without distinction. Further, the term “(meth) acrylic” comprehensively indicates a compound having an acrylic group or a methacrylic group (that is, an acrylic or methacrylic compound) without distinction.

  In the present specification, the “(meth) acrylic monomer compound” refers to a polymerizable (meth) acrylic acid derivative having an acrylic group or a methacrylic group.

The (meth) acrylic monomer compound of the present invention is a derivative obtained by substituting a hydrogen atom of a carboxyl group of (meth) acrylic acid, and an amide methylol structure moiety (—CO—NH—CH ₂ is contained in the substituent. The main feature is that it contains at least one -O-). The reason why the (meth) acrylic monomer compound of the present invention suppresses the volume shrinkage during photocuring compared to the conventional (meth) acrylic monomer having a large volume shrinkage during photopolymerization is completely elucidated. Not. However, after the photocuring of the monomer compound of the present invention containing an amide methylol structure portion, it was observed that the methylene and oxygen atoms in the amide methylol structure portion were cleaved along with the suppression of volume shrinkage. Therefore, the (meth) acrylic monomer compound having an amide methylol structure portion of the present invention, when photocured, coupled with polymerization of carbon-carbon double bonds derived from (meth) acrylic acid, between methylene and oxygen in the amide methylol structure portion. By cleaving, thus preventing free molecules generated independently of the polymer chain of the polymer from interfering with their proximity by intervening between adjacent polymer chains, or amide methylol structural moieties. In the case of a monomer compound having an included ring, the polymer chain itself of the polymer becomes bulky by opening the ring, so that the volume shrinkage of the system accompanying the polymerization is at least partially compensated. It is strongly suggested that is suppressed. This also indicates that two or more amide methylol structural moieties may be included per monomer compound molecule. At the same time, both the acrylic or methacrylic group and the amide methylol structure moiety are incorporated into the molecule as long as free molecules independent of the polymer chain are generated by irradiation with light used for photocuring or the ring that the monomer compound has opened. Regarding the points other than the inclusion, it indicates that the (meth) acrylic acid monomer compound of the present invention may have various appropriate structures.

  There is no clear upper limit to the molecular size of the (meth) acrylic monomer compound of the present invention, but since it is used for polymerization purposes, it may be inconvenient for some purposes to make it too large. obtain. Considering this, when looking at only the carbon number as an index, the (meth) acrylic monomer compound of the present invention is generally preferably in the range of 5 to 99 carbon atoms. This is because when the number of carbon atoms is less than 5, the stability of the monomer becomes low, and when the number of carbon atoms is 100 or more, the viscosity becomes very high. More preferably, the carbon number is in the range of 5 to 49.

In the above (meth) acrylic monomer compound, the amide methylol structure portion only needs to exist somewhere, and there is no particular limitation on the manner of introduction of the structure portion. Therefore, the introduction of the amide methylol structure can be carried out by appropriately introducing an appropriate group containing an amide methylol structure portion into the (meth) acrylic acid or (meth) acrylic acid ester in such a manner that the (meth) acrylic group can be retained. It can be carried out. For example, an amide methylol structure part can be introduced in a form incorporating a carbonyl group part of (meth) acrylic acid. More specifically, for example:
(i) An amide is formed by a carboxyl group possessed by (meth) acrylic acid and a compound having an NH ₂ —CH ₂ —O— group [so that it contains an amide bond with the carboxyl group of (meth) acrylic acid. Constitutes an amidomethylol structure), or
(ii) A side chain can be introduced by forming an ester bond or an amide bond using the carboxyl group of (meth) acrylic acid. For example, an amide methylol structure portion is provided in advance in such a side chain. ,
Thereby, the (meth) acrylic acid monomer compound which has an amide methylol structure part in a side chain can be obtained.

  (Meth) acrylic monomer compound of formula (1) of the present invention,

R ² is a hydrocarbon group which may be divided into a plurality of hydrocarbon group portions each consisting of two or more carbon atoms by inserting one or two or more oxygen atoms between adjacent carbon atoms. And the carbon number is preferably 1-30. This is because the viscosity increases when the number of carbon atoms exceeds 30. When each hydrocarbon group part is a saturated hydrocarbon group, the carbon number of R ² is more preferably 2 to 24, still more preferably 2 to 18, and each hydrocarbon group part is aromatic. When it is a group, the carbon number of R ² is more preferably 6 to 25, still more preferably 6 to 18, and particularly preferably 6 to 10 aromatic groups. R ² may be a combination of two or more of these. X ¹ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyloxy group having 1 to 30 carbon atoms, a phenoxy group, a glycidyloxy group, an allyloxy group, or a vinyloxy group.

Specific examples of R ² include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, etc. as hydrocarbon groups, and oxygen between adjacent carbons of the hydrocarbon group. As a structural portion formed by inserting an atom, —CH ₂ CH ₂ (0CH ₂ CH ₂ ) _n —, where n is an integer of 1 to 14, and —CH ₂ CH ₂ CH ₂ (0CH ₂ CH ₂ CH ₂ ) _m —, where m is an integer of 1 to 9, aromatic groups include phenylene, naphthylene, anthrylene, phenanthrylene, and each of these groups and structures Although it is a combination of any one of the portions and has 6 to 25 carbon atoms, it is not limited thereto. Of these, particularly preferred are ethylene, —CH ₂ CH ₂ (0CH ₂ CH ₂ ) _n —, where n is an integer of 1 to 8, phenylene, naphthylene, and anthrylene.

Further, particularly preferred specific examples of the X ¹ moiety are a hydrogen atom, a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group, a 1-decylpentyloxy group, a glycidyloxy group, and an allyloxy group. .

  (Meth) acrylic monomer compound of formula (2) of the present invention,

, Y may be either an oxygen atom or —NH—, and R ³ is a plurality of two or more carbon atoms each formed by inserting one or more oxygen atoms between adjacent carbon atoms. The hydrocarbon group may be divided into a hydrocarbon group, preferably a saturated hydrocarbon group having 1 to 18 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms, preferably 6 to 6 carbon atoms. 25, more preferably 6-18, particularly preferably 6-10 aromatic groups, or combinations thereof, wherein R ⁴ is one or more oxygen atoms The number of carbon atoms that may be divided into a plurality of hydrocarbon group portions each consisting of two or more carbon atoms by being inserted between adjacent carbon atoms is preferably 1-30, more preferably 2-18, and further Preferably 6 to 10 saturated hydrocarbons The group preferably has 6 to 20 carbon atoms, more preferably 6 to 18, more preferably 6 to 10 aromatic groups, or a combination thereof. X ² may be a hydrogen atom, a hydroxyl group, a linear or branched alkyloxy group having 1 to 30 carbon atoms, a phenoxy group, a glycidyloxy group, an allyloxy group, or a vinyloxy group.

