(METH)acrylate compound production method

Abstract

This (meth)acrylate compound production method includes a step (A1) for generating a (meth)acrylate compound (a) that includes an allophanate bond by reacting an iso(thio)cyanate compound containing two or more iso(thio)cyanate groups and a (meth)acrylate compound (b) containing one or more hydroxy groups and one or more (meth)acryloyl groups in the presence of a zinc compound at a content ratio at which the contained molar ratio of the iso(thio)cyanate groups in the iso(thio)cyanate compound to the hydroxy groups in the (meth)acrylate compound (b) is greater than 1.

Description

Method for producing (meth)acrylate compounds

[0001] The present disclosure relates to a method for producing a (meth)acrylate compound.

[0002] (Meth)acrylate compounds containing allophanate bonds are used, for example, as monomers in coating technology. For example, Patent Document 1 discloses a method for producing a (meth)acrylate compound containing an allophanate bond, in which a diisocyanate compound and a hydroxy(meth)acrylate compound are reacted in the presence of a tin catalyst, and then a tertiary amine and zinc octanoate are added to produce the (meth)acrylate compound containing an allophanate bond.

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. 2009-074070

[0004] However, in the method for producing a (meth)acrylate compound described in the above-mentioned Patent Document 1, the obtained product may gel.

[0005] An object of one aspect of the present disclosure is to provide a method for producing a (meth)acrylate compound that can suppress gelation of the product when producing a (meth)acrylate compound containing an allophanate bond.

[0006] Specific means for solving the above problems are as follows: <1> A method for producing a (meth)acrylate compound, comprising: a step (A1) of reacting an iso(thio)cyanate compound containing two or more iso(thio)cyanate groups with a (meth)acrylate compound (b) containing one or more hydroxy groups and one or more (meth)acryloyl groups in the presence of a zinc compound, at a charge ratio such that the charge molar ratio of the iso(thio)cyanate groups in the iso(thio)cyanate compound to the hydroxy groups in the (meth)acrylate compound (b) is greater than 1, thereby producing a (meth)acrylate compound (a) containing an allophanate bond.

[0007] <2> The method for producing a (meth)acrylate compound according to <1>, wherein the iso(thio)cyanate compound containing two or more iso(thio)cyanate groups is an iso(thio)cyanate compound containing two iso(thio)cyanate groups, and the (meth)acrylate compound (a) is a compound represented by the following formula (A):

[0008]

[0009] In formula (A), R １Ａａ , R １Ａｂ and R １Ａｃ are each independently a hydrogen atom or a methyl group, R ２Ａａ , R ２Ａｂ and R ２Ａｃ are each independently a residue obtained by removing one hydroxy group and one (meth)acryloyl group from the (meth)acrylate compound (b), and R ３Ａａ and R ３Ａｂ are each independently a residue obtained by removing two iso(thio)cyanate groups from the iso(thio)cyanate compound, and Z Ａ１ and Z Ａ２ are each independently a hydrogen atom, a group represented by the following formula (1a), a group represented by the following formula (1b), or a group represented by the following formula (1c).

[0010]

[0011] In formula (1a), R １Ａｄ is a hydrogen atom or a methyl group, R ２Ａｄ is a residue obtained by removing one hydroxy group and one (meth)acryloyl group from the (meth)acrylate compound (b), and R ３Ａｃ is a residue obtained by removing two iso(thio)cyanate groups from the iso(thio)cyanate compound, and * indicates a bonding position.

[0012]

[0013] In formula (1b), R １Ａｄ and R １Ａｅ are each independently a hydrogen atom or a methyl group, R ２Ａｄ and R ２Ａｅare each independently a residue obtained by removing one hydroxy group and one (meth)acryloyl group from the (meth)acrylate compound (b), and R ３Ａｃ and R ３Ａｄ are each independently a residue obtained by removing two iso(thio)cyanate groups from the iso(thio)cyanate compound, and * indicates a bonding position.

[0014]

[0015] In formula (1c), R １Ａｄ , R １Ａｅ and R １Ａｆ are each independently a hydrogen atom or a methyl group, R ２Ａｄ , R ２Ａｅ and R ２Ａｆ are each independently a residue obtained by removing one hydroxy group and one (meth)acryloyl group from the (meth)acrylate compound (b), and R ３Ａｃ , R ３Ａｄ and R ３Ａｅ are each independently a residue obtained by removing two iso(neo)nate groups from the iso(thio)cyanate compound, and * indicates a bonding position.

[0016] <3> The method for producing a (meth)acrylate compound according to <1> or <2>, wherein the zinc compound is a compound represented by the following formula (2):

[0017]

[0018] In formula (2), X １ and X ２ are each independently an oxygen atom, a sulfur atom, —C(═S)—S— or —C(═O)—O—; R ３ and R ４ are each independently a monovalent organic group having 2 to 40 carbon atoms, or R ３ and R ４ are bonded to each other to form a ring structure, and are organic groups having 2 to 40 carbon atoms.

[0019] <4> The method for producing a (meth)acrylate compound according to any one of <1> to <3>, wherein the charge molar ratio in the step (A1) is 1.1 to 7.0. <5> The method for producing a (meth)acrylate compound according to any one of <1> to <4>, wherein the charge amount of the zinc compound in the step (A1) is 0.01% by mass to 1% by mass with respect to the total charge amount of the zinc compound, the iso(thio)cyanate compound, and the (meth)acrylate compound (b). <6> The method for producing a (meth)acrylate compound according to any one of <1> to <5>, wherein the reaction in the step (A1) is carried out under conditions in which a tin compound is not present, or, if present, the amount of the tin compound relative to the total charge amount of the zinc compound, the iso(thio)cyanate compound, and the (meth)acrylate compound (b) is less than 0.01% by mass. <7> The method for producing a (meth)acrylate compound according to any one of <1> to <6>, wherein the reaction in the step (A1) is performed under conditions in which a tertiary amine compound is not present, or, if present, the amount of the tertiary amine compound relative to the total amount of the zinc compound, the iso(thio)cyanate compound, and the (meth)acrylate compound (b) is less than 0.01% by mass.

