(METH)acrylate compound

Abstract

To provide a novel compound, a method for producing the same, or a use thereof.SOLUTION: The problem has been solved by providing a predetermined 2-[(1-methylalkyl)oxy]ethyl (meth)acrylate. The (meth)acrylate can be produced by an esterification reaction or a transesterification reaction using raw materials such as 2-[(1-methylalkyl)oxy]ethanol in the presence of a catalyst. The (meth)acrylate compound is considered to be usable as a component of a water-repellent and oil-repellent agent.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a certain (meth)acrylate compound. [Background technology]

[0002] The following Patent Document 1) introduces a water-dispersible fluorine-based water / oil repellent composition in which a fluorine-based water / oil repellent is dispersed in water using a surfactant consisting of an alkylene oxide adduct of a higher aliphatic secondary alcohol.

[0003] Patent Document 1 listed below introduces a water-dispersible fluorine-based water / oil repellent composition in which a fluorine-based water / oil repellent is dispersed in water using a surfactant consisting of an alkylene oxide adduct of a higher aliphatic secondary alcohol. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 6-33043 [Patent Document 2] Patent Publication No. 08-071429 [Patent Document 3] Patent Publication No. 2002-326974 [Patent Document 4] Patent Publication No. 2002-201463 Summary of the Invention [Problem to be solved by the invention]

[0005] It is well known that long-chain alkyl (meth)acrylates are used as components of water- and oil-repellent compositions. Long-chain alkyl acrylates have melting points: those with 12 alkyl carbon atoms are approximately 4°C, those with 14 carbon atoms are approximately 14°C, those with 16 carbon atoms are approximately 17°C, and those with 18 carbon atoms are approximately 28°C. Therefore, crystals precipitate depending on the ambient temperature. For example, when removing a product from a drum, it must be heated above its melting point. However, if heated above the melting point, this product contains polymerizable groups, which can initiate polymerization upon heating, causing heat inside the drum and potentially leading to an explosion. For this reason, handling is complicated, as the product must be slowly dissolved over time at temperatures 20°C to 30°C higher than its melting point. [Means for solving the problem]

[0006] As a result of extensive research, the present inventors have discovered a compound that has a structure similar to that of a long-chain alkyl (meth)acrylate, but whose melting point has been reduced to make it easier to handle. They have also discovered a novel compound and a method for producing the same. Based on this finding, the present inventors have completed the present invention. [Effects of the Invention]

[0007] We have provided a novel compound, its production method, use, etc. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a chart obtained by performing H-NMR on 2-[(1-methylundecyl)oxy]ethyl (meth)acrylate of Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0009] (definition) "(Meth)acrylic" means "acrylic or methacrylic". "(Meth)acrylate" means "acrylate or methacrylate". In this specification, "structural unit derived from a monomer" means a structural unit formed by polymerization of a monomer, and more specifically, means a structure formed by cleavage of a carbon-carbon double bond of a monomer.

[0010] (Example of the present invention) The preferred configurations of the present invention are described in the following items (1) to (8). (1) A (meth)acrylate represented by the following general formula (1):

[0011] [ka] (In the formula, R represents a hydrogen atom or a methyl group, and n represents 4 to 20.) (2) A method for producing a (meth)acrylate according to (1) above, which comprises esterifying an alcohol represented by the following general formula (2) with (meth)acrylic acid in the presence of an esterification catalyst, characterized in that a mixture of the alcohol compound and a polymerization inhibitor is subjected to a heat treatment as a pretreatment for the esterification:

[0012] [ka] (In the formula, n represents 4 to 20.) (3) A method for producing a (meth)acrylate according to (1) above, which comprises transesterifying an alcohol represented by the following general formula (2) with an alkyl (meth)acrylate in the presence of a transesterification catalyst, characterized in that a mixture of the alcohol compound and a polymerization inhibitor is subjected to a heat treatment as a pretreatment for the esterification.