Specific examples of R ³ include hydrocarbon groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetra Examples include decamethylene, pentadecamethylene, hexadecamethylene, heptacamethylene, octadecamethylene, and the like, and —CH ₂ CH ₂ (0CH _{2) is a} structural portion formed by inserting an oxygen atom between adjacent carbons of a hydrocarbon group. CH ₂ ) _n — and n is any integer from 1 to 8, and —CH ₂ CH ₂ CH ₂ (0CH ₂ CH ₂ CH ₂ ) _m —, where m is 1 to 8. include those wherein Kano integer, and _{-CH 2 CH 2 CH 2 (0CH} 2 CH 2 CH 2) m - is a by m is 1-8 Any of these integers can be used, and examples of the aromatic group include phenylene, naphthylene, anthrylene, and phenanthrylene, and combinations of any of these groups and structural parts, which have 6 to 25 carbon atoms. But are not limited to these. Of these, particularly preferred are ethylene, tetramethylene, hexamethylene, —CH ₂ CH ₂ (0CH ₂ CH ₂ ) _n —, where n is an integer from 1 to 8, and —CH ₂ CH ₂ CH ₂ (0CH ₂ CH ₂ CH ₂ ) _m — and m is an integer of 1 to 8, and aromatic groups include phenylene, naphthylene, anthrylene, and phenanthrylene. And combinations of any one of these groups and structural moieties, including but not limited to those having 6 to 25 carbon atoms.

Specific examples of R ⁴ include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, etc. as hydrocarbon groups, and oxygen between adjacent carbons of the hydrocarbon group. As a structural portion formed by inserting an atom, —CH ₂ CH ₂ (0CH ₂ CH ₂ ) _n —, where n is an integer of 1 to 14, and —CH ₂ CH ₂ CH ₂ (0CH ₂ CH ₂ CH ₂ ) _m —, where m is an integer of 1 to 9, aromatic groups include phenylene, naphthylene, anthrylene, phenanthrylene, and each of these groups and structures Although it is a combination of any one of the portions and has 6 to 25 carbon atoms, it is not limited thereto. Of these, particularly preferred are ethylene, —CH ₂ CH ₂ (0CH ₂ CH ₂ ) _n —, where n is any integer of 1 to 8, phenylene, naphthylene, and anthrylene.
Particularly preferred specific examples of X ² are hydrogen atom, hydroxyl group, methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, 1-decylpentyloxy group, glycidyloxy group and allyloxy group. It is not limited to.

  The (meth) acrylic monomer compound of the formula (3) of the present invention,

Y may be either an oxygen atom or —NH—, and R ⁵ is preferably a saturated hydrocarbon group having 1 to 15 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 4 carbon atoms. A structural part in which an oxygen atom is inserted between one or two or more adjacent carbon atoms among the carbon atoms constituting the saturated hydrocarbon group, preferably 6 to 25 carbon atoms, more preferably 6 to 18 carbon atoms , More preferably 6 to 10 aromatic groups, or a combination of two or more thereof, and R ⁶ is a single bond or preferably 1 to 12 carbon atoms, more preferably 1 to 8, more preferably 1 to 4 saturated hydrocarbon groups or a structure in which an oxygen atom is inserted between one set or two or more adjacent carbon atoms among the carbon atoms constituting the saturated hydrocarbon group Part, carbon number is preferably 6 ~ 25, more preferably 6 to 18, more preferably 6 to 10 aromatic groups, or a combination thereof. R ⁵ and R ⁶ may be covalently bonded between any one of those atoms (between carbon-carbon or carbon-hydrogen, etc.) to form a ring.

Specific examples of R ⁵ include, but are not limited to, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene. Of these, methylene, ethylene, propylene and butylene are particularly preferred.

Specific examples of R ⁶ include a single bond and a hydrocarbon group such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, undecamethylene, dodecamethylene, and the like. As a structural part in which an oxygen atom is inserted between adjacent carbons of a hydrocarbon group, —CH ₂ CH ₂ (0CH ₂ CH ₂ ) _n —, wherein n is an integer of 1 to 5, and —CH ₂ CH ₂ CH ₂ (0CH ₂ CH ₂ CH ₂ ) _m —, where m is any integer of 1 to 3, and aromatic groups include phenylene, naphthylene, anthrylene, and phenanthrylene. And combinations of any one of these groups and structural parts, and those having 6 to 25 carbon atoms. Not.

  The (meth) acrylic monomer compound of the formula (4) of the present invention,

Y may be either an oxygen atom or —NH—, and the aromatic ring which may be a condensed ring having 6 to 14 carbon atoms indicated by a broken line includes a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. For example, but not limited to. Of these, a benzene ring and a naphthalene ring are particularly preferred. Moreover, the bonding position of the (meth) acrylic side chain in the aromatic ring is not limited.

Specific examples of the compound of the above formula (4) include the following.

[Outline of Synthesis Method of the Present Invention]
The outline of a general synthesis method of the monomer compound of the present invention is shown below.
(A) Synthesis of compound of formula (1)

  The ether compound represented by the formula (1) can be synthesized by dehydration reaction of an N-hydroxymethyl (meth) acrylamide derivative and an alcohol or polyoxyalkylene glycol monoether compound in the presence of an acid catalyst. Examples of the acid catalyst include catalysts that promote etherification, such as inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid and oxalic acid. The reaction between the alcohol or polyoxyalkylene glycol monoether compound and the N-hydroxymethyl (meth) acrylamide derivative can be carried out in the absence of a solvent. It becomes easy to adjust the temperature. Solvents include aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl isobutyl ketone, halogenated hydrocarbons such as dichloromethane and dichloroethane, tetrahydrofuran, 1,4-dioxane, and the like. Aprotic organic solvents such as ether, acetonitrile, nitrobenzene, nitromethane, and the like. Of these, aromatic hydrocarbons such as toluene and esters such as ethyl acetate can be preferably used. The reaction temperature is preferably about 30 to 110 ° C., although it depends on the raw material alcohol or polyoxyalkylene glycol monoether compound and the type of acid catalyst. The pH of the reaction solution is preferably 3 to 7 from the viewpoint of reaction rate and raw material stability. Although the reaction time is not particularly limited, for example, in the liquid chromatography <LC> chart, the end point of the reaction is that the area ratio of the target compound in the reaction mixture is 10% or more, The point at which the area ratio and the change disappear is regarded as the end point of the reaction. After completion of the reaction, the solvent is distilled off under reduced pressure and concentrated, and then the precipitated (meth) acrylic monomer represented by the formula (1) can be isolated by filtering off the precipitated solid. The crude product of (meth) acrylic monomer isolated from the reaction solution is preferably washed with an aromatic hydrocarbon such as benzene, toluene or xylene, or an aliphatic hydrocarbon solvent such as hexane, heptane or octane. For example, the reaction product can be dissolved in a solvent, filtered, and the resulting filtrate can be concentrated to wash the crude product. In the present invention, the <meth> acrylic monomer obtained by synthesis is preferably subjected to a purification step for further purification by column chromatography. As a developing solvent for column chromatography, for example, it is preferable to use a hydrocarbon solvent, then use a mixed solution of the hydrocarbon solvent and an ester solvent, and further use a single solvent of the ester solvent. Here, examples of the hydrocarbon solvent include hexane, cyclohexane, heptane, octane, benzene, toluene, xylene and the like. Examples of ester solvents include ethyl acetate and butyl acetate. The volume ratio of the hydrocarbon-based solvent and the ester-based solvent in the mixed solution is appropriately selected in consideration of a material that easily isolates and elutes the target product.