[0020] According to the present disclosure, there is provided a method for producing a (meth)acrylate compound that can suppress gelation of the product when producing a (meth)acrylate compound containing an allophanate bond.

[0021] In this disclosure, a numerical range indicated using "to" means a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In this disclosure, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved. In this disclosure, when there are multiple substances corresponding to each component, the amount of each component means the total amount of multiple substances unless otherwise specified. In this disclosure, "(meth)acryloyl group" means acryloyl group and methacryloyl group, "(meth)acrylate" means acrylate and methacrylate, and "iso(thio)cyanate" means isocyanate and isothiocyanate.

[0022] [Method for producing (meth)acrylate compound] The method for producing a (meth)acrylate compound of the present disclosure includes step (A1) of reacting an iso(thio)cyanate compound containing two or more iso(thio)cyanate groups (hereinafter also referred to as a "polyiso(thio)cyanate compound") with a (meth)acrylate compound (b) containing one or more hydroxy groups and one or more (meth)acryloyl groups in the presence of a zinc compound at a charge ratio such that the charge molar ratio of the iso(thio)cyanate groups in the iso(thio)cyanate compound to the hydroxy groups in the (meth)acrylate compound (b) is greater than 1 (i.e., the two are charged at this charge ratio and reacted), thereby producing a (meth)acrylate compound (a) containing an allophanate bond. The method for producing a (meth)acrylate compound of the present disclosure may include steps other than step (A1) as necessary.

[0023] In the present disclosure, an allophanate bond means a bond represented by the following formula (AL):

[0024]

[0025] In formula (AL), * indicates a bonding position.

[0026] In step (A1) of the present disclosure, the allophanate bond (i.e., the bond represented by formula (AL)) is formed by charging and reacting a polyiso(thio)cyanate compound and a (meth)acrylate compound (b) at a charge molar ratio (hereinafter also referred to as the "charge molar ratio [iso(thio)cyanate group / OH]") of the iso(thio)cyanate group in the polyiso(thio)cyanate compound to the hydroxy group (hereinafter also referred to as the OH group) in the (meth)acrylate compound (b) such that the charge molar ratio is greater than 1 (i.e., a charge ratio in which the iso(thio)cyanate group is in excess relative to the OH group). In this reaction, the iso(thio)cyanate group reacts with the OH group to form a urethane bond, and the excess iso(thio)cyanate group reacts with the formed urethane bond to form an allophanate bond. This produces a (meth)acrylate compound (a) containing an allophanate bond.

[0027] According to the present disclosure, gelation of the product can be suppressed during the production of an allophanate bond-containing (meth)acrylate compound (a). The gelation suppression effect is achieved by reacting an iso(thio)cyanate compound with a (meth)acrylate compound (b) in the presence of a zinc compound at a charge molar ratio [iso(thio)cyanate group / OH] of greater than 1.

[0028] In contrast to the method for producing a (meth)acrylate compound disclosed herein, the aforementioned Patent Document 1 involves reacting a diisocyanate compound with a hydroxy(meth)acrylate compound in the presence of a tin-based catalyst in the first reaction stage, and then adding a tertiary amine and zinc octanoate in the second reaction stage to produce a (meth)acrylate compound containing an allophanate bond. In this production method, in the first reaction stage, a reaction between an isocyanate group in the diisocyanate compound and a hydroxy group in the hydroxy(meth)acrylate compound proceeds in the presence of a tin-based catalyst. During this reaction, the molar ratio of the isocyanate group charged is greater than the molar ratio of the hydroxy group charged. Therefore, by the time zinc octanoate is added in the second reaction stage, no hydroxy groups remain. As a result, it is believed that the reaction does not involve "reacting a polyiso(thio)cyanate compound with a (meth)acrylate compound (b) in the presence of a zinc compound." For this reason, it is considered that Patent Document 1 does not provide the effect of inhibiting gelation that is achieved by the method for producing a (meth)acrylate compound of the present disclosure.

[0029] Preferred embodiments of the raw materials for producing the (meth)acrylate compound (a) are shown below.

[0030] <Polyiso(thio)cyanate compound> Among the raw materials for producing the (meth)acrylate compound (a), as an iso(thio)cyanate compound containing two or more iso(thio)cyanate groups (hereinafter also referred to as “polyiso(thio)cyanate compound”), for example, WO 2021 / 29406, WO 2021 / 157701, etc. Polyiso(thio)cyanate compounds described in publicly known documents can be appropriately used.

[0031] The polyiso(thio)cyanate compound is preferably a polyisocyanate compound, and more preferably pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, or phenylene diisocyanate. Xylylene diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, or bis(isocyanatomethyl)cyclohexane is more preferred.

[0032] <(Meth)acrylate Compound (b)> Among the raw materials for producing the (meth)acrylate compound (a), the (meth)acrylate compound (b) containing one or more hydroxy groups and one or more (meth)acryloyl groups is preferably a compound having one hydroxy group and n-1 (meth)acryloyloxy groups in an n-valent linking group. Here, n is an integer of 2 or more, preferably 2 to 4, more preferably 2 or 3, and even more preferably 2. The (meth)acrylate compound (b) may be used alone or in combination of two or more.