[0013] [ka] (In the formula, n represents 4 to 20.) (4) The manufacturing method according to (2) or (3) above, characterized in that the heat treatment is carried out using at least one polymerization inhibitor selected from the group consisting of quinone-based polymerization inhibitors, alkylphenol-based polymerization inhibitors, amine-based polymerization inhibitors, N-oxyl-based polymerization inhibitors, and phenothiazine at a temperature in the range of 25°C to 100°C for 10 minutes to 120 hours. (5) The method according to (2) or (3) above, wherein the amount of the polymerization inhibitor is in the range of 10 ppm by weight to 10% by weight relative to 100% by weight of the alcohol represented by the general formula (2). (6) A composition comprising the (meth)acrylate described in (1) above. (7) A polymer containing structural units derived from the (meth)acrylate described in (1) above. (8) A water and oil repellent containing the polymer described in (7) above. (9) A method of applying the polymer described in (7) above onto a substrate, and then introducing crosslinks between the polymers to form a coating layer, thereby imparting water and oil repellency to the substrate.

[0014] <Compound of the Present Invention> The present invention relates to 2-[(1-methylalkyl)oxy]ethyl (meth)acrylate (hereinafter also referred to as "the (meth)acrylate of the present invention") or a method for producing the same, and the compound is represented by the following general formula (1).

[0015] [ka] In the above formula (1), R represents a hydrogen atom or a methyl group, and n represents 4 to 20. n is preferably 8-18, and more preferably 10-16.

[0016] <Composition> The composition of the present disclosure contains a compound represented by the above general formula (1). The composition of the present disclosure is not particularly limited, but preferably contains 0.1 parts by mass or more and 100 parts by mass or less of the compound represented by the above general formula (1) per 100 parts by mass of the composition of the present disclosure. The composition of the present disclosure may contain any compound. The composition of the present disclosure may contain a compound represented by the following general formula (2). The composition of the present disclosure is not particularly limited, but it is preferable that the content of the compound represented by the following general formula (2) is in the range of 0 to 10 parts by mass per 100 parts by mass of the compound represented by the above general formula (1).

[0017] [ka] In the above general formula (2), n represents a number of 4 to 20. In the above general formula (2), n is preferably 8 to 18, and more preferably 10 to 16. The composition of the present disclosure may contain a polymerization inhibitor. The composition of the present disclosure is not particularly limited, but preferably contains 0.00001 parts by mass or more and 5 parts by mass or less of the polymerization inhibitor per 100 parts by mass of the compound represented by the general formula (1). If the amount is within the above range, the storage stability of the composition of the present disclosure tends to be improved. The polymerization inhibitor is not particularly limited, but examples thereof include the compounds described below. The composition of the present disclosure may contain a polymerization initiator (sometimes referred to as the "polymerizable composition of the present disclosure"). Examples of the polymerization initiator include compounds that generate radicals when exposed to heat or light. Specific examples include the polymerization initiators described below. The composition of the present disclosure is not particularly limited and may be any, but preferably contains 0.01 parts by mass or more and 5 parts by mass or less of a polymerization initiator relative to 100 parts by mass of the compound represented by the general formula (1). If the amount is within the above range, the polymerizability of the composition of the present disclosure tends to be less delayed. The composition of the present disclosure may contain a radical polymerizable compound other than the compound represented by the general formula (1). Examples of the radical polymerizable compound include compounds that undergo radical polymerization by heat or light. Specific examples include the monomers described below. The composition of the present disclosure is not particularly limited, but it is preferable that the radical polymerizable compound other than the compound represented by general formula (1) is 0 mass % or more and 99 mass % or less relative to 100 mass parts of the radical polymerizable compound.

[0018] <Production method> The (meth)acrylates of the present invention can be prepared by esterification or transesterification, as described below.