(B) Synthesis of compound of formula (2)

  An amide (meth) acrylic monomer can be obtained by reacting an amide derivative with a (meth) acrylic acid halide. Specific examples of (meth) acrylic acid halides include (meth) acrylic acid chloride, (meth) acrylic acid bromide, (meth) acrylic acid iodide, among these, from the viewpoint of reactivity and cost. , (Meth) acrylic acid chloride is preferred. The reaction between the amide derivative and the (meth) acrylic acid halide is preferably performed in a solvent in the presence of an organic base catalyst. Specifically, for example, after mixing an amide derivative, an organic base catalyst, and a solvent, adjusting the temperature of the mixture to an appropriate reaction temperature, stirring while dropping (meth) acrylic acid halide. Can do. Examples of the organic base catalyst include triethylamine, tributylamine, tripentylamine, N, N-dimethylaniline, N, N-diethylaniline, pyridine, quinoline, and the like, among which triethylamine is preferable. Solvents include aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl isobutyl ketone, alcohols such as methanol, ethanol, propanol and butanol, and halogenations such as dichloromethane and dichloroethane. Examples include hydrocarbons, tetrahydrofuran, ethers such as 1,4-dioxane, aprotic organic solvents such as acetonitrile, nitrobenzene, and nitromethane. The reaction temperature is preferably from 0 to 50 ° C, more preferably from 5 to 20 ° C, from the viewpoint of reaction efficiency. Further, the pressure in the reaction system is not particularly limited, and may be normal pressure. Although reaction time is not specifically limited, It is preferable to carry out until the time when the production rate of the amide (meth) acrylic monomer produced by the reaction between the amide derivative and (meth) acrylic acid halide does not change. The production rate of amide (meth) acrylic monomer can be confirmed by liquid chromatography. After completion of the reaction, for example, the amide (meth) acrylic monomer can be isolated from the obtained reaction solution by a separation operation such as extraction or concentration.

  The N-hydroxymethyl (meth) acrylamide derivative is obtained, for example, by reacting paraformaldehyde and the above amide (meth) acrylic monomer in the presence of a methylolation catalyst. Examples of the methylolation catalyst include organic amine compounds such as pyridine, triethylamine, dioctylmethylamine, triethanolamine, and triisopropanolamine. The reaction is preferably performed in a solvent. Solvents include aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl isobutyl ketone, alcohols such as methanol, ethanol, propanol and butanol, and halogenations such as dichloromethane and dichloroethane. Examples include hydrocarbons, tetrahydrofuran, ethers such as 1,4-dioxane, aprotic organic solvents such as acetonitrile, nitrobenzene, and nitromethane. Among these, alcohols with high solubility of raw materials are preferable. The reaction between the amide <meth> acrylic monomer and paraformaldehyde can be performed, for example, by mixing an amide <meth> acrylic monomer, paraformaldehyde, a methylolation catalyst, and, if necessary, a solvent with stirring. The reaction temperature is preferably 0 to 90 ° C, more preferably 10 to 60 ° C, from the viewpoint of improving the reaction rate and suppressing the formation of by-products. Further, the pressure in the reaction system is not particularly limited, and may be normal pressure. The pH of the reaction solution is preferably 7 to 12 from the viewpoint of improving the reaction rate. The reaction time is not particularly limited, but it is preferable to carry out the reaction until the conversion rate of the N-hydroxymethylamide derivative reaches 20% or more. After completion of the reaction, a solid having a low content of the target compound is appropriately removed from the obtained reaction solution, and then the solvent is distilled off to obtain a mixture containing an N-hydroxymethylamide derivative as a main component. . In addition, an extremely small amount of methylolation catalyst may remain in the N-hydroxymethylamide derivative. Even when such a methylolation catalyst is present, the content thereof is extremely small, so that practically no serious trouble is caused, but a higher purity N-hydroxymethylamide derivative is used. In order to obtain the derivative, the derivative may be purified by simple distillation or column chromatography.

  The amide (meth) acrylate represented by the formula (2) can be synthesized by dehydration reaction of the above N-hydroxymethyl (meth) acrylamide derivative and an alcohol or polyoxyalkylene glycol monoether compound in the presence of an acid catalyst. Examples of the acid catalyst include catalysts that promote etherification of inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid and oxalic acid. The reaction between the alcohol or polyoxyalkylene glycol monoether compound and the N-hydroxymethylamide derivative can be carried out in the absence of a solvent, but the temperature can be adjusted during the reaction by using a solvent to make the system uniform. Becomes easier. Solvents include aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl isobutyl ketone, halogenated hydrocarbons such as dichloromethane and dichloroethane, tetrahydrofuran, 1,4-dioxane, and the like. Aprotic organic solvents such as ether, acetonitrile, nitrobenzene, nitromethane, and the like. Among them, the reaction temperature at which an aromatic hydrocarbon such as toluene and an ester such as ethyl acetate can be suitably used depends on the type of alcohol or polyoxyalkylene glycol monoether compound and acid catalyst as raw materials. About 30-110 degreeC is preferable. The pH of the reaction solution is preferably 3 to 7 from the viewpoint of reaction rate and raw material stability. The reaction time is not particularly limited, but the end point of the reaction is, for example, in the liquid chromatography (LC) chart, the area ratio of the target compound in the reaction mixture is 10% or more, The point at which the area ratio and the change disappear is regarded as the end point of the reaction. After completion of the reaction, the solvent is distilled off under reduced pressure and concentrated, and then the precipitated amide (meth) acrylate represented by the formula (2) can be isolated by filtering off the precipitated solid. The crude product of amide (meth) acrylate isolated from the reaction solution is preferably washed using an aromatic hydrocarbon such as benzene, toluene or xylene, or an aliphatic hydrocarbon solvent such as hexane, heptane or octane. . For example, the reaction product can be dissolved in a solvent, filtered, and the resulting filtrate can be concentrated to wash the crude product. In the present invention, it is preferable that the amide (meth) acrylic monomer obtained by synthesis is further subjected to a purification step for purification by column chromatography. As a developing solvent for column chromatography, for example, it is preferable to use a hydrocarbon solvent, then use a mixed solution of the hydrocarbon solvent and an ester solvent, and further use a single solvent of the ester solvent. Here, examples of the hydrocarbon solvent include hexane, cyclohexane, heptane, octane, benzene, toluene, xylene and the like. Examples of ester solvents include ethyl acetate and butyl acetate. The volume ratio of the hydrocarbon-based solvent and the ester-based solvent in the mixed solution is appropriately selected in consideration of a material that easily isolates and elutes the target product.