[0033] The n-valent linking group is not particularly limited, and is preferably, for example, a straight-chain or branched divalent acyclic hydrocarbon group having 1 to 50 carbon atoms, a divalent cyclic hydrocarbon group having 3 to 50 carbon atoms, or a divalent organic group having 1 to 50 carbon atoms and containing an oxygen atom in the main chain. The divalent cyclic hydrocarbon group having 3 to 50 carbon atoms may be composed only of a cyclic hydrocarbon portion, or may be a combination of a cyclic hydrocarbon portion and an acyclic hydrocarbon portion.

[0034] Here, examples of the divalent acyclic hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group, and examples of the divalent cyclic hydrocarbon group include a cycloalkylene group, a cycloalkenylene group, a cycloalkynylene group, and an arylene group. Furthermore, the divalent organic group containing an oxygen atom in the main chain preferably does not have a structure in which oxygen atoms are consecutively present in the main chain, such as "-O-O-", and the structure other than the oxygen atoms is preferably a hydrocarbon group. Furthermore, the hydrogen atoms in the acyclic hydrocarbon group and the hydrocarbon group may be substituted with a substituent such as a halogen atom (e.g., a chlorine atom or a bromine atom), an alkoxy group, a nitro group, a hydroxy group, or a carbonyl group, and the hydrogen atoms in the cyclic hydrocarbon group may be substituted with a substituent such as a halogen atom (e.g., a chlorine atom or a bromine atom), an alkoxy group, a nitro group, a hydroxy group, a carbonyl group, or an alkyl group.

[0035] As the divalent linear or branched acyclic hydrocarbon group having 1 to 50 carbon atoms, a divalent linear or branched acyclic hydrocarbon group having 1 to 20 carbon atoms is preferred, and a divalent linear or branched acyclic hydrocarbon group having 1 to 10 carbon atoms is more preferred.

[0036] As the divalent cyclic hydrocarbon group having 3 to 50 carbon atoms, a divalent cyclic hydrocarbon group having 6 to 30 carbon atoms is preferred, and a divalent cyclic hydrocarbon group having 10 to 25 carbon atoms is more preferred.

[0037] The divalent organic group having 1 to 50 carbon atoms and containing an oxygen atom in the main chain is preferably an oxyalkylene group having 1 to 50 carbon atoms, more preferably an oxyalkylene group having 2 to 30 carbon atoms.

[0038] The (meth)acrylate compound (b) is particularly preferably a (meth)acrylate compound containing one hydroxy group and one (meth)acryloyl group.

[0039] The (meth)acrylate compound (b) is not particularly limited, and examples thereof include 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl acrylate (HPA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl methacrylate (HPMA), 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate (4HBA), 2-hydroxy-3-phenoxypropyl acrylate, and 1,4-cyclohexanedimethanol monoacrylate.

[0040] The (meth)acrylate compound (b) preferably contains at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate (4HBA), 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 1,4-cyclohexanedimethanol mono(meth)acrylate.

[0041] <Zinc Compound> In step (A1), a polyiso(thio)cyanate compound is reacted with a (meth)acrylate compound (b) in the presence of a zinc compound. The zinc compound can function as a catalyst for the reaction in step (A1) (i.e., the reaction between the polyiso(thio)cyanate compound and the (meth)acrylate compound (b)). The zinc compound used in step (A1) may be one type or two or more types.

[0042] The zinc compound may be any compound containing at least one zinc atom. The zinc compound preferably further contains at least one of a sulfur atom and an oxygen atom. The zinc compound containing at least one of a sulfur atom and an oxygen atom is preferably at least one of a dithiocarbamate catalyst containing a zinc atom and a zinc compound containing a zinc atom and a ring structure.

[0043] The dithiocarbamate catalyst containing a zinc atom is preferably a zinc dithiocarbamate compound. The zinc compound containing a zinc atom and a ring structure is preferably a zinc compound containing a zinc atom and an aromatic ring or a heterocyclic ring, and more preferably a zinc compound containing a bisthiozinc skeleton (—S—Zn—S—) or a bisoxyzinc skeleton (—O—Zn—O—) and an aromatic ring or a heterocyclic ring.

[0044] The zinc compound is preferably a compound represented by the following formula (2).

[0045]

[0046] In formula (2), X １ and X ２ are each independently an oxygen atom, a sulfur atom, —C(═S)—S— or —C(═O)—O—; R ３ and R ４ are each independently a monovalent organic group having 2 to 40 carbon atoms, or R ３ and R ４ are bonded to each other to form a ring structure, and are organic groups having 2 to 40 carbon atoms.

[0047] Zn in formula (2) is R ３ or R ４ The bond between Zn and X1 and the bond between Zn and X2 may each be a covalent bond, an ionic bond, or a coordinate bond.

[0048] Specific examples of the zinc compound (e.g., a compound represented by formula (2)) in the present disclosure include the following compounds (Z-1) to (Z-14), but the zinc compound in the present disclosure is not limited to the following compounds.

[0049]

[0050] The amount of the zinc compound charged in step (A1) is preferably 0.01% by mass to 1% by mass, more preferably 0.03% by mass to 0.7% by mass, and even more preferably 0.05% by mass to 0.5% by mass, based on the total amount of the zinc compound, polyiso(thio)cyanate compound, and (meth)acrylate compound (b).