[0019] <Esterification> The (meth)acrylate of the present invention can be obtained by esterifying 2-[(1-methylalkyl)oxy]ethanol represented by the following general formula (2) (the same applies hereinafter) with (meth)acrylic acid. The esterification may be carried out using a catalyst. For example, an acid catalyst such as hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, paratoluenesulfonic acid, a strongly acidic ion exchange resin, a heteropolyacid, or a metal oxide is generally used, and sulfuric acid, methanesulfonic acid, paratoluenesulfonic acid, or a strongly acidic ion exchange resin is preferred. Before the esterification, it is desirable to heat-treat 2-[(1-methylalkyl)oxy]ethanol together with a polymerization inhibitor as a pretreatment. The heat treatment can be carried out in a solvent (particularly an organic solvent). The solvent is preferably selected from the solvents used in the subsequent esterification or transesterification reaction. In the case of esterification, a solvent that forms an azeotrope with water and forms two liquid phases with water is preferred, and benzene, toluene, xylene, hexane, heptane, octane, or cyclohexane is more preferred. Furthermore, the heat treatment is preferably carried out at a temperature in the range of 25°C to 100°C for 10 minutes to 120 hours, more preferably at a temperature in the range of 40°C to 90°C for 30 minutes to 50 hours, and even more preferably at a temperature in the range of 50°C to 80°C for 60 minutes to 20 hours. Examples of the polymerization inhibitor include quinone-based polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone, and p-tert-butylcatechol; alkylphenol-based polymerization inhibitors such as 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,4,6-tri-tert-butylphenol; alkylated diphenylamine, N,N'-diphenyl-p-phenylenediamine, phenothiazine, 4-hydrogen methyl ester, N,N'-diphenyl-p-phenylenediamine, phenothiazine, and 4-hydroxybenzoyl methyl ester. amine-based polymerization inhibitors such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, and 1-hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine; and N-oxyl-based polymerization inhibitors such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl. Among these, at least one selected from hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol, phenothiazine, 2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl is preferred, and hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol, phenothiazine, 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl are more preferred. The amount of the polymerization inhibitor used is 10 ppm by weight to 10% by weight, preferably 100 ppm by weight to 5% by weight, more preferably 200 ppm by weight to 1% by weight, and even more preferably 500 ppm by weight to 0.5% by weight, relative to 100% by weight of 2-[(1-methylalkyl)oxy]ethanol.

[0020] 2-[(1-methylalkyl)oxy]ethanol, which is used as a raw material in the above-mentioned esterification or transesterification in the present invention, is an alcohol represented by the following general formula (2).

[0021] [ka] In the above formula (2), n represents 4 to 20. n is preferably 8 to 18, and more preferably 10 to 16. The alcohol represented by the above general formula (2) is not particularly limited, but specific examples thereof include 2-[(1-methylpentyl)oxy]ethanol, 2-[(1-methylhexyl)oxy]ethanol, 2-[(1-methylheptyl)oxy]ethanol, 2-[(1-methyloctyl)oxy]ethanol, 2-[(1-methylnonyl)oxy]ethanol, 2-[(1-methyldecyl)oxy]ethanol, 2-[(1-methylundecyl)oxy]ethanol, 2-[(1-methyldodecyl)oxy]ethanol, 2-[(1-methyltridecyl)oxy]ethanol, and 2-[(1-methyltetradecyl)oxy]ethanol. , 2-[(1-methylpentadecyl)oxy]ethanol, 2-[(1-methylhexadecyl)oxy]ethanol, 2-[(1-methylheptadecyl)oxy]ethanol, 2-[(1-methyloctadecyl)oxy]ethanol, 2-[(1-methylnonadecyl)oxy]ethanol, 2-[(1-methyleicosadecyl)oxy]ethanol, etc., and among these, 2-[(1-methylundecyl)oxy]ethanol, 2-[(1-methyltridecyl)oxy]ethanol, 2-[(1-methylpentadecyl)oxy]ethanol, and 2-[(1-methylheptadecyl)oxy]ethanol are preferred.

[0022] <Interesterification> The (meth)acrylate of the present invention is obtained by transesterifying 2-[(1-methylalkyl)oxy]ethanol with an alkyl (meth)acrylate. Examples of alkyl (meth)acrylates include linear, branched, or cyclic alkyl groups having 1 to 8 carbon atoms, and aromatic groups having 6 to 10 carbon atoms which may be substituted. Among these, alkyl groups having 1 to 4 carbon atoms are preferably used. Specific examples of alkyl (meth)acrylates include the following compounds: (meth)acrylic acid lower alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, and t-butyl (meth)acrylate. These can be used alone or in combination.