(C) Synthesis of compound of formula (3)

  First, N-hydroxymethylacrylamide and formula (5),

An alkenyl acrylic monomer can be obtained by dehydration reaction with an alcohol represented by the above in the presence of an acid catalyst. Specific examples of the alcohol represented by the formula (5) include allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 2-allylphenol, 1-phenyl- Examples include 3-buten-1-ol, 2-phenyl-4-penten-2-ol, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, and ethylene glycol monoallyl ether. Examples of the acid catalyst include catalysts that promote etherification of inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid and oxalic acid. Although the above reaction can be carried out without a solvent, the temperature inside the reaction can be easily adjusted by using a solvent and making the system uniform. Solvents include aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl isobutyl ketone, halogenated hydrocarbons such as dichloromethane and dichloroethane, tetrahydrofuran, 1,4-dioxane, and the like. Aprotic organic solvents such as ether, acetonitrile, nitrobenzene, nitromethane, and the like. Of these, aromatic hydrocarbons such as toluene and esters such as ethyl acetate can be preferably used. The reaction temperature is preferably about 30 to 110 ° C., although depending on the types of alcohol and acid catalyst as raw materials. The pH of the reaction solution is preferably 3 to 7 from the viewpoint of reaction rate and raw material stability. The reaction time is not particularly limited, but the end point of the reaction is, for example, in the liquid chromatography (LC) chart, the area ratio of the target compound in the reaction mixture is 10% or more, The point at which the area ratio and the change disappear is regarded as the end point of the reaction. After completion of the reaction, the solvent is distilled off under reduced pressure and concentrated, and then the precipitated alkenyl acrylic monomer can be isolated by filtering the precipitated solid. The crude product of the alkenyl acrylic monomer isolated from the reaction solution is preferably washed with an aromatic hydrocarbon such as benzene, toluene or xylene, or an aliphatic hydrocarbon solvent such as hexane, heptane or octane. For example, the reaction product can be dissolved in a solvent, filtered, and the resulting filtrate can be concentrated to wash the crude product. In the present invention, the alkenyl acrylic monomer obtained by the synthesis is preferably subjected to a purification step for further purification by column chromatography. As a developing solvent for column chromatography, for example, it is preferable to use a hydrocarbon solvent, then use a mixed solution of the hydrocarbon solvent and an ester solvent, and further use a single solvent of the ester solvent. Here, examples of the hydrocarbon solvent include hexane, cyclohexane, heptane, octane, benzene, toluene, xylene and the like. Examples of ester solvents include ethyl acetate and butyl acetate. The volume ratio of the hydrocarbon-based solvent and the ester-based solvent in the mixed solution is appropriately selected in consideration of a material that easily isolates and elutes the target product.

  By treating the alkenyl acrylic monomer obtained above with sodium borohydride and a cyclization catalyst in the presence of a solvent, a cyclic amide (meth) acryl monomer represented by the formula (3) can be obtained. Specific examples of the cyclization catalyst include palladium (II) acetate, palladium (II) chloride, bistriphenylphosphine palladium (II) dichloride, and the like. The reaction can be carried out without a solvent, but the temperature can be easily adjusted during the reaction by using a solvent and making the system uniform. Solvents include aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl isobutyl ketone, halogenated hydrocarbons such as dichloromethane and dichloroethane, tetrahydrofuran, 1,4-dioxane, and the like. Aprotic organic solvents such as ether, acetonitrile, nitrobenzene, nitromethane, and the like. Of these, aromatic hydrocarbons such as toluene and esters such as ethyl acetate can be preferably used. The reaction temperature is preferably about 5 to 25 ° C., although it depends on the raw material alkenyl acrylic monomer and the type of catalyst. The reaction time is not particularly limited, but the end point of the reaction is, for example, in the liquid chromatography (LC) chart, the area ratio of the target compound in the reaction mixture is 10% or more, The point at which the area ratio and the change disappear is regarded as the end point of the reaction. After completion of the reaction, the cyclic amide (meth) acrylic monomer produced by distilling off the solvent under reduced pressure can be obtained.

(D) Synthesis of compound of formula (4)

  An amide (meth) acrylate can be obtained by reacting an amide derivative with a (meth) acrylic acid halide. Specific examples of (meth) acrylic acid halides include (meth) acrylic acid chloride, (meth) acrylic acid bromide, (meth) acrylic acid iodide, among these, from the viewpoint of reactivity and cost. , (Meth) acrylic acid chloride is preferred. The reaction between the amide derivative and the (meth) acrylic acid halide is preferably performed in a solvent in the presence of an organic base catalyst. Specifically, for example, after mixing an amide derivative, an organic base catalyst, and a solvent, adjusting the temperature of the mixture to an appropriate reaction temperature, stirring while dropping (meth) acrylic acid halide. Can do. Examples of the organic base catalyst include triethylamine, tributylamine, tripentylamine, N, N-dimethylaniline, N, N-diethylaniline, pyridine, quinoline, and the like, among which triethylamine is preferable. Solvents include aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl isobutyl ketone, alcohols such as methanol, ethanol, propanol and butanol, and halogenations such as dichloromethane and dichloroethane. Examples include hydrocarbons, tetrahydrofuran, ethers such as 1,4-dioxane, aprotic organic solvents such as acetonitrile, nitrobenzene, and nitromethane. The reaction temperature is preferably from 0 to 50 ° C, more preferably from 5 to 20 ° C, from the viewpoint of reaction efficiency. Further, the pressure in the reaction system is not particularly limited, and may be normal pressure. Although reaction time is not specifically limited, It is preferable to carry out until the time when the production rate of the amide (meth) acrylate derivative produced by the reaction of the amide derivative and (meth) acrylic acid halide does not change. The production rate of the amide (meth) acrylate derivative can be confirmed by liquid chromatography. After completion of the reaction, for example, the amide (meth) acrylate derivative can be isolated from the obtained reaction solution by a separation operation such as extraction or concentration.