[0051] In step (A1), a catalyst other than a zinc compound (hereinafter also referred to as "other catalyst") may or may not be used as the catalyst. Examples of other catalysts include tin compounds.

[0052] The reaction in step (A1) is preferably carried out under conditions in which a tin compound is not present, or, if present, the amount of the tin compound relative to the total amount of the zinc compound, polyiso(thio)cyanate compound, and (meth)acrylate compound (b) charged is less than 0.01 mass %, thereby more effectively achieving the effect of the production method of the present disclosure achieved by using a zinc compound as a catalyst (i.e., suppression of gelation of the product).

[0053] The reaction in step (A1) is preferably carried out by reacting a tertiary amine compound (i.e., NR ３ wherein each of the three R's represents a hydrocarbon group) is not present, or, if present, the amount of the tertiary amine compound relative to the total amount of the zinc compound, polyiso(thio)cyanate compound, and (meth)acrylate compound (b) is less than 0.01% by mass. This makes it possible to more effectively obtain the effect of the production method of the present disclosure achieved by using a zinc compound as a catalyst (i.e., suppression of gelation of the product).

[0054] <(Meth)acrylate Compound (a)> Hereinafter, the (meth)acrylate compound (a), which is the target of the method for producing a (meth)acrylate compound according to the present disclosure, will be described. The (meth)acrylate compound (a) is a (meth)acrylate compound containing an allophanate bond.

[0055] The molecular weight of the (meth)acrylate compound (a) is not particularly limited. The molecular weight of the (meth)acrylate compound (a) is preferably 10,000 or less, more preferably 5,000 or less. The lower limit of the molecular weight of the (meth)acrylate compound (a) is not particularly limited as long as it contains an allophanate bond and a (meth)acryloyl group, but the lower limit is preferably 300, more preferably 500.

[0056] The number of allophanate bonds in the (meth)acrylate compound (a) is preferably 1 to 20, more preferably 1 to 10. The number of (meth)acryloyl groups in the (meth)acrylate compound of the present disclosure is preferably 3 to 20, more preferably 3 to 10.

[0057] (Compound Represented by Formula (A)) The (meth)acrylate compound (a) is preferably a compound represented by the following formula (A): The compound represented by formula (A) can be produced by using an iso(thio)cyanate compound containing two iso(thio)cyanate groups as the above-mentioned "iso(thio)cyanate compound containing two or more iso(thio)cyanate groups."

[0058]

[0059] In formula (A), R １Ａａ , R １Ａｂ and R １Ａｃ are each independently a hydrogen atom or a methyl group, R ２Ａａ , R ２Ａｂ and R ２Ａｃ are each independently a residue obtained by removing one hydroxy group and one (meth)acryloyl group from a (meth)acrylate compound (b) containing one or more hydroxy groups and one or more (meth)acryloyl groups, and R ３Ａａ and R ３Ａｂ are each independently a residue obtained by removing two iso(thio)cyanate groups from an iso(thio)cyanate compound containing two iso(thio)cyanate groups, and Z Ａ１ and Z Ａ２are each independently a hydrogen atom, a group represented by the following formula (1a), a group represented by the following formula (1b), or a group represented by the following formula (1c).

[0060]

[0061] In formula (1a), R １Ａｄ is a hydrogen atom or a methyl group, R ２Ａｄ is a residue obtained by removing one hydroxy group and one (meth)acryloyl group from a (meth)acrylate compound (b) containing one or more hydroxy groups and one or more (meth)acryloyl groups, and R ３Ａｃ is a residue obtained by removing two iso(thio)cyanate groups from an iso(thio)cyanate compound containing two iso(thio)cyanate groups, and * indicates a bonding position.

[0062]

[0063] In formula (1b), R １Ａｄ and R １Ａｅ are each independently a hydrogen atom or a methyl group, R ２Ａｄ and R ２Ａｅ are each independently a residue obtained by removing one hydroxy group and one (meth)acryloyl group from a (meth)acrylate compound (b) containing one or more hydroxy groups and one or more (meth)acryloyl groups, and R ３Ａｃ and R ３Ａｄ are each independently a residue obtained by removing two iso(thio)cyanate groups from an iso(thio)cyanate compound containing two iso(thio)cyanate groups, and * indicates a bonding position.

[0064]

[0065] In formula (1c), R １Ａｄ , R １Ａｅ and R １Ａｆ are each independently a hydrogen atom or a methyl group, R ２Ａｄ , R ２Ａｅ and R ２Ａｆare each independently a residue obtained by removing one hydroxy group and one (meth)acryloyl group from a (meth)acrylate compound (b) containing one or more hydroxy groups and one or more (meth)acryloyl groups, and R ３Ａｃ , R ３Ａｄ and R ３Ａｅ are each independently a residue obtained by removing two iso(thio)cyanate groups from an iso(thio)cyanate compound containing two iso(thio)cyanate groups, and * indicates a bonding position.

[0066] Specific examples and preferred embodiments of the (meth)acrylate compound (b) and the iso(thio)cyanate compound containing two iso(thio)cyanate groups (i.e., polyiso(thio)cyanate compound) for producing the compound represented by formula (A) (i.e., for forming each of the above-mentioned "residues") are as described above.

[0067] <Charge Molar Ratio [Iso(thio)cyanate Group / OH]> As described above, in the step (A1) of the present disclosure, a polyiso(thio)cyanate compound and a (meth)acrylate compound (b) are reacted at a charge ratio such that the charge molar ratio [iso(thio)cyanate group / OH] is greater than 1, thereby producing a (meth)acrylate compound (a).