[0023] The above transesterification may be carried out using a catalyst, and the catalyst is not particularly limited, and specific examples thereof include oxides such as calcium oxide, barium oxide, lead oxide, zinc oxide, and zirconium oxide; hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, thallium hydroxide, tin hydroxide, lead hydroxide, and nickel hydroxide; halides such as lithium chloride, calcium chloride, tin chloride, lead chloride, zirconium chloride, and nickel chloride; carbonates such as potassium carbonate, rubidium carbonate, cesium carbonate, lead carbonate, zinc carbonate, and nickel carbonate; bicarbonates such as potassium bicarbonate, rubidium bicarbonate, and cesium bicarbonate; phosphates such as sodium phosphate, potassium phosphate, rubidium phosphate, lead phosphate, zinc phosphate, and nickel phosphate; nitrates such as lithium nitrate, calcium nitrate, lead nitrate, zinc nitrate, and nickel nitrate; carboxylates such as lithium acetate, calcium acetate, lead acetate, zinc acetate, and nickel acetate; sodium methoxide, sodium ethoxide, potassium methoxide, and potassium ethoxide. Examples of suitable alkoxy compounds include potassium t-butoxide, calcium methoxide, calcium ethoxide, barium methoxide, barium ethoxide, tetraethoxytitanium, tetrabutoxytitanium, and tetra(2-ethylhexanoxy)titanium; acetylacetonate complexes such as lithium acetylacetonate, zirconia acetylacetonate, zinc acetylacetonate, dibutoxytin acetylacetonate, and dibutoxytitanium acetylacetonate; quaternary ammonium alkoxides such as tetramethylammonium methoxide, tetramethylammonium t-butoxide, and trimethylbenzylammonium ethoxide; dialkyltin compounds such as dimethyltin oxide, methylbutyltin oxide, dibutyltin oxide, and dioctyltin oxide; distannoxanes such as bis(dibutyltin acetate)oxide and bis(dibutyltin laurate)oxide; and dialkyltin dicarboxylates such as dibutyltin diacetate and dibutyltin dilaurate. These may be used alone or in combination of two or more.Among these transesterification catalysts, potassium carbonate, cesium carbonate, tetraethoxytitanium, tetrabutoxytitanium, tetra(2-ethylhexanoxy)titanium, zirconia acetylacetonate, dibutyltin oxide, dioctyltin oxide, bis(dibutyltin acetate)oxide, bis(dibutyltin laurate)oxide, dibutyltin diacetate, and dibutyltin dilaurate are preferably used. The amount of the transesterification catalyst used is not particularly limited, but specifically, it is preferably 0.001 mol% or more, more preferably 0.005 mol% or more, even more preferably 0.01 mol% or more, particularly preferably 0.05 mol% or more, and preferably 20 mol% or less, more preferably 15 mol% or less, even more preferably 10 mol% or less, particularly preferably 5 mol% relative to the 2-[(1-methylalkyl)oxy]ethanol represented by general formula (2). The above range of the transesterification catalyst amount is preferred from the viewpoints of yield and economy.

[0024] When carrying out the above transesterification reaction, it is desirable to heat-treat 2-[(1-methylalkyl)oxy]ethanol together with a polymerization inhibitor as a pretreatment. The heat treatment can be carried out in a solvent (especially an organic solvent). The solvent is preferably one that forms an azeotrope with the by-produced alcohol and forms two phases with the by-produced alcohol in the liquid phase, and more preferably hexane, heptane, octane, cyclohexane, etc. Furthermore, the heat treatment is preferably carried out at a temperature in the range of 25°C to 100°C for 10 minutes to 120 hours, more preferably at a temperature in the range of 40°C to 90°C for 30 minutes to 50 hours, and even more preferably at a temperature in the range of 50°C to 80°C for 60 minutes to 20 hours. Examples of the polymerization inhibitor include quinone-based polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone, and p-tert-butylcatechol; alkylphenol-based polymerization inhibitors such as 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,4,6-tri-tert-butylphenol; alkylated diphenylamine, N,N'-diphenyl-p-phenylenediamine, phenothiazine, 4-hydrogen methyl ester, N,N'-diphenyl-p-phenylenediamine, phenothiazine, and 4-hydroxybenzoyl methyl ester. amine-based polymerization inhibitors such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, and 1-hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine; and N-oxyl-based polymerization inhibitors such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl. Among these, at least one selected from hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol, phenothiazine, 2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl is preferred, and hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol, phenothiazine, 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl are more preferred. The amount of the polymerization inhibitor used is 10 ppm by weight to 10% by weight, preferably 100 ppm by weight to 5% by weight, more preferably 200 ppm by weight to 1% by weight, and even more preferably 500 ppm by weight to 0.5% by weight, relative to 100% by weight of 2-[(1-methylalkyl)oxy]ethanol.