  The N-hydroxymethylamide (meth) acrylate derivative can be obtained, for example, by reacting paraformaldehyde with the above amide (meth) acrylate derivative in the presence of a methylolation catalyst. Examples of the methylolation catalyst include organic amine compounds such as pyridine, triethylamine, dioctylmethylamine, triethanolamine, and triisopropanolamine. The reaction is preferably performed in a solvent. Solvents include aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl isobutyl ketone, alcohols such as methanol, ethanol, propanol and butanol, and halogenations such as dichloromethane and dichloroethane. Examples include hydrocarbons, tetrahydrofuran, ethers such as 1,4-dioxane, aprotic organic solvents such as acetonitrile, nitrobenzene, and nitromethane. Among these, alcohols with high solubility of raw materials are preferable. The reaction of the amide (meth) acrylate derivative and paraformaldehyde can be performed by, for example, mixing an amide (meth) acrylate derivative, paraformaldehyde, a methylolation catalyst, and, if necessary, a solvent with stirring. The reaction temperature is preferably 0 to 90 ° C, more preferably 10 to 60 ° C, from the viewpoint of improving the reaction rate and suppressing the formation of by-products. Further, the pressure in the reaction system is not particularly limited, and may be normal pressure. The pH of the reaction solution is preferably 7 to 12 from the viewpoint of improving the reaction rate. Although reaction time is not specifically limited, It is preferable to carry out until the conversion rate of N-hydroxymethylamide (meth) acrylate derivative becomes 20% or more. After completion of the reaction, solids having a low content of the target compound are appropriately removed from the obtained reaction solution, and then the solvent is distilled off to mix mainly the N-hydroxymethylamide (meth) acrylate derivative. The body is obtained. An extremely small amount of methylolation catalyst may remain in the N-hydroxymethylamide (meth) acrylate derivative. Even when such a methylolation catalyst is present, its content is extremely small, so that there is no particular problem in practical use, but a higher purity N-hydroxymethylamide (metathelium) is present. ) In order to obtain an acrylate derivative, the derivative may be used after being purified by simple distillation or column chromatography.

  The amide (meth) acrylate represented by the formula (4) can be synthesized by dehydration reaction of the above N-hydroxymethylamide (meth) acrylate derivative in the presence of an acid catalyst. Examples of the acid catalyst include catalysts that promote etherification of inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid and oxalic acid. Although it can be carried out in the absence of a solvent, it is easy to adjust the temperature during the reaction by using a solvent and making the system uniform. Solvents include aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl isobutyl ketone, halogenated hydrocarbons such as dichloromethane and dichloroethane, tetrahydrofuran, 1,4-dioxane, and the like. Aprotic organic solvents such as ether, acetonitrile, nitrobenzene, nitromethane, and the like. Among them, the reaction temperature at which aromatic hydrocarbons such as toluene and esters such as ethyl acetate can be suitably used depends on the type of N-hydroxymethylamide (meth) acrylate derivative and acid catalyst as raw materials. 30 to 110 ° C. is preferable. The pH of the reaction solution is preferably 3 to 7 from the viewpoint of reaction rate and raw material stability. The reaction time is not particularly limited, but the end point of the reaction is, for example, in the liquid chromatography (LC) chart, the area ratio of the target compound in the reaction mixture is 10% or more, The point at which the area ratio and the change disappear is regarded as the end point of the reaction. After completion of the reaction, the solvent is distilled off under reduced pressure and concentrated, and then the precipitated amide (meth) acrylate represented by the formula (4) can be isolated by filtering off the precipitated solid. The crude product of amide (meth) acrylate isolated from the reaction solution is preferably washed using an aromatic hydrocarbon such as benzene, toluene or xylene, or an aliphatic hydrocarbon solvent such as hexane, heptane or octane. . For example, the reaction product can be dissolved in a solvent, filtered, and the resulting filtrate can be concentrated to wash the crude product. In the present invention, it is preferable that the amide (meth) acrylic monomer obtained by synthesis is further subjected to a purification step for purification by column chromatography. As a developing solvent for column chromatography, for example, it is preferable to use a hydrocarbon solvent, then use a mixed solution of the hydrocarbon solvent and an ester solvent, and further use a single solvent of the ester solvent. Here, examples of the hydrocarbon solvent include hexane, cyclohexane, heptane, octane, benzene, toluene, xylene and the like. Examples of ester solvents include ethyl acetate and butyl acetate. The volume ratio of the hydrocarbon-based solvent and the ester-based solvent in the mixed solution is appropriately selected in consideration of a material that easily isolates and elutes the target product.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not intended to be limited to the examples.

Example 1 Synthesis of methoxypolyethylene glycol acrylamide (1)

In a 1 liter separable flask equipped with a stirrer, a thermometer, a condenser and an air introduction tube, 209 g (0.54 mol) of octaethylene glycol monomethyl ether (Uniox (registered trademark: NOF Corporation)) at room temperature, N-hydroxymethylacrylamide 50 g (0.50 mol) and 60 g of toluene were charged, and 0.2 g (1.6 mmol) of oxalic acid was added. The pH of the obtained solution was 3.3. The solution was heated under normal pressure so that the liquid temperature became 90 to 100 ° C., and then reacted for 21 hours. After completion of the reaction, the conversion rate of N-hydroxymethylacrylamide was 96.6 mol%. Subsequently, the obtained reaction liquid was heated under reduced pressure so that the liquid temperature became 50 to 60 ° C., and then toluene was distilled off over 2 hours and concentrated. The resulting concentrate was cooled to 30 ° C. After the solid precipitated, the solid was filtered off to obtain 247 g of a crude product. The crude product was purified by open column chromatography. Alumina was used as the stationary phase and developed with 600 mL of hexane single solution, then with 3000 mL of a mixed solution of hexane and ethyl acetate (hexane / ethyl acetate = 80/20 (volume ratio)), and further with 2000 mL of ethyl acetate single solution. To obtain 240 g (purity 97.5%) of the target acrylamide monomer (1). The structure of the acrylamide monomer (1) was identified by ¹ H-NMR measurement (300 MHz, CDCl ₃ ) using a JEOL-JNM-AL300-FTNMR spectrum meter (manufactured by JEOL Ltd.).
[Peak attribution]
3.38 ppm: Methyl group of polyethylene glycol methyl ether
3.55 ppm: Ethylene glycol group of polyethylene glycol methyl ether
4.79 to 4.86 ppm: methylol group
5.68 ppm, 6.08-6.24 ppm and 6.27-6.38 ppm: acryloyl group

[Comparative Example 1] Methoxypolyethylene glycol acrylate (1)
Methoxypolyethylene glycol acrylate (manufactured by Kyoeisha Co., Ltd., trade name: Light Acrylate 130A) was used.