[0068] The charge molar ratio [iso(thio)cyanate group / OH] is preferably 1.1 to 7.0, more preferably 1.1 to 6.0, and even more preferably 1.2 to 5.0. When the charge molar ratio [iso(thio)cyanate group / OH] is 1.1 or higher, allophanate bonds are more likely to be formed, and as a result, the (meth)acrylate compound (a) containing an allophanate bond is more likely to be produced. When the charge molar ratio [iso(thio)cyanate group / OH] is 7.0 or less (preferably 5.0 or less, more preferably 3.0 or less), a higher gelation suppression effect can be obtained. Furthermore, when the charge molar ratio [iso(thio)cyanate group / OH] is 7.0 or less (preferably 5.0 or less, more preferably 3.0 or less), the remaining unreacted iso(thio)cyanate groups are suppressed, thereby further stabilizing the product and further suppressing the generation of by-products.

[0069] <Solvent> The reaction in step (A1) may be carried out in a solvent or without a solvent. Any known solvent can be used as the solvent as long as it is inert to the reaction. Examples of known solvents that can be used as the solvent include hydrocarbon solvents such as n-hexane, benzene, toluene, and xylene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and perclene; and polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylimidazolidinone, dimethyl sulfoxide, and sulfolane. These solvents may be used alone or in combination of two or more.

[0070] <Polymerization Inhibitor> A polymerization inhibitor may be used in the reaction in step (A1). Examples of the polymerization inhibitor include dibutylhydroxytoluene (BHT), hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ), and phenothiazine (PTZ).

[0071] The amount of the polymerization inhibitor used may be 0.001% by mass to 0.5% by mass, 0.002% by mass to 0.3% by mass, or 0.005% by mass to 0.3% by mass, relative to the total amount of the polyiso(thio)cyanate compound and the (meth)acrylate compound (b).

[0072] The reaction temperature is not particularly limited and is, for example, 20°C to 120°C, preferably 30°C to 100°C, and more preferably 50°C to 100°C.

[0073] The reaction time is not particularly limited as it depends on conditions such as the reaction temperature, and is, for example, 5 minutes to 50 hours. The end point of the reaction can be confirmed by analysis by HPLC (high performance liquid chromatography), etc.

[0074] Examples of the present disclosure will be shown below, but the present disclosure is not limited to the following examples. Hereinafter, the term "monomer" simply means a (meth)acrylate compound unless otherwise specified.

[0075] The abbreviations for the compounds used in this example are as follows: <Isocyanate> XDI: m-xylylene diisocyanate NBDI: mixture of 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane and 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane <Hydroxy(meth)acrylate> HPA: hydroxypropyl acrylate <Catalyst> DBDLSn: dibutyltin dilaurate TPZr: tetrakis(2,4-pentanedionato)zirconium(IV) ZnC4: zinc(II) dibutyldithiocarbamate BzPhZn: bis[2-(2-benzoxazolyl)phenolato]zinc(II) OCZn: zinc octanoate DiMeBzA: N,N-dimethylbenzylamine

[0076] The structures of the catalysts are as follows: ZnC4 is the aforementioned compound (Z-1), BzPhZn is the aforementioned compound (Z-3), and OCZn is the aforementioned compound (Z-8).

[0077]

[0078] <Polymerization inhibitor> BHT: 2,6-di-tert-butyl-p-cresol PhSM: 2-methoxyphenothiazine PhS: phenothiazine

[0079] <Measurement of NCO %> As an index of the amount of isocyanate groups (NCO) present in the products obtained in each Example and Comparative Example, NCO % was measured as follows: A larger value of NCO % means a larger amount of isocyanate groups (NCO) present.

[0080] (Blank titration) 10 mL of dibutylamine toluene solution (a solution of 3.1 g of dibutylamine dissolved in 235.7 g of toluene), 10 mL of N,N-dimethylformamide, and 50 mL of methanol were added to a 200 mL Erlenmeyer flask and stirred, followed by the addition of 5 drops of bromophenol blue indicator. 0.1 N hydrochloric acid was added dropwise to the resulting solution using a burette. The endpoint was determined when the color of the solution changed from blue to yellow.

[0081] (Titration of Product) 3.0 g of the product obtained in each Example and Comparative Example was weighed into a 200 mL Erlenmeyer flask. 10 mL of a dibutylamine toluene solution (a solution prepared by dissolving 3.1 g of dibutylamine in 235.7 g of toluene) and 10 mL of N,N-dimethylformamide were added thereto and stirred for 20 minutes. 50 mL of methanol was added thereto and stirred for an additional minute, after which 5 drops of bromophenol blue indicator were added. 0.1 N hydrochloric acid was added dropwise to the resulting solution using a burette. The end point was when the color of the solution changed from blue to yellow.

[0082] Based on the results of the titration described above, the NCO % of the product was calculated using the following formula.