[0025] <Polymer> Since the (meth)acrylate of the present invention has a carbon-carbon double bond, it can be used as a monomer to obtain a polymer. The polymer may be composed of structural units derived from the (meth)acrylate of the present invention, or may contain other structural units. For example, the polymer may contain structural units derived from the (meth)acrylate of the present invention in an amount of 1 to 100 mol %, preferably 10 to 100 mol %, more preferably 20 to 100 mol %, and even more preferably 25 to 100 mol %, based on the total structural units. Copolymerizable monomers include alkyl acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, and octadecyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethylene glycol (meth)acrylate, and methoxydiethylene glycol (meth)acrylate. alkyl polyoxyalkyl (meth)acrylates such as methoxypropylene glycol (meth)acrylate, ethoxypropylene glycol (meth)acrylate, and methoxydipropylene glycol (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; carboxyl group-containing monomers such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid; glycidyl (meth)acrylate; glycidyl group-containing compounds such as acrylate, aminoacrylates such as 2-(dimethylamino)ethyl (meth)acrylate and 2-(diethylamino)ethyl (meth)acrylate, ring-containing (meth)acrylates such as phenoxyethyl (meth)acrylate and isobornyl (meth)acrylate, styrene, α-methylstyrene, vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, One or more of the following can be used: silicon-containing monomers such as 3-methacryloxypropylmethyldiethoxysilane and 3-methacryloxypropyltriethoxysilane; vinyl chloride; (meth)acrylates having an Rf group (a group in which two or more hydrogen atoms of an alkyl group have been substituted with fluorine atoms) (the Rf group may contain a halogen atom other than a fluorine atom. The other halogen atom is preferably a chlorine atom. Furthermore, an ethereal oxygen atom or a thioethereal sulfur atom may be inserted between the carbon-carbon bonds in the Rf group).In addition to the above, other copolymerizable monomers that can be used include polyether aliphatic urethane acrylate, polycarbonate urethane acrylate, epoxy (meth)acrylate oligomer, polyester (meth)acrylate oligomer, isobornyl (meth)acrylate, ethoxylated trimethylolpropane triacrylate, and tricyclodecane dimethanol diacrylate.

[0026] The weight average molecular weight of the polymer in the present invention is preferably, for example, 1,000 to 10,000,000 as determined by static light scattering method.

[0027] The glass transition temperature of the polymer in the present invention is desirably, for example, −40° C. or higher. The upper limit of the glass transition temperature of the polymer of the present disclosure is desirably, for example, 80° C. or lower. The glass transition temperature is calculated using the glass transition temperature of a homopolymer of the monomer used in the monomer component constituting the polymer. Formula (I): 1 / Tg=Σ(Wm / Tgm) / 100 (I) [In the formula, Wm is the content (mass%) of monomer m in the monomer components constituting the polymer, and Tgm is the glass transition temperature (absolute temperature: K) of a homopolymer of monomer m].

[0028] <Polymerization method> The polymerization to obtain the polymer of the present invention is expected to be carried out in the presence of a polymerization initiator. Examples of the polymerization initiator include azo compounds such as azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(2-diaminopropane) hydrochloride, 4,4-azobis(4-cyanovaleric acid), and 2,2-azobis(2-methylpropionamidine); persulfates such as potassium persulfate; and peroxides such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide. The polymerization initiators may be used alone or in combination of two or more.