[Example 2] Synthesis of isoalkoxy polyethylene glycol acrylamide (2)

In a 1-liter separable flask equipped with a stirrer, thermometer, condenser and air introduction tube, 389 g of polyoxyethylene (C12 to C14) ether (Fine Surf 290 (registered trademark: manufactured by Aoki Yushi)) at room temperature (0 .50 mol), 50 g (0.50 mol) of N-hydroxymethylacrylamide and 60 g of toluene were charged, and 5.3 g (42 mmol) of oxalic acid was added. The pH of the obtained solution was 4.0. Under normal pressure, the solution was heated to 90 to 100 ° C. and then reacted for 6 hours. After completion of the reaction, the conversion rate of N-hydroxymethylacrylamide was 100.0 mol%. Subsequently, the obtained reaction liquid was heated under reduced pressure so that the liquid temperature became 50 to 60 ° C., and then toluene was distilled off over 2 hours and concentrated. The resulting concentrate was cooled to 30 ° C. After the solid precipitated, the solid was filtered off to obtain 375 g of a crude product. The crude product was purified by open column chromatography. Alumina was used as the stationary phase and developed with 600 mL of hexane single solution, then with 3000 mL of a mixed solution of hexane and ethyl acetate (hexane / ethyl acetate = 80/20 (volume ratio)), and further with 2000 mL of ethyl acetate single solution. To obtain 347 g (purity 92.7%) of the target acrylamide monomer (1). The structure of the acrylamide monomer (2) was identified by ¹ H-NMR measurement (300 MHz, CDCl ₃ ) using a JEOL-JNM-AL300-FTNMR spectrum meter (manufactured by JEOL Ltd.).
[Peak attribution]
0.86-0.92 ppm: Methyl group at the isoalkoxy moiety
1.26 to 1.51 ppm: alkyl group at the isoalkoxy moiety
3.24 ppm: methine group at the isoalkoxy moiety
3.54 to 3.75 ppm: ethylene glycol group of polyethylene glycol methyl ether
4.84 to 4.86 ppm: methylol group
5.67 ppm, 6.15-6.28 ppm and 6.33-6.39 ppm: acryloyl group

[Comparative Example 2] Synthesis of isoalkoxy polyethylene glycol acrylate (3)

Polyoxyethylene (C12-C14) ether (Finesurf 290 (registered trademark: manufactured by Aoki Yushi)), tetrahydrofuran, in a 100 ml 5-neck flask equipped with a stirrer, thermometer, cooling tube and air introduction tube, tetrahydrofuran After adding 20.0 g and 2.7 g of triethylamine, the mixture was stirred and cooled until the temperature of the mixture became 20 ° C. or lower. The mixture was stirred while gradually dropping 2.3 g of acrylic acid chloride so that the temperature of the mixture did not exceed 20 ° C. The reaction was terminated when the production rate of the desired compound (3) produced in the mixed solution reached 99.0% or more. 20 g of purified water and 40 g of ethyl acetate were added to the resulting reaction solution, stirred, and allowed to stand to separate into an aqueous layer and an organic layer, and the organic layer was extracted. Further, extraction separation in which 40 g of ethyl acetate was added to the separated aqueous layer was performed twice. After mixing the organic layers obtained by extraction and separation three times in total, the organic layer was concentrated under reduced pressure conditions at 55 ° C. and 0.06 MPa using an evaporator to remove the ethyl acetate, thereby removing the crude product 22. 7 g was obtained. The crude product was purified by column chromatography using alumina as a filler. Using a mixed solvent of ethyl acetate and hexane (ethyl acetate / hexane (volume ratio) = 80/20) as a developing solvent, 18.9 g (purity: 98.9%) of the target compound (3) was obtained (yield). (Rate: 88.5%). The structure of the acrylic monomer (3) was identified by ¹ H-NMR measurement (300 MHz, CDCl ₃ ) using a JEOL-JNM-AL300-FTNMR spectrum meter (manufactured by JEOL Ltd.).
[Peak attribution]
0.96 ppm: Methyl group at the isoalkoxy moiety
1.29 to 1.42 ppm: alkyl group at the isoalkoxy moiety
3.22 ppm: Methine group at the isoalkoxy moiety
3.54 to 4.32 ppm: Ethylene glycol group of polyethylene glycol methyl ether
5.80 ppm, 6.05 ppm and 6.43 ppm: acryloyl group

Example 3 Synthesis of N- (2-phenoxy-ethoxymethyl) -acrylamide (E4)

A 300 ml separable flask equipped with a stirrer, thermometer, condenser and air introduction tube was charged with 54.7 g of ethylene glycol monophenyl ether, 40.0 g of N-hydroxymethylacrylamide and 48 g of toluene at room temperature, and oxalic acid. 0.6 g was added. The pH of the obtained solution was 4.0. Under normal pressure, the solution was heated to 90 to 100 ° C. and then reacted for 6 hours. After completion of the reaction, the conversion rate of N-hydroxymethylacrylamide was 98.2%. Subsequently, the obtained reaction liquid was heated under reduced pressure so that the liquid temperature became 50 to 60 ° C., and then toluene was distilled off over 2 hours and concentrated. The resulting concentrate was cooled to 30 ° C. After the solid precipitated, the solid was filtered off to obtain 99.5 g of a crude product. The crude product was purified by open column chromatography. Alumina was used as the stationary phase and developed with 600 mL of hexane single solution, then with 3000 mL of a mixed solution of hexane and ethyl acetate (hexane / ethyl acetate = 80/20 (volume ratio)), and further with 2000 mL of ethyl acetate single solution. To obtain 97.2 g (purity 95.4%) of the target acrylamide monomer (4). The structure of the acrylamide monomer (4) was identified by ¹ H-NMR measurement (300 MHz, CDCl ₃ ) using a JEOL-JNM-AL300-FTNMR spectrum meter (manufactured by JEOL Ltd.).
[Peak attribution]
3.89 to 3.94 ppm: Ethylene group of phenoxyethylene site
4.07 to 4.12 ppm: Ethylene group of phenoxyethylene site
4.93 ppm: methylol group
5.72 ppm, 6.12 to 6.18 ppm and 6.22 to 6.38 ppm: acryloyl group
6.65 ppm: Amide group
6.88-7.32 ppm: Phenyl group

[Comparative Example 3] Phenoxyethyl acrylate (1)
Phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Biscote # 192) was used.

Example 4 Synthesis of 4-acryloylamide-N- (2-propoxy-ethoxymethyl) -benzamide (E5)

The compound E5 was synthesized by the following steps.
(Step 1) Synthesis of 4-acryloylaminobenzamide (E5-1)

  Into a 300 ml five-necked flask equipped with a stirrer, thermometer, cooling pipe and air introduction pipe, 25.0 g of 4-aminobenzamide, 80.9 g of ethyl acetate and 19.5 g of triethylamine were added and stirred. It cooled until the temperature of a liquid mixture became 20 degrees C or less. The mixture was stirred while gradually dropping 16.6 g of acrylic acid chloride so that the temperature of the mixture did not exceed 20 ° C. The reaction was terminated when the production rate of the target compound (E5-1) produced in the mixed solution reached 95.0% or more. 20 g of purified water and 40 g of ethyl acetate were added to the resulting reaction solution, stirred, and allowed to stand to separate into an aqueous layer and an organic layer, and the organic layer was extracted. Further, extraction separation in which 40 g of ethyl acetate was added to the separated aqueous layer was performed twice. After mixing the organic layers obtained by extraction and separation three times in total, the organic layer was concentrated under reduced pressure at 55 ° C. and 0.06 MPa using an evaporator to remove the ethyl acetate, thereby removing the crude product (E5 -1) 34.2 g was obtained.