[0083] NCO% = ((V - v) x 0.42 x f) / sample mass (g) V: titration volume (mL) of 0.1 N hydrochloric acid for the blank v: titration volume (mL) of 0.1 N hydrochloric acid for the sample f = 1 (factor of 0.1 N hydrochloric acid)

[0084] Comparative Example 1 DBDLSn (0.09 parts by mass), XDI (37.6 parts by mass), and BHT (0.13 parts by mass) were placed in a 300 mL four-neck flask equipped with a thoroughly dried stirring blade and a thermometer and dissolved to form a homogeneous solution. While maintaining the temperature of the resulting homogeneous solution at 70 to 80°C, HPA (52.1 parts by mass) was added dropwise to the solution over 15 minutes. After the dropwise addition, the reaction temperature was maintained at 90 to 100°C, and the reaction was carried out for 16 hours. LC / MS analysis of the resulting product detected the following compound (AX-1) containing a urethane bond and the following compound (AX-2) containing a urethane bond, but no reaction product of the following compound (AX-1) and the following compound (AX-2) (i.e., a compound containing an allophanate bond (i.e., monomer (1A) described below)) was detected. From the above results, it was confirmed that in Comparative Example 1, the urethane-forming reaction proceeded, but the allophanate-forming reaction did not proceed. The NCO% of the obtained product was 1.0 or more, and it was confirmed that an isocyanate group (NCO) remained. It is understood that this isocyanate group is the isocyanate group contained in the following compound (A-2).

[0085]

[0086] Comparative Example 2 The same procedure as in Comparative Example 1 was carried out, except that DBDLSn (0.09 parts by mass) was replaced with TPZr (0.09 parts by mass). The results of LC / MS analysis of the obtained product were the same as those of the product obtained in Comparative Example 1, and it was confirmed that, as in Comparative Example 1, the urethanization reaction had proceeded, but the allophanate formation reaction had not.

[0087] [Comparative Example 3] DBDLSn (0.09 parts by mass), XDI (37.6 parts by mass), PhS (0.01 parts by mass), and BHT (0.13 parts by mass) were charged into a 300 mL four-neck flask equipped with a thoroughly dried stirring blade and a thermometer, and dissolved to form a homogeneous solution. While maintaining the temperature of the resulting homogeneous solution at 70 to 80 ° C, HPA (52.1 parts by mass) was added dropwise over 15 minutes. LC / MS analysis of the resulting product revealed that the above-mentioned compound (AX-1) and the above-mentioned compound (AX-2) were detected (reaction stage 1). DiMeBzA (0.07 parts by mass) and OCZn (0.09 parts by mass) were added to this product, and the reaction was continued while maintaining the reaction temperature at 70 to 80 ° C., resulting in gelation after 6 hours. Due to gelation, the NCO% could not be measured.

[0088] Example 1 Production of Monomer (1A) ZnC4 (0.05 parts by mass), XDI (45.1 parts by mass), BHT (0.09 parts by mass), and PhSM (0.018 parts by mass) were charged into a 300 mL four-neck flask equipped with a thoroughly dried stirring blade and a thermometer, and dissolved to form a homogeneous solution. While maintaining the temperature of the resulting homogeneous solution at 70 to 80°C, HPA (46.9 parts by mass) was added dropwise thereto over 15 minutes. After the dropwise addition, the reaction temperature was maintained at 90 to 100°C, and the reaction was carried out for 6 hours. LC / MS measurement was performed to track the progress of the reaction, and it was confirmed that the allophanation reaction (i.e., the reaction between the above-mentioned compound (AX-1) and the above-mentioned compound (AX-2)) had progressed. LC / MS measurement confirmed that all of the compound (AX-2) had reacted with the compound (AX-1), marking the end point of the reaction. The product was discharged from the reactor to obtain 92.0 g of a product containing a monomer (1A) having an allophanate bond, which was a reaction product of the compound (AX-1) and the compound (AX-2). The NCO % of the obtained product was less than 0.01.

[0089] <Structure of Monomer (1A)> Monomer (1A) includes the following six compounds.

[0090]

[0091]

[0092] The LC / MS analysis results (min and peak area ratios) derived from the LC / MS chart for Monomer (1A) are shown below. In the LC / MS chart for Monomer (1A), the six compounds were observed as, in order from the lowest molecular weight compound, a peak near 12.80 min (peak area ratio = 23.4%), a peak near 14.70 min (peak area ratio = 19.8%), a peak near 16.00 min (peak area ratio = 14.0%), a peak near 17.00 min (peak area ratio = 8.6%), a peak near 17.70 min (peak area ratio = 4.6%), and a peak near 18.30 min (peak area ratio = 2.5%). The peak near 9.60 min (peak area ratio = 27.1%) in the LC / MS chart is the aforementioned compound (AX-1), a compound in which two urethane bonds have not reacted with isocyanate groups.

[0093] Example 2 Production of Monomer (2A) ZnC4 (0.09 parts by mass), XDI (35.9 parts by mass), BHT (0.16 parts by mass), and PhS (0.09 parts by mass) were charged into a 300 mL four-neck flask equipped with a thoroughly dried stirring blade and a thermometer, and dissolved to form a homogeneous solution. While maintaining the temperature of the resulting homogeneous solution at 70 to 80°C, HPA (27.3 parts by mass) was added dropwise thereto over 15 minutes. After the dropwise addition, the reaction temperature was maintained at 90 to 100°C, and the reaction was carried out for 6 hours. LC / MS measurement was performed to monitor the progress of the reaction, and it was confirmed that the allophanation reaction (i.e., the reaction between the above-mentioned compound (AX-1) and the above-mentioned compound (AX-2)) had progressed. LC / MS measurement confirmed that all of the compound (AX-2) had reacted with the compound (AX-1), marking the end point of the reaction. The product was discharged from the reactor to obtain 63.2 g of a product containing a monomer (2A) having an allophanate bond, which was a reaction product of the compound (AX-1) and the compound (AX-2). The NCO % of the obtained product was less than 0.01.

[0094] <Structure of Monomer (2A)> Monomer (2A) includes the following 10 compounds.