[0029] The amount of the polymerization initiator used may be appropriately set depending on the type of polymerization initiator, etc., and is not particularly limited. For example, it may be 0.05 parts by mass or more, preferably 0.1 parts by mass or more, and may be, for example, 2 parts by mass or less, preferably 1 part by mass or less, relative to 100 parts by mass of the monomer component.

[0030] In the above polymerization reaction, an additive such as a chain transfer agent may be contained in the reaction system. Any suitable additive may be used as the additive. For example, mercaptoethanol, Additives such as thioglycolic acid, sodium disulfite, etc. may be added during the polymerization.

[0031] The polymerization reaction may be carried out, if necessary, in the presence of a reducing agent (e.g., sodium hydrogen sulfite), a decomposing agent for the polymerization initiator (e.g., a transition metal salt such as ferrous sulfate), a chain transfer agent [e.g., a compound having a thiol group (e.g., tert-dodecyl mercaptan)], a pH buffer, a chelating agent, etc.

[0032] <Application A> The compound of the present invention can be used, for example, as an ink, a paint, a pressure sensitive adhesive, a UV curable resin diluent, a water repellent, an oil repellent, etc., and is preferably used as a water repellent, an oil repellent. The water- and oil-repellent agent can be applied to a substrate. In this case, a polymer can be synthesized in advance using the compound of the present invention as a monomer, and then a water- and oil-repellent agent containing the polymer can be applied. In this case, functional groups that react with urethane resins, epoxy resins, etc., such as hydroxyl groups, carboxyl groups, and silanol groups, are added to the polymer chain, and crosslinking and curing are performed to form a coating layer that imparts water- and oil-repellent properties to the substrate.

[0033] <Application B> From the viewpoint of specific products, the compound of the present invention is expected to be used as an adhesive or sealing material for electronic components or semiconductor elements, a raw material for a constituent material of a film or prepreg, an ink for 3D printing, a quantum dot ink, an adhesive such as a UV-curable laminating adhesive or a UV-curable hot melt adhesive, a sealant, or the like. [Example]

[0034] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, parts and percentages in the examples are by weight. [Example]

[0035] <Direct esterification with acrylic acid> Into a four-neck flask equipped with a thermometer, a stirrer, a condenser, and a gas inlet tube, 139 g (0.60 mol) of 2-[(1-methylundecyl)oxy]ethanol, 100 g of toluene as an organic solvent, and 0.14 g of phenothiazine (1000 ppm by weight relative to the alcohol) as a polymerization inhibitor were heated at 80°C for 4 hours. To this liquid, 65.3 g (0.91 mol) of acrylic acid and 5.3 g of methanesulfonic acid as an acid catalyst were added, and esterification reaction was carried out by removing condensed water while refluxing toluene at 350 mmHg while blowing in 7% oxygen / nitrogen gas. The amount of condensation water generated was 10.8 g. The reaction solution was transferred to a separatory funnel and washed twice with 100 g of 4% aqueous sodium hydroxide solution, and then washed twice with 100 g of water. The upper organic layer was transferred to a four-necked flask equipped with a thermometer, stirrer, condenser, and gas inlet tube, and heated under reduced pressure while blowing in 7% oxygen / nitrogen gas to distill off the toluene, yielding 159 g of the product (2-[(1-methylundecyl)oxy]ethyl acrylate). This product was stored in a refrigerator at -20°C for 70 hours, but no crystal precipitation was observed. The H-NMR of the product was measured, and the NMR chart is shown in Figure 1.

[0036] [Comparative Example 1] In contrast to the production method described in Example 1, the esterification reaction was carried out by charging all the ingredients into a flask at once without the heat treatment at 80°C for 4 hours. After about 1 hour, the production of a polymer of acrylic acid was observed. [Example]

[0037] <Transesterification reaction with methyl acrylate> A flask equipped with a stirrer, a thermometer, and a fractionating column was charged with 164 g (0.63 mol) of 2-[(1-methyltridecyl)oxy]ethanol and 0.16 g (1000 ppm by weight relative to the alcohol) of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl as a polymerization inhibitor, and the mixture was heated at 80°C for 4 hours with stirring. To this liquid, 273 g (3.17 mol) of methyl acrylate and 9.0 g of tetraisopropoxy titanate as a catalyst were charged and heated with stirring. After refluxing began, a mixture of methanol and methyl acrylate was removed from the fractionating column, while an equal amount of methyl acrylate was added to the removed liquid, and the reaction was carried out, yielding 189 g of the product (2-[(1-methyltridecyl)oxy]ethyl acrylate). Analysis of the reaction liquid revealed that the conversion of 2-[(1-methyltridecyl)oxy]ethanol to the product was 95 mol%.