(Step 2) Synthesis of 4-acryloylamino-N-hydroxymethyl-benzamide (E5-2)

  A 100 ml flask equipped with a stirrer, thermometer, condenser and air inlet tube was charged with 35 g of methanol at room temperature, and 14.0 g of 4-acryloylaminobenzamide (E5-1) and paraformaldehyde (Sigma Aldrich) 6.6 g) was dissolved while gradually adding over 20 minutes while heating so that the liquid temperature became 30 to 35 ° C. Next, 28.5 g of triethylamine was added to adjust the pH to be in the range of 9-10. This was heated and held at 50 to 55 ° C. for 5 hours for aging. The obtained reaction liquid was subjected to suction filtration, and the solid matter was separated to obtain a filtrate. It was confirmed by NMR that the residue did not contain the desired 4-acryloylamino-N-hydroxymethyl-benzamide. The obtained filtrate was concentrated under reduced pressure at a liquid temperature of 40 ° C. over 2 hours to remove methanol and the like to obtain 22.1 g of 4-acryloylamino-N-hydroxymethyl-benzamide (E5-2). .

(Step 3) Synthesis of 4-acryloylamide-N- (2-propoxy-ethoxymethyl) -benzamide (E5) In a 50 ml flask equipped with a stirrer, thermometer, condenser and air introduction tube at room temperature, ethylene 4.7 g of glycol monopropyl ether, 10.0 g of 4-acryloylamino-N-hydroxymethyl-benzamide (E5-2) and 12 g of toluene were added, and 0.3 g of oxalic acid was added. The pH of the obtained solution was 4.0. The solution was heated under normal pressure so that the liquid temperature became 90 to 100 ° C., and then reacted for 21 hours. After completion of the reaction, the conversion rate of N-hydroxymethylacrylamide was 50.1%. Subsequently, the obtained reaction liquid was heated under reduced pressure so that the liquid temperature became 50 to 60 ° C., and then toluene was distilled off over 2 hours and concentrated. The resulting concentrate was cooled to 30 ° C. After the solid precipitated, the solid was filtered off to obtain 12.3 g of a crude product. The crude product was purified by open column chromatography. Alumina is used as the stationary phase, developed with a single hexane solution, then developed with a mixture of hexane and ethyl acetate (hexane / ethyl acetate = 80/20 (volume ratio)), and further developed with a single ethyl acetate solution. As a result, 4.2 g (purity 97.1%) of the target acrylamide monomer (E5) was obtained. The structure of the acrylamide monomer (E5) was identified by ¹ H-NMR measurement (300 MHz, CDCl ₃ ) using a JEOL-JNM-AL300-FTNMR spectrum meter (manufactured by JEOL Ltd.).
[Peak attribution]
0.96 ppm: methyl group at the propoxy site
1.50 ppm: methylene group at the propoxy site
3.37 to 3.54 ppm: Methylene group of propoxy moiety and ethoxy moiety
5.28 ppm: methylol group
5.72 ppm, 6.14-6.20 ppm and 6.22-6.38 ppm: acryloyl group
7.82 to 7.93 ppm: Phenyl group

[Comparative Example 4] Synthesis of 4-acryloylaminobenzoic acid 2-propoxy-ethyl ester (E6)

  The compound E6 was synthesized by the following steps.

(Step 1) Synthesis of 4-acryloylaminobenzoic acid (E6-1)

  To a 300 ml five-necked flask equipped with a stirrer, thermometer, cooling tube and air introduction tube, 25.0 g of 4-aminobenzoic acid, 150 g of ethyl acetate and 19.4 g of triethylamine were added, followed by stirring and mixing. It cooled until the temperature of the liquid became 20 degrees C or less. The mixture was stirred while gradually dropping 16.5 g of acrylic acid chloride so that the temperature of the mixture did not exceed 20 ° C. The reaction was terminated when the production rate of the target compound (E6-1) produced in the mixed solution reached 95.0% or more. 20 g of purified water and 40 g of ethyl acetate were added to the resulting reaction solution, stirred, and allowed to stand to separate into an aqueous layer and an organic layer, and the organic layer was extracted. Further, extraction separation in which 40 g of ethyl acetate was added to the separated aqueous layer was performed twice. After mixing the organic layers obtained by extraction and separation three times in total, the organic layer was concentrated under reduced pressure at 55 ° C. and 0.06 MPa using an evaporator to remove the ethyl acetate and remove the crude product (E6 -1) 35.3 g was obtained.

(Step 2) Synthesis of 4-acryloylaminobenzoic acid 2-propoxy-ethyl ester (E6) Ethylene glycol monopropyl ether 5 at room temperature in a 50 ml flask equipped with a stirrer, thermometer, condenser and air inlet tube .5 g, 10.0 g of 4-acryloylaminobenzoic acid (E6-1) and 12 g of toluene were added, and 0.3 g of oxalic acid was added. The pH of the obtained solution was 4.0. Under normal pressure, the solution was heated to 90 to 100 ° C. and then reacted for 6 hours. After completion of the reaction, the conversion of 4-acryloylaminobenzoic acid was 95.8%. Subsequently, the obtained reaction liquid was heated under reduced pressure so that the liquid temperature became 50 to 60 ° C., and then toluene was distilled off over 2 hours and concentrated. The resulting concentrate was cooled to 30 ° C. After the solid precipitated, the solid was filtered off to obtain 15.1 g of a crude product. The crude product was purified by open column chromatography. Alumina is used as the stationary phase, developed with a single hexane solution, then developed with a mixture of hexane and ethyl acetate (hexane / ethyl acetate = 80/20 (volume ratio)), and further developed with a single ethyl acetate solution. Thus, 5.1 g (purity 96.9%) of the target acrylamide monomer (E6) was obtained. The structure of the acrylamide monomer (E6) was identified by ¹ H-NMR measurement (300 MHz, CDCl ₃ ) using a JEOL-JNM-AL300-FTNMR spectrum meter (manufactured by JEOL Ltd.).
[Peak attribution]
0.96 ppm: methyl group at the propoxy site
1.50 ppm: methylene group at the propoxy site
3.37 to 4.42 ppm: Methylene group of propoxy moiety and ethoxy moiety
5.72 ppm, 6.14-6.20 ppm and 6.22-6.38 ppm: acryloyl group
7.75-7.95 ppm: Phenyl group

Example 5 Synthesis of 7-acryloyl-2H-1,3-benzoxazin-4 (3H) -one (E7)