[0095]

[0096]

[0097]

[0098]

[0099] In the LC / MS chart for Monomer (2A), the above 10 compounds were observed as, in order from the lowest molecular weight side, a peak around 12.80 min (peak area ratio = 8.9%), a peak around 14.70 min (peak area ratio = 11.4%), a peak around 16.00 min (peak area ratio = 11.6%), a peak around 17.00 min (peak area ratio = 12.0%), a peak around 17.70 min (peak area ratio = 10.6%), a peak around 18.30 min (peak area ratio = 10.5%), a peak around 18.70 min (peak area ratio = 8.4%), a peak around 19.10 min (peak area ratio = 9.0%), a peak around 19.40 min (peak area ratio = 7.5%), and a peak around 19.60 min (peak area ratio = 6.4%). The peak at around 9.60 min (peak area ratio=3.9%) in the LC / MS chart was the aforementioned compound (AX-1), which is a compound in which two urethane bonds have not reacted with isocyanate groups.

[0100] Example 3 Production of Monomer (3A) ZnC4 (0.09 parts by mass), NBDI (30.9 parts by mass), BHT (0.09 parts by mass), and PHSM (0.08 parts by mass) were charged into a 300 mL four-neck flask equipped with a thoroughly dried stirring blade and a thermometer, and dissolved to form a homogeneous solution. While maintaining the temperature of the resulting homogeneous solution at 70°C to 80°C, HPA (29.3 parts by mass) was added dropwise thereto over 15 minutes. After the dropwise addition, the reaction temperature was maintained at 90°C to 100°C, and the reaction was carried out for 9 hours. During this time, LC / MS measurement was performed to monitor the progress of the reaction, and it was confirmed that the allophanation reaction (i.e., the reaction between the following compound (AN-1) and the following compound (AN-2)) had progressed.

[0101]

[0102] LC / MS measurement confirmed that all of compound (AN-2) had reacted with compound (AN-1), marking this as the end point of the reaction. By discharging the product from the reactor, 60.2 g of a product containing monomer (3A) having an allophanate bond, which was a reaction product of compound (AN-1) and compound (AN-2), was obtained. The NCO% of the obtained product was less than 0.01.

[0103] <Structure of Monomer (3A)> Monomer (3A) includes the following four compounds.

[0104]

[0105] In the LC / MS chart for monomer (4A), the above four compounds were observed as, in order from the lowest molecular weight side, a peak near 14.30 min (peak area ratio = 35.7%), a peak near 16.70 min (peak area ratio = 21.9%), a peak near 18.70 min (peak area ratio = 9.5%), and a peak near 19.60 min (peak area ratio = 2.0%). The peak near 11.10 min (peak area ratio = 30.9%), which is even lower in molecular weight than these peaks, is the following compound in which each of the two urethane bonds has not reacted with an isocyanate group: The following compound in which each of the two urethane bonds has not reacted with an isocyanate group was observed as a peak near 11.10 min (peak area ratio = 30.9%) in the LC / MS chart:

[0106]

[0107] Example 4 Production of Monomer (4A) BzPhZn (0.06 parts by mass), XDI (30.1 parts by mass), and BHT (0.12 parts by mass) were charged into a 300 mL four-neck flask equipped with a thoroughly dried stirring blade and a thermometer, and dissolved to form a homogeneous solution. While maintaining the temperature of the resulting homogeneous solution at 70 to 80°C, HPA (31.2 parts by mass) was added dropwise thereto over 15 minutes. After the dropwise addition, the reaction temperature was maintained at 70 to 80°C, and the reaction was carried out for 16 hours. LC / MS measurement was performed to track the progress of the reaction, and it was confirmed that the allophanation reaction (i.e., the reaction between the above-mentioned compound (AX-1) and the above-mentioned compound (AX-2)) had progressed. LC / MS measurement confirmed that all of the compound (AX-2) had reacted with the compound (AX-1), marking the end point of the reaction. The product was discharged from the reactor to obtain 92.0 g of a product containing a monomer (4A) having an allophanate bond, which was a reaction product of the compound (AX-1) and the compound (AX-2). The NCO % of the obtained product was less than 0.01.

[0108] The production of Monomer (4A) and the production of Monomer (1A) described above use different catalysts, but the feed ratio [XDI / HPA] is the same. Therefore, the structure of Monomer (4A) is considered to be similar to the structure of Monomer (1A).

[0109] Example 5 Production of Monomer (5A) OCZn (0.10 parts by mass), XDI (45.1 parts by mass), BHT (0.09 parts by mass), and PhSM (0.018 parts by mass) were charged into a 300 mL four-neck flask equipped with a thoroughly dried stirring blade and a thermometer, and dissolved to form a homogeneous solution. While maintaining the temperature of the resulting homogeneous solution at 70°C to 80°C, HPA (46.9 parts by mass) was added dropwise thereto over 15 minutes. After the dropwise addition, the reaction temperature was maintained at 90°C to 100°C, and the reaction was carried out for 6 hours. LC / MS measurement was performed to track the progress of the reaction, and it was confirmed that the allophanation reaction (i.e., the reaction between the above-mentioned compound (AX-1) and the above-mentioned compound (AX-2)) had progressed. LC / MS measurement confirmed that all of the compound (AX-2) had reacted with the compound (AX-1), marking the end point of the reaction. The product was discharged from the reactor to obtain 92.0 g of a product containing a monomer (5A) having an allophanate bond, which was a reaction product of the compound (AX-1) and the compound (AX-2). The NCO % of the obtained product was less than 0.01.