[0038] Comparative Example 2 In contrast to the production method described in Example 2, the transesterification reaction was carried out by charging the entire mixture into a flask all at once without the heat treatment at 80°C for 4 hours. After about 1 hour, the reaction solution began to thicken, indicating the formation of a methyl acrylate polymer. [Example]

[0039] A four-neck flask equipped with a thermometer, a stirrer, a condenser, and a gas inlet tube was charged with 164 g (0.63 mol) of 2-[(1-methyltridecyl)oxy]ethanol, 100 g of toluene as an organic solvent, and 1.64 g of phenothiazine (1 ppm by weight relative to the alcohol) as a polymerization inhibitor, and the mixture was heated at 40°C for 80 hours with stirring. To this liquid, 68.2 g (0.95 mol) of acrylic acid and 5.5 g of methanesulfonic acid as an acid catalyst were added, and esterification reaction was carried out by removing condensed water while refluxing toluene at 350 mmHg while blowing in 7% oxygen / nitrogen gas. The amount of condensation water generated was 11 g. The reaction solution was transferred to a separatory funnel and washed twice with 100 g of 4% aqueous sodium hydroxide solution, and then washed twice with 100 g of water. The upper organic layer was transferred to a four-necked flask equipped with a thermometer, stirrer, condenser, and gas inlet tube, and heated under reduced pressure while blowing in 7% oxygen / nitrogen gas to distill off the toluene, yielding 190 g of the product (2-[(1-methyltridecyl)oxy]ethyl acrylate). This product was stored in a refrigerator at -10°C for 70 hours, but no crystal precipitation was observed.

[0040] It was demonstrated that the compounds of the present invention can be obtained by the production methods described in Examples 1 to 3 above.

Claims

1. A (meth)acrylate represented by the following general formula (1): 【Chemistry 1】 (wherein R represents a hydrogen atom or a methyl group, and n represents an integer of 4 to 20.)

2. 2. The method for producing a (meth)acrylate according to claim 1, which comprises esterifying an alcohol represented by the following general formula (2) with (meth)acrylic acid in the presence of an esterification catalyst, wherein a mixture of the alcohol compound and a polymerization inhibitor is subjected to a heat treatment as a pretreatment for the esterification: 【Chemistry 2】 (wherein n is 4 to 20.)

3. 2. The method for producing a (meth)acrylate according to claim 1, comprising transesterifying an alcohol represented by the following general formula (2) with an alkyl (meth)acrylate in the presence of a transesterification catalyst, wherein a mixture of the alcohol compound and a polymerization inhibitor is subjected to a heat treatment as a pretreatment for the esterification: 【Transformation 3】 (wherein n is 4 to 20.)

4. 4. The method according to claim 2, wherein the heat treatment is carried out using at least one polymerization inhibitor selected from the group consisting of a quinone-based polymerization inhibitor, an alkylphenol-based polymerization inhibitor, an amine-based polymerization inhibitor, an N-oxyl-based polymerization inhibitor, and a phenothiazine at a temperature in the range of 25°C to 100°C for 10 minutes to 120 hours.

5. 4. The method according to claim 2, wherein the amount of the polymerization inhibitor is in the range of 10 ppm by weight to 10% by weight based on 100% by weight of the alcohol represented by the general formula (2).

6. A composition comprising the (meth)acrylate of claim 1.

7. A polymer comprising structural units derived from the (meth)acrylate of claim 1.

8. A water and oil repellent agent comprising the polymer according to claim 7.

9. A method for imparting water and oil repellency to a substrate, comprising applying the polymer according to claim 7 onto the substrate and then introducing crosslinks between the polymers to form a coating layer.

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