The compound E7 was synthesized by the following steps.
(Step 1) Synthesis of 4-acryloyl-2-hydroxybenzamide (E7-1)

  Into a 1 liter 5-neck flask equipped with a stirrer, thermometer, cooling pipe and air introduction pipe, 100.0 g of 2,4-dihydroxybenzamide, 575.3 g of ethyl acetate and 69.4 g of triethylamine were added and stirred. The mixture was cooled until the temperature of the mixture became 20 ° C. or lower. The mixture was stirred while gradually dropping 59.1 g of acrylic acid chloride so that the temperature of the mixture did not exceed 20 ° C. The reaction was terminated when the production rate of the target compound (E7-1) produced in the mixed solution reached 95.0% or more. 20 g of purified water and 40 g of ethyl acetate were added to the resulting reaction solution, stirred, and allowed to stand to separate into an aqueous layer and an organic layer, and the organic layer was extracted. Further, extraction separation in which 40 g of ethyl acetate was added to the separated aqueous layer was performed twice. After mixing the organic layers obtained by extraction and separation three times in total, the organic layer was concentrated under reduced pressure at 55 ° C. and 0.06 MPa using an evaporator to remove the ethyl acetate, thereby removing the crude product (E7 -1) 59.5 g was obtained.

(Step 2) Synthesis of 4-acryloyl-2-hydroxy-N-hydroxymethylbenzamide (E7-2)

  A 200 ml flask equipped with a stirrer, thermometer, condenser and air inlet tube was charged with 50.0 g of methanol at room temperature, to which 50.0 g of 4-acryloyl-2-hydroxybenzamide (E7-1) and para 21.7 g of formaldehyde (manufactured by Sigma-Aldrich) was dissolved while gradually adding over 20 minutes while heating the solution to a temperature of 30 to 35 ° C. Next, 21.2 g of triethylamine was added to adjust the pH to be within the range of 9-10. This was heated and held at 50 to 55 ° C. for 5 hours for aging. The obtained reaction liquid was subjected to suction filtration, and the solid matter was separated to obtain a filtrate. The obtained filtrate was concentrated under reduced pressure at a liquid temperature of 40 ° C. over 2 hours to remove methanol and the like, and 17.2 g of 4-acryloyl-2-hydroxy-N-hydroxymethylbenzamide (E7-2). Obtained.

(Step 3) Synthesis of 7-acryloyl-2H-1,3-benzoxazin-4 (3H) -one (E7) In a 50 ml flask equipped with a stirrer, thermometer, condenser and air inlet tube at room temperature , 4-acryloyl-2-hydroxy-N-hydroxymethylbenzamide (E7-2) 15.0 g and toluene 12 g were added, and 1.1 g of oxalic acid was added. The pH of the obtained solution was 4.0. The mixture was heated under normal pressure so that the liquid temperature became 90 to 100 ° C., and then reacted for 36 hours. After completion of the reaction, the conversion of 4-acryloyl-2-hydroxy-N-hydroxymethylbenzamide was 88.6%. Subsequently, the obtained reaction liquid was heated under reduced pressure so that the liquid temperature became 50 to 60 ° C., and then toluene was distilled off over 2 hours and concentrated. The resulting concentrate was cooled to 30 ° C. After the solid precipitated, the solid was filtered off to obtain 14.1 g of a crude product. The crude product was purified by open column chromatography. Alumina is used as the stationary phase, developed with a single hexane solution, then developed with a mixture of hexane and ethyl acetate (hexane / ethyl acetate = 80/20 (volume ratio)), and further developed with a single ethyl acetate solution. As a result, 4.9 g (purity 97.3%) of the target acrylic monomer (E7) was obtained. The structure of the acrylic monomer (E7) was identified by ¹ H-NMR measurement (300 MHz, CDCl ₃ ) using a JEOL-JNM-AL300-FTNMR spectrum meter (manufactured by JEOL Ltd.).
[Peak attribution]
5.85 ppm: methylol moiety
5.71 ppm, 6.03 ppm and 6.26 ppm: acryloyl group
6.76 to 7.81 ppm: Phenyl group

[Comparative Example 5] Dicyclopentenyl acrylate (1)
Dicyclopentenyl acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-511A) was used.

[Evaluation of monomer compounds]
Each of the compounds of Examples and Comparative Examples was photocured according to the following procedure, and the volume shrinkage before and after photocuring was measured and compared with each other.

<Preparation of photocurable resin composition>
5.0 g of each monomer of the above Examples and Comparative Examples and 0.25 g of 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: IRGACURE184, manufactured by Ciba Japan Co., Ltd.) are mixed to obtain a photocurable resin composition. It was.

<Photocuring of curing resin composition>
0.3 g of the photocurable resin composition prepared in a Teflon (registered trademark) container having a diameter of 2 cm and a height of 1 mm was added. UV exposure (exposure amount: 20500 mJ) was performed with a metal halide lamp to obtain a transparent cured resin.

<Measurement of photocured volume shrinkage>
The photocurable resin composition was added to a 10 mL graduated cylinder, the weight was measured, and the liquid density was determined. The solid density of the transparent curable resin obtained by UV curing the photocurable resin composition was determined using an analytical balance (XS-204, manufactured by METTLER TOLEDO). The liquid density of the obtained photocurable resin composition and the solid density of the photocurable resin were measured, and the photocuring volume shrinkage was determined from the formula (1).

<Result>
The following table shows the volumetric shrinkage before and after photocuring in each of the examples and comparative examples.

  As shown in Table 1, the compounds of Examples 1 to 5 have a corresponding structure but have a volume shrinkage during photocuring as compared with the compounds of Comparative Examples 1 to 5 that do not have an amide methylol structure portion. Is significantly suppressed.

  The (meth) acrylic monomer compound of the present invention can be photocured, and at this time, volume shrinkage is suppressed as compared with the conventional (meth) acrylic monomer. Therefore, the present invention is suitable for applications in which volume shrinkage is required to be avoided as much as possible, particularly for UV curable inks, resist materials, nanoimprint materials, and hologram memory materials.

Claims (1)

The following formula (1),

[Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a saturated hydrocarbon group having 1 to 30 carbon atoms, or one or two or more oxygen atoms represent 4 to 30 carbon atoms. Represents a group divided into a plurality of hydrocarbon group parts each consisting of two or more carbon atoms by being inserted between adjacent carbon atoms of one saturated hydrocarbon group, or an aromatic having 6 to 25 carbon atoms X ¹ represents a hydrogen atom, a linear or branched alkyloxy group having 27 to 30 carbon atoms, a phenoxy group, a glycidyloxy group, an allyloxy group, or a vinyloxy group. was Table, provided that when R ² represents a 1-30 saturated hydrocarbon group having a carbon number, X ¹ is not represent hydrogen atoms. ] (Meth) acrylic-type monomer compound which is shown by this.