[0110] The catalysts used in the production of Monomer (5A) and the production of Monomer (1A) are different, but the feed ratio [XDI / HPA] is the same. Therefore, the structure of Monomer (4A) is considered to be similar to that of Monomer (1A).

[0111] The results of the NCO % and the progress of the allophanation reaction for each Example and Comparative Example are shown in Table 1. In the results of the progress of the allophanation reaction, "A" indicates that the allophanation reaction proceeded, and "B" means that the allophanation reaction did not proceed and / or gelation of the product occurred.

[0112]

[0113] As shown in Table 1, the allophanation reaction did not proceed in Comparative Examples 1 and 2, in which a zinc compound was not used as a catalyst. Furthermore, in Comparative Example 3, in which a diisocyanate compound was reacted with a hydroxy(meth)acrylate compound in the presence of a tin catalyst, and then a tertiary amine and zinc octanoate were added, the product gelled during the reaction. On the other hand, in Examples 1 to 5, in which an iso(thio)cyanate compound was reacted with a (meth)acrylate compound (b) in the presence of a zinc compound, the allophanation reaction was allowed to proceed and gelation of the product was suppressed.

[0114] The disclosure of Japanese Patent Application No. 2024-040474, filed on March 14, 2024, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A method for producing a (meth)acrylate compound, comprising: a step (A1) of reacting an iso(thio)cyanate compound containing two or more iso(thio)cyanate groups with a (meth)acrylate compound (b) containing one or more hydroxy groups and one or more (meth)acryloyl groups in the presence of a zinc compound, at a charge ratio such that the charge molar ratio of the iso(thio)cyanate groups in the iso(thio)cyanate compound to the hydroxy groups in the (meth)acrylate compound (b) is greater than 1, thereby producing a (meth)acrylate compound (a) containing an allophanate bond.

2. The method for producing a (meth)acrylate compound according to claim 1, wherein the iso(thio)cyanate compound containing two or more iso(thio)cyanate groups is an iso(thio)cyanate compound containing two iso(thio)cyanate groups, and the (meth)acrylate compound (a) is a compound represented by the following formula (A): [In formula (A), R １Ａａ , R １Ａｂ and R １Ａｃ are each independently a hydrogen atom or a methyl group, R ２Ａａ , R ２Ａｂ and R ２Ａｃ are each independently a residue obtained by removing one hydroxy group and one (meth)acryloyl group from the (meth)acrylate compound (b), and R ３Ａａ and R ３Ａｂ are each independently a residue obtained by removing two iso(thio)cyanate groups from the iso(thio)cyanate compound, and Z Ａ１ and Z Ａ２ are each independently a hydrogen atom, a group represented by the following formula (1a), a group represented by the following formula (1b), or a group represented by the following formula (1c): [In formula (1a), R １Ａｄ is a hydrogen atom or a methyl group, R ２Ａｄ is a residue obtained by removing one hydroxy group and one (meth)acryloyl group from the (meth)acrylate compound (b), and R ３Ａｃ is a residue obtained by removing two iso(thio)cyanate groups from the iso(thio)cyanate compound, and * indicates a bonding position. [In formula (1b), R １Ａｄ and R １Ａｅ are each independently a hydrogen atom or a methyl group, R ２Ａｄ and R ２Ａｅ are each independently a residue obtained by removing one hydroxy group and one (meth)acryloyl group from the (meth)acrylate compound (b), and R ３Ａｃ and R ３Ａｄ are each independently a residue obtained by removing two iso(thio)cyanate groups from the iso(thio)cyanate compound, and * indicates a bonding position. [In formula (1c), R １Ａｄ , R １Ａｅ and R １Ａｆ are each independently a hydrogen atom or a methyl group, R ２Ａｄ , R ２Ａｅ and R ２Ａｆ are each independently a residue obtained by removing one hydroxy group and one (meth)acryloyl group from the (meth)acrylate compound (b), and R ３Ａｃ , R ３Ａｄ and R ３Ａｅ are each independently a residue obtained by removing two iso(neo)nate groups from the iso(thio)cyanate compound, and * indicates the bonding position.

3. The method for producing a (meth)acrylate compound according to claim 1, wherein the zinc compound is a compound represented by the following formula (2): [In formula (2), X １ and X ２ are each independently an oxygen atom, a sulfur atom, —C(═S)—S— or —C(═O)—O—; R ３ and R ４ are each independently a monovalent organic group having 2 to 40 carbon atoms, or R ３ and R ４ are bonded to each other to form a ring structure, and are organic groups having 2 to 40 carbon atoms.

4. The method for producing a (meth)acrylate compound according to claim 1, wherein the molar ratio of the feed in step (A1) is 1.1 to 7.

0.

5. The method for producing a (meth)acrylate compound according to claim 1, wherein the amount of the zinc compound charged in step (A1) is 0.01% by mass to 1% by mass with respect to the total amount of the zinc compound, the iso(thio)cyanate compound, and the (meth)acrylate compound (b).

6. The method for producing a (meth)acrylate compound according to claim 1, wherein the reaction in step (A1) is carried out under conditions in which a tin compound is not present, or, if present, the amount of the tin compound relative to the total amount of the zinc compound, the iso(thio)cyanate compound, and the (meth)acrylate compound (b) charged is less than 0.01 mass%.

7. The method for producing a (meth)acrylate compound according to claim 1, wherein the reaction in step (A1) is carried out under conditions in which a tertiary amine compound is not present, or, if present, the amount of the tertiary amine compound relative to the total amount of the zinc compound, the iso(thio)cyanate compound, and the (meth)acrylate compound (b) is less than 0.01 mass%.